This application is a national application of CN201811006339.7, filed on Aug. 30, 2018. The contents of CN201811006339.7 are all hereby incorporated by reference.
The disclosure relates to a preparation method, a product and an application of phosphor, and in particular to a preparation method for manganese-doped red phosphor, a product, a device and a backlight module.
With the development of a display technology, new-type display technologies are developed endlessly, such as Organic Light-Emitting Diode (OLED) curved flexible display, a quantum dot display technology, virtual and augmented reality display. However, mainstream displays that are widely used at present are still a liquid crystal display technology that uses Light-Emitting Diode (LED) as a backlight source. Because liquid crystal display is light-emitting passively, an external light source must be used for image display. Therefore, the luminous quality of the backlight source often determines the quality of a liquid crystal display image.
LED has the advantages of high energy efficiency, low energy consumption, high reliability, long service life, small size and the like. LED is a very excellent backlight source for liquid crystal displays, and the white light LED used for the display backlight source mainly uses a blue light chip to excite a fluorescence conversion-type LED device packaged by red and green phosphor. A color picture of a liquid crystal display is realized through R, G, B color filters. In order to improve a color gamut range and a color saturation of the liquid crystal display, red, green, and blue spectral ranges of the backlight source should be matched with a range of the corresponding display filter. Therefore, the development of wide color gamut and high color saturation display requires the development of a narrow-band LED fluorescent material which is matched with the display filter, especially red and green narrow-band fluorescent materials suitable for blue chip excitation.
Compared with the parity-allowed f-d transition of Eu2+ or Ce3+, d-d transition emission of Me which is parity-forbidden has a narrower spectral range. Therefore, the use of red emission of the Mn4+ is expected to broaden the color gamut. Furthermore, phonon energy of a fluoride system is low, so the fluoride system activated by the Mn4+ is expected to produce high-efficiency luminescence. The fluoride activated by the Me is good red phosphor for the display backlight source. However, the fluoride red phosphor currently used in the display backlight source mainly includes K2SiF6:Mn4+ and K2GeF6:Mn4+ two systems.
K2TiF6:Mn4+ also emits light under the excitation of 450 nm to 460 nm of blue light, but due to the low external quantum efficiency of K2TiF6:Mn4+, the K2TiF6:Mn4+ red phosphor is not commercialized all the time. A document (Nature Communications, 2014, 5:4312) and a patent with a patent document number CN103980896A disclose that while the Mn concentration is 1.40%, the internal quantum efficiency of K2TiF6:Mn4+ reaches 98% maximally and the absorption rate is only 36% (the corresponding external quantum efficiency is 35.28%); and while the Me concentration is 6.50%, the absorption rate reaches 60% but the internal quantum efficiency is only 78% (the corresponding external quantum efficiency is 46.8%). It is reported by a document (Optical Materials Express, 2018, 8(1): 73) that the internal quantum efficiency of K2TiF6:Mn4+ synthesized by ball-milling at 100 RPMs for 15 minutes is 62.5%, and the maximum external quantum efficiency is 47% (namely, the absorption rate is 75.2%). It is reported by a document (Optical Materials Express, 2018, 8(1): 73) that the maximum internal quantum efficiency of K2TiF6:Mn4+ synthesized by ball-milling at 100 RPMs for 5 minutes is 65.9%, and the external quantum efficiency is 42.8%. It is reported by a document (J. Mater. Chem. C, 2015, 3, 1935) that the internal quantum efficiency of K2TiF6:Mn4+ red powder is 98%, but a diffuse reflectance spectrum in
Although there are many documents and patents for the research of the synthesis and luminescence properties of the K2TiF6:Mn4+ red phosphor, the external quantum efficiency of the manganese-doped red phosphor prepared in the prior art is generally 47% or less, therefore, the prior art has a technical problem that the external quantum efficiency of the manganese-doped red phosphor is lower.
A technical problem to be solved by the disclosure is to provide a preparation method for manganese-doped red phosphor, a product, a device and a backlight module, so as to solve the technical problem in the prior art that the external quantum efficiency of the manganese-doped red phosphor is lower.
The disclosure solves the above technical problem through the following technical schemes.
An embodiment of the disclosure provides a preparation method for manganese-doped red phosphor, and the method includes:
Optionally, a secondary crystallization treatment process in the step 2) is performed in a sealed reactor.
Optionally, the step 3) includes:
Optionally, a preparation method for A2MnF6 in the step 4) includes:
Optionally, the step 5) includes:
Optionally, the monovalent cation A includes one or a combination of a group consist of a hydrogen ion, a lithium ion, a sodium ion and a cesium ion; and
An embodiment of the disclosure further provides a product prepared by any one of the above preparation methods for the manganese-doped red phosphor.
An embodiment of the disclosure further provides a device packaged by a product prepared by any one of the above preparation methods for the manganese-doped red phosphor, the device includes: an excitation source, phosphor, an electrode, a packaging material, and a support, herein,
An embodiment of the disclosure further provides a backlight module packaged by a product prepared by any one of the above preparation methods for the manganese-doped red phosphor.
Compared with the prior art, the disclosure has the following advantages:
Embodiments of the disclosure are described in detail below. The embodiments are implemented on the premise of technical schemes of the disclosure, and detailed implementation modes and specific operation processes are provided, but a scope of protection of the disclosure is not limited to the following embodiments.
The embodiments of the disclosure provide a preparation method for manganese-doped red phosphor, a product, a device and a backlight module, and the preparation method for the manganese-doped red phosphor provided by the embodiment of the disclosure are firstly introduced below.
An embodiment of the disclosure provides a preparation method for manganese-doped red phosphor, the method includes:
An embodiment of the disclosure further provides a product prepared according to the above method.
An embodiment of the disclosure further provides a device packaged by a product prepared according to the above method, and
An embodiment of the disclosure further provides a backlight module packaged by a product prepared according to the above method.
Technical schemes in the embodiments of the disclosure are clearly and completely described below, herein Table 1 is a table of process parameters used in Embodiments 1 to 9 of the disclosure; and Table 2 is a table of process parameters used in Embodiments 10 to 19 of the disclosure; as shown in Table 1 and Table 2.
Relative Light Intensity Test
An F4600 fluorescence spectrometer produced by Hitachi Manufacture Co., Ltd. is used to test the products prepared in Embodiments 1 to 19, and test results are shown in Table 3.
Table 3 is the test results of luminous intensities, color coordinates, color temperatures and color rendering indexes of the products prepared in Embodiments 1 to 19 provided by the embodiments of the disclosure, herein the relative intensity is obtained by integrating an emission spectrum within a range of 580 nm to 680 nm; and the color coordinates, correlated color temperatures, and color rendering indexes are calculated by using “CIE13_3w.exe” software.
In
A F4600 fluorescence spectrometer produced by Hitachi Manufacture Co., Ltd. is used to perform a relative luminous intensity test according to the above dosage, and
External Quantum Efficiency Comparison Test
A QY-2000-type integrating sphere fluorescence spectrometer produced by Tianjin Dongfang Kejie Technology Co., Ltd. is used to test the products prepared in Embodiments 1 to 19, the KSF (K2SiF6:Mn4+) red powder (brand name BR-301/C) produced by Mitsubishi Chemical Corporation, and the KGF (K2GeF6:Mn4+) red powder (brand name 690F-103B) produced by Grinm Advanced Materials Co., Ltd. Test results are as shown in Table 4.
Table 4 is a result comparison table of testing the products prepared in Embodiments 1 to 19, the KSF (K2SiF6:Mn4+) red powder (brand name BR-301/C) produced by Mitsubishi Chemical Corporation, and the KGF (K2GeF6:Mn4+) red powder (brand name 690F-103B) produced by Grinm Advanced Materials Co., Ltd. according to the embodiments of the disclosure.
It can be seen from Table 4 that the external quantum efficiency, absolute quantum efficiency and absorption rate of the products prepared in Embodiments 1 to 19 of the disclosure are all higher than the KSF red powder (brand name BR-301/C) produced by Mitsubishi Chemical Corporation and the KGF (K2GeF6:Me) red powder (brand name 690F-103B) produced by Grinm Advanced Materials Co., Ltd.
Phosphor Dosage Comparison Test
The products prepared in Embodiments 1 to 19, the KSF red powder (brand name BR-3011C) produced by Mitsubishi Chemical Corporation, and the KGF red powder (brand name 690F-103B) produced by Grinm Advanced Materials Co., Ltd. are used to be packaged into a white light LED device of a display backlight source, and a weight test is performed. Test results are as shown in Table 5.
Table 5 is a result comparison table of testing the products prepared in Embodiments 1 to 19, the KSF red powder (brand name BR-301/C) produced by Mitsubishi Chemical Corporation, and the KGF red powder (brand name 690F-103B) produced by Grinm Advanced Materials Co., Ltd. according to the embodiments of the disclosure.
It can be seen from Table 5 that the amounts of the products prepared in Embodiments 1 to 19 of the disclosure are all less than that of the KSF red powder (brand name BR-301/C) produced by Mitsubishi Chemical Corporation, and the KGF red powder (brand name 690F-103B) produced by Grinm Advanced Materials Co., Ltd.
The above are only the preferred embodiments of the disclosure, and are not intended to limit the disclosure. Any modifications, equivalent replacements and improvements and the like made within the spirit and principle of the disclosure shall be included in a scope of protection of the disclosure.
Number | Date | Country | Kind |
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201811006339.7 | Aug 2018 | CN | national |
Filing Document | Filing Date | Country | Kind |
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PCT/CN2018/112158 | 10/26/2018 | WO |
Publishing Document | Publishing Date | Country | Kind |
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WO2020/042319 | 3/5/2020 | WO | A |
Number | Name | Date | Kind |
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20160133799 | Park | May 2016 | A1 |
20160289553 | Beers | Oct 2016 | A1 |
20170040505 | You | Feb 2017 | A1 |
Number | Date | Country |
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103980896 | Aug 2014 | CN |
204885214 | Dec 2015 | CN |
105793389 | Jul 2016 | CN |
106687562 | May 2017 | CN |
107955604 | Apr 2018 | CN |
Entry |
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Congzhi Zhang et al., “Mn4+-dopedfluoride phosphorsrapidly synthesizedby ball milling”, OPTICALMATERIALSEXPRESS, Dec. 14, 2017, pp. 73-81. |
Enhai Song et al., “Highly Efficient and Stable Narrow-Band Red Phosphor Cs2SiF6:Mn4+ for High-Power Warm White LED Applications”, ACS Photonics, Sep. 16, 2017, pp. 2556-2565. |
Number | Date | Country | |
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20210324265 A1 | Oct 2021 | US |