CN112551892B - Wide-color-gamut glass for LED display and preparation method thereof - Google Patents

Wide-color-gamut glass for LED display and preparation method thereof Download PDF

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CN112551892B
CN112551892B CN202011500696.6A CN202011500696A CN112551892B CN 112551892 B CN112551892 B CN 112551892B CN 202011500696 A CN202011500696 A CN 202011500696A CN 112551892 B CN112551892 B CN 112551892B
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glass
preparation
gamut
color
phosphor
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CN112551892A (en
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张乐
甄方正
康健
邱凡
赵超
陈东顺
陈浩
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Xinyi Xiyi High Tech Material Industry Technology Research Institute Co Ltd
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Xinyi Xiyi High Tech Material Industry Technology Research Institute Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B19/00—Other methods of shaping glass
    • C03B19/06—Other methods of shaping glass by sintering, e.g. by cold isostatic pressing of powders and subsequent sintering, by hot pressing of powders, by sintering slurries or dispersions not undergoing a liquid phase reaction
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/12—Compositions for glass with special properties for luminescent glass; for fluorescent glass
    • 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
    • C09K11/0883—Arsenides; Nitrides; Phosphides
    • 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
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
    • C09K11/7734—Aluminates

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Geochemistry & Mineralogy (AREA)
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  • General Chemical & Material Sciences (AREA)
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  • Manufacturing & Machinery (AREA)
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  • Led Device Packages (AREA)
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Abstract

A wide color gamut glass for LED display and a preparation method thereof belong to the technical field of photoelectric display material preparation and application. The chemical composition of the material is 65SiO2‑25Na2O‑5BaO‑5ZnO‑xNd2O3Wherein x is more than or equal to 3 mol% and less than or equal to 5 mol%, and 0.3 wt% (beta-SiAlON: Eu) is doped2+) Phosphor, and yCaAlSiN3:Eu2+The phosphor powder has the mass ratio of 1 wt% to y3 wt%; prepared by a melt quenching method through doping Nd in silicate glass2O3The emission bandwidths of the green and red fluorescent powder are effectively reduced, the color gamut is further improved, and the NTSC color gamut of the prepared glass is 87-88%. The preparation method provided by the invention has the advantages of simple process and stable product performance, and is suitable for industrial production.

Description

Wide-color-gamut glass for LED display and preparation method thereof
Technical Field
The invention provides wide-color-gamut glass for LED display and a preparation method thereof, belonging to the technical field of preparation and application of photoelectric display materials.
Background
White light emitting diodes (wleds) are used as a white light source in Liquid Crystal Display (LCD) applications because of various advantages including high efficiency, low power consumption, and low cost. The wfled is manufactured by combining red and green phosphors with an InGaN-based blue LED chip (RG-LED), and embedding the phosphors on the blue LED using a silicone resin or an organic epoxy resin. However, conventional RG-LEDs suffer from performance and durability problems because the thermal and chemical stability of the silicone is low over long periods of operation, resulting in a decrease in the efficiency and reliability of the wLED. In addition, commercial phosphors such as Y3Al5O12:Ce3+(YAG:Ce3+Yellow) and Lu3Al5O12:Ce3+(LuAG:Ce3+Green) and CaAlSiN3 Eu2+(CASN:Eu2+Red), resulting in a limited color gamut, only 72%, of the NTSC (national television standards committee) standard region within the CIE color space.
As the requirement of people for image quality is higher and higher, Quantum Dots (QDs) reach 100% of NTSC standard due to narrower emission bandwidth and corresponding wide color gamut, and are recently applied to high-end displays. But even though QDs have high quantum yields and narrow emission bandwidths, they are sensitive to moisture and oxygen, resulting in poor chemical and thermal stability, resulting in high production costs.
A glass-in-glass (PiG) is an inorganic color converter composed of Phosphor and an inorganic glass matrix. This arrangement ensures long-term stability and accordingly such a PiG is also commercialized in high power wLED applications, such as automotive headlamps. The PiG and the phosphor with narrow emission bandwidth can be used to realize a robust wLED with wide color gamut and cost effectiveness, thereby reducing the production cost of high quality image displays.
Among various ceramic phosphor materials, Eu2+Doped beta-Si6-xAlxOxN8-x(β-SiAlON:Eu2+) Exhibits green emission under blue excitation. It has been widely studied because of its narrow emission bandwidth, full width at half maximum (FWHM) of 55 nm, and high thermal stability. beta-SiAlON Eu2+With CASN: Eu2+The combination increased the color gamut to 82.1% of NTSC. Introduction of K2SiF6:Mn4+(KSF:Mn4+) As red fluorescent powder with narrow emission bandwidth of 3nm, with beta-SiAlON: Eu2+Constituting a wLED, can produce up to 85.9% NTSC color gamut. However, these glasses use silicone to embed the phosphor, and the wfeds lack long-term reliability due to the weak thermal and chemical stability of the silicone. Further, KSF: Mn4+There is also a problem of weak thermal and chemical stability, which limits its commercial application.
Using Nd2O3Or NdF3Doped glasses have also been used in an attempt to improve the color gamut of wLED, Y3(Al, Ga)5O12:Ce3+Or LuAG: Ce3+Phosphor and CASN Eu2+Mixing by using Nd3+：4I9/2→4G5/2，2G7/2The generated hypersensitive absorption at the position of minus 580nm is converted to change the broad emission bandwidth of the fluorescent powder. These glasses successfully reduced the emission bandwidths of the red and green phosphors, but the color gamut was limited to-80% of NTSC due to the broad emission bandwidth of the phosphors.
Disclosure of Invention
1. In order to solve the problems, the invention provides wide-color-gamut glass for LED display and a preparation method thereof. The chemical composition of the material is 65SiO2-25Na2O-5BaO-5ZnO-xNd2O3Wherein x is more than or equal to 3 mol% and less than or equal to 5 mol%, and 0.3 wt% (beta-SiAlON: Eu) is doped2+) Phosphor, and yCaAlSiN3:Eu2+The phosphor powder has the mass ratio of 1 wt% to y3 wt%; prepared by a melt quenching method through doping Nd in silicate glass2O3The emission bandwidths of the green and red fluorescent powder are effectively reduced, the color gamut is further improved, and the NTSC color gamut of the prepared glass is 87-88%. The preparation method provided by the invention has the advantages of simple process and stable product performance, and is suitable for industrial production.
2. The technical scheme of the invention is as follows:
weighing SiO with purity of more than 99.9 percent according to stoichiometric ratio2、Na2O、BaO、ZnO、Nd2O3And (3) placing the glass in an alumina crucible, melting the glass for 30-60 minutes at 1300-1450 ℃, and then quenching and drying the glass to obtain the glass without the fluorescent powder. Crushing the glass, and mixing with commercial beta-SiAlON with the purity of more than 99.99 percent2+Phosphor and CaAlSiN3:Eu2+The fluorescent powder is uniformly mixed according to the mass ratio. And pressing the mixture, sintering the mixture in air at 500-600 ℃ for 1-2 hours, and naturally cooling to obtain the glass.
Advantageous effects
1. The invention provides wide-color-gamut glass for LED display and wide-color-gamut glass NTSC prepared by the preparation method thereof, wherein the color gamut of the wide-color-gamut glass NTSC is 87-88%.
2. In the process of preparing the glass, the method selects the high-purity raw material powder, strictly controls the introduction of impurities, and is very suitable for preparing the glass.
3. The preparation method provided by the invention has the advantages of high yield and productivity, simple preparation process and no strict requirements on preparation time arrangement, can effectively improve the yield and reduce the production cost, and is very suitable for industrial production.
Drawings
FIG. 1 SEM image of glass made in example 1;
FIG. 2 illustrates the (a) EL emission spectrum and (b) CIE coordinates of the display color gamut of the glass prepared in the example.
Detailed Description
The present invention is further illustrated by the following specific examples, which should not be construed as limiting the scope of the invention.
Example 1: 65SiO2-25Na2O-5BaO-5ZnO-3mol%Nd2O30.3 wt% of beta-SiAlON: Eu is doped2+Phosphor, and 1 wt.% CaAlSiN3:Eu2+Fluorescent powder;
weighing SiO with purity of more than 99.9 percent according to stoichiometric ratio2、Na2O、BaO、ZnO、Nd2O3Placing the glass in an alumina crucible, melting the glass at 1450 ℃ for 30 minutes, and then quenching the glass with water and drying the glass to obtain the glass without the fluorescent powder. Crushing the glass, and mixing with commercial beta-SiAlON with the purity of more than 99.99 percent2+Phosphor and CaAlSiN3:Eu2+The fluorescent powder is uniformly mixed according to the mass ratio. The mixture is pressed, then sintered for 1h in the air at 600 ℃, and then naturally cooled to obtain the glass.
Example 2: 65SiO2-25Na2O-5BaO-5ZnO-4mol%Nd2O30.3 wt% of beta-SiAlON: Eu is doped2+Phosphor, and 2 wt.% CaAlSiN3:Eu2+Fluorescent powder;
weighing SiO with purity of more than 99.9 percent according to stoichiometric ratio2、Na2O、BaO、ZnO、Nd2O3Placing the glass in an alumina crucible, melting the glass at 1300 ℃ for 60 minutes, and then quenching and drying the glass to obtain the glass without the fluorescent powder. Crushing the glass, and mixing with commercial beta-SiAlON with the purity of more than 99.99 percent2+Phosphor and CaAlSiN3:Eu2+The fluorescent powder is uniformly mixed according to the mass ratio. The mixture is pressed, then sintered for 2 hours in air at 500 ℃, and then naturally cooled to obtain the glass.
Example 3: 65SiO2-25Na2O-5BaO-5ZnO-5mol%Nd2O30.3 wt% of beta-SiAlON: Eu is doped2+Phosphor, and 3wt.% CaAlSiN3:Eu2+Fluorescent powder;
weighing SiO with purity of more than 99.9 percent according to stoichiometric ratio2、Na2O、BaO、ZnO、Nd2O3Placing the glass in an alumina crucible, melting the glass for 40 minutes at 1400 ℃, and then quenching and drying the glass to obtain the glass without the fluorescent powder. Crushing the glass, and mixing with commercial beta-SiAlON with the purity of more than 99.99 percent2+Phosphor and CaAlSiN3:Eu2+The fluorescent powder is uniformly mixed according to the mass ratio. The mixture was pressed, then sintered in air at 550 ℃ for 1.5h, and then naturally cooled to obtain the glass.
Example 4: 65SiO2-25Na2O-5BaO-5ZnO, 0.3 weight percent of beta-SiAlON: Eu is doped2+Phosphor, and 1 wt.% CaAlSiN3:Eu2+Fluorescent powder;
weighing SiO with purity of more than 99.9 percent according to stoichiometric ratio2、Na2And placing O, BaO and ZnO in an alumina crucible, melting for 40 minutes at 1400 ℃, and then quenching with water and drying to obtain the glass without the fluorescent powder. Crushing the glass, and mixing with commercial beta-SiAlON with the purity of more than 99.99 percent2+Phosphor and CaAlSiN3:Eu2+The fluorescent powder is uniformly mixed according to the mass ratio. The mixture was pressed, then sintered in air at 550 ℃ for 1.5h, and then naturally cooled to obtain the glass.
Taking example 1 as an example, the SEM spectrum in FIG. 1 shows that beta-SiAlON: Eu2+And CASN:Eu2+The fluorescent powder is well dispersed in the glass matrix and does not have obvious reaction with the glass. EL and PL emission spectra in FIG. 2 show, Nd3+After ion introduction, due to Nd3+:4I9/2→4G5/2，2G7/2Absorption characteristics, green and red emission are well separated. As can be seen from the CIE coordinate diagram, the Nd is not introduced3+Compared with the prior art, the color gamut is obviously wider and reaches 87-88% of the color gamut of NTSC, so that the color gamut is very suitable for LED display.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and are not limited. Although the present invention has been described in detail with reference to the above embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the scope of the present invention.

Claims (2)

1. A preparation method of wide-color-gamut glass for LED display is characterized in that the prepared wide-color-gamut glass meets the following components:
65SiO2-25Na2O-5BaO-5ZnO-xNd2O3
wherein x is more than or equal to 3 mol percent and less than or equal to 5 mol percent, and 0.3 weight percent of beta-SiAlON is doped2+Phosphor, and yCaAlSiN3:Eu2+Fluorescent powder, wherein y is more than or equal to 1 wt% and less than or equal to 3 wt%; the alloy is prepared by a melt quenching method, and comprises the following specific steps:
weighing SiO with purity of more than 99.9 percent according to stoichiometric ratio2、Na2O、BaO、ZnO、Nd2O3Placing the glass in an alumina crucible, melting the glass for 30 to 60 minutes at 1300 to 1450 ℃, and then quenching and drying the glass to obtain the glass without the fluorescent powder; crushing glass, mixing with beta-SiAlON with Eu, the purity of which is more than 99.99%2+Phosphor and CaAlSiN3:Eu2+Uniformly mixing the fluorescent powder according to the mass ratio; and pressing the mixture, sintering the mixture in air at 500-600 ℃ for 1-2 hours, and naturally cooling to obtain the glass.
2. A wide color gamut glass for LED display, which is prepared by the preparation method of claim 1, and has an NTSC color gamut of 87-88%.
CN202011500696.6A 2020-12-17 2020-12-17 Wide-color-gamut glass for LED display and preparation method thereof Active CN112551892B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107879623A (en) * 2017-11-20 2018-04-06 上海应用技术大学 A kind of white light LEDs emitting red light glass ceramics and preparation method thereof
CN110615613A (en) * 2019-07-01 2019-12-27 上海大学 Red light compensation fluorescent glass ceramic, preparation method thereof and application thereof in white light LED device
CN111574062A (en) * 2020-03-31 2020-08-25 温州大学 Nitride red-light glass and application thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107879623A (en) * 2017-11-20 2018-04-06 上海应用技术大学 A kind of white light LEDs emitting red light glass ceramics and preparation method thereof
CN110615613A (en) * 2019-07-01 2019-12-27 上海大学 Red light compensation fluorescent glass ceramic, preparation method thereof and application thereof in white light LED device
CN111574062A (en) * 2020-03-31 2020-08-25 温州大学 Nitride red-light glass and application thereof

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