CN110963711B - Composite quantum dot glass and preparation method thereof - Google Patents

Composite quantum dot glass and preparation method thereof Download PDF

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CN110963711B
CN110963711B CN201911285596.3A CN201911285596A CN110963711B CN 110963711 B CN110963711 B CN 110963711B CN 201911285596 A CN201911285596 A CN 201911285596A CN 110963711 B CN110963711 B CN 110963711B
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quantum dot
glass
matrix
composite
composite quantum
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CN110963711A (en
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杨波波
梅时良
熊志勇
郭睿倩
张万路
解凤贤
叶怀宇
张国旗
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Southern University of Science and Technology
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Shenzhen Third Generation Semiconductor Research Institute
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    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C14/00Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix
    • C03C14/006Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix the non-glass component being in the form of microcrystallites, e.g. of optically or electrically active material
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03BMANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B19/00Other methods of shaping glass
    • C03B19/02Other methods of shaping glass by casting molten glass, e.g. injection moulding
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C4/00Compositions for glass with special properties
    • C03C4/12Compositions for glass with special properties for luminescent glass; for fluorescent glass
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C2214/00Nature of the non-vitreous component
    • C03C2214/30Methods of making the composites

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  • Organic Chemistry (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
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  • General Chemical & Material Sciences (AREA)
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Abstract

The invention discloses composite quantum dot glass and a preparation method thereof, wherein the composite quantum dot glass comprises a glass matrix and a quantum dot matrix, wherein the quantum dot matrix accounts for 10-20 mol% of the glass matrix; the quantum dot matrix is an inorganic perovskite-binary semiconductor composite quantum dot; the binary semiconductor in the quantum dot matrix is 5-10% mol of the inorganic perovskite. The inorganic perovskite-binary semiconductor composite quantum dot is a cesium halide lead perovskite-zinc sulfide composite quantum dot. The invention uses B2O3‑SiO2ZnO is used as a matrix glass system, the physical and chemical properties are stable, the melting temperature of the glass can be effectively reduced by ZnO, the network structure of the glass can be adjusted by BaO, perovskite quantum dots can be easily grown in situ in the glass, the melting point of the glass can be reduced by PbO in the quantum dot raw material, the stability and the color purity of the perovskite quantum dots can be further improved by adding trace zinc sulfide, and blue ZnS quantum dots can be simultaneously separated out from the glass under the annealing condition by adding proper amount of zinc sulfide.

Description

Composite quantum dot glass and preparation method thereof
Technical Field
The invention relates to the technical field of quantum dot luminescent materials, in particular to composite quantum dot glass and a preparation method thereof.
Background
Recently, all-inorganic halides (CsPbX)3) The perovskite quantum dot has great potential application value in the fields of light-emitting diodes, lasers, polaroids, solar cells, photodetectors and the like by virtue of adjustable light-emitting wavelength, high fluorescence quantum efficiency and narrow emission peak. CsPbX3The quantum dots can be well dispersed in a plurality of non-polar solutions, and the oil phase perovskite quantum dots can be packaged into low-cost photoelectric devices. So far, the pure color CsPbX with the quantum size of 4-15nm, the luminous wavelength of which covers the whole visible spectrum (410 nm-700 nm), the luminous quantum efficiency of which reaches 90 percent3Quantum dots have been reported. However, the perovskite quantum dots synthesized by the liquid phase have poor stability in air and poor water resistance, and the packaged devices have poor performances in the aspects of heat resistance, light aging resistance and the like, so that the further development of the perovskite quantum dots in the fields of photoelectric materials and devices is hindered.
In order to improve the stability of perovskite quantum dots, researchers have tried various methods including ligand exchange, high molecular materials or organosilicon coated quantum dots, and the like. The Zeng group in 2016 embeds quantum dots into a high molecular material PMMA, and protects the excellent optical performance of the quantum dots. Liu and collaborators thereof use mesoporous silica to coat CsPbBr in nonpolar solution3The perovskite quantum dot, Zhang and Rogach teams use organosilicon (3-aminopropyl) triethoxysilane and polyhedral oligomeric silsesquioxane as end-capping agents respectively to generate the quantum dot/organosilicon composite material through hydrolysis. Further, Mn is concerned2+:CsPbCl3/CsPbCl3Quantum dots, CsPbX3/ZnS heterostructure quantum dots, and phosphoric acid enhanced CsPbX3The quantum dots can be reported to improve the stability of the quantum dots. However, because of the high oxygen dispersion coefficient in the organic matter, these methods cannot ensure that the quantum dots can effectively avoid photooxidation. Therefore, the improvement of the stability of the quantum dot organic composite material under extreme conditions needs to be further researched, especially the thermal stability of the quantum dot organic composite material. So far, no quantum dot can prepare a high-efficiency device which is stable for a long time.
The traditional preparation process of the quantum dot film is directly prepared by coating a quantum dot solution or colloid on a substrate, the luminous stability of the traditional preparation process is limited by the stability of the quantum dot solution, the quantum efficiency of the traditional preparation process is greatly reduced, and the application of the traditional preparation process in a luminescent device is limited.
The glass in-situ growth of quantum dots is an effective way for preparing a quantum dot material with long-term stability, but in the preparation process of the quantum dot glass, halogen atoms, lead atoms, cesium atoms and the like are unevenly distributed in a glass precursor due to the fact that the internal and external temperatures of a glass melt are inconsistent in the cooling process, so that perovskite quantum dots precipitated in the heat treatment process are uneven, and the color purity of the quantum dot glass is not high.
In order to ensure the sufficient strength and transparency of the glass, the glass substrate is generally selected to be silicate glass, and the melting point of the silicon oxide raw material is high, so that the melting point of the quantum dot glass precursor is also high.
Disclosure of Invention
In order to solve the problems, the invention provides a composite quantum dot glass, which comprises a glass matrix and a quantum dot matrix, wherein the glass matrix is B2O3-SiO2-ZnO system said quantum dot matrix molar ratio is between 10% and 20% of said glass matrix; the quantum dot matrix is an inorganic perovskite-binary semiconductor composite quantum dot; the molar ratio of the binary semiconductor in the quantum dot matrix is 5-10% of that of the inorganic perovskite.
Preferably, the inorganic perovskite-binary semiconductor composite quantum dot is a cesium-lead perovskite-zinc sulfide composite quantum dot.
Preferably, the glass substrate comprises 10-20 mol% of sodium oxide, 10-20 mol% of zinc oxide, 50 mol% of boron oxide, 20 mol% of silicon oxide and 5-10 mol% of barium oxide.
Preferably, the thickness of the quantum dot glass is 0.05mm-1.05 mm.
Preferably, the emission wavelength of the inorganic perovskite is 500mm-550nm, and the emission wavelength of the zinc sulfide is 430mm-500 nm.
Based on the same inventive concept, the invention provides a preparation method of composite quantum dot glass, which comprises the following steps
S1: adding the quantum dot matrix into the glass matrix and sintering to obtain a molten mass;
s2: casting and molding the molten mass to obtain transparent glass;
s3: and annealing and cooling the transparent glass to obtain the composite quantum dot glass.
Preferably, the sintering temperature in S1 is 1000-1350 ℃, and the sintering time is 5-30 min.
Preferably, the S2 is specifically that the melt is cast in a mold with the preheating temperature of 200-300 ℃ for molding, and the temperature is kept for 1-3 h.
Preferably, the annealing temperature of S3 is 400-450 ℃, and the annealing time is 3-10 h.
Preferably, the mold is an iron plate, a copper plate, or a stainless steel plate.
Preferably, the thickness of the quantum dot glass is 0.05mm-1.05 mm.
The invention also provides a preparation method of the composite quantum dot glass, which comprises the following steps
S1: adding quantum dot matrix into the glass matrix and sintering to obtain molten mass;
s2: casting and molding the molten mass to obtain transparent glass;
s3: and annealing and cooling the transparent glass to obtain the composite quantum dot glass.
Preferably, the sintering temperature in the S1 is 1000-1350 ℃, and the sintering time is 5-30 min.
Preferably, the S2 is specifically that the melt is cast in a mold with a preheating temperature of 200-300 ℃ for molding, and the temperature is kept for 1-3 hours.
Preferably, the annealing temperature of S3 is 400-450 ℃, and the annealing time is 3-10 h.
Preferably, the mold is an iron plate, a copper plate, or a stainless steel plate.
The invention has the beneficial effects that:
(1) the composite quantum dot glass of the invention is prepared by mixing B2O3-SiO2ZnO is used as a matrix glass system, the borosilicate glass has high transparency and stable physical and chemical properties, and simultaneously ZnO can effectively reduce the melting temperature of glass, BaO can adjust the glass network structure, make in situ grow out perovskite quantum dot in the glass more easily, PbO can reduce the glass melting point in the quantum dot raw materials, make glass stability improve, can provide Pb element as the quantum dot raw materials again, make the glass separate out perovskite quantum dot under the annealing condition, trace zinc sulfide adds and can further promote perovskite quantum dot stability and colour purity, the addition of appropriate amount zinc sulfide makes glass separate out blue light ZnS quantum dot simultaneously under the annealing condition.
(2) The preparation method of the composite quantum dot glass is simple, the raw materials of the matrix glass and the composite quantum dot raw materials are fully mixed according to a certain proportion, the precursor glass can be obtained by one-step sintering, and then the composite quantum dot glass can be obtained by low-temperature heat treatment. In particular, the invention can be used in LED and display technology.
Drawings
FIG. 1 is a fluorescence emission spectrum of the composite quantum dot prepared in example 1 of the present invention;
FIG. 2 is a coupling luminescence diagram of the composite quantum dot and the chip manufactured in example 1 of the present invention;
FIG. 3 is a fluorescence emission spectrum of the composite quantum dot prepared in example 2 of the present invention;
fig. 4 is a coupling luminescence diagram of the composite quantum dot and the chip manufactured in embodiment 2 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to the accompanying drawings and examples. It should be understood, however, that the description herein of specific embodiments is only intended to illustrate the invention and not to limit the scope of the invention.
The composite quantum dot glass provided by the invention comprises a glass matrix and a quantum dot matrix, wherein the quantum dot matrix accounts for 10-20 mol% of the glass matrix; the quantum dot matrix is an inorganic perovskite-binary semiconductor composite quantum dot; the binary semiconductor in the quantum dot matrix is 2-10 mol% of the inorganic perovskite. Wherein the inorganic perovskite-binary semiconductor composite quantum dots are cesium halide lead perovskite-zinc sulfide composite quantum dots. The thickness of the quantum dot glass is 0.05-1.05 mm. The emission wavelength of the inorganic perovskite is 500-550nm, and the emission wavelength of the zinc sulfide is 430-500 nm. The cesium-lead-perovskite halide component comprises: cesium carbonate, lead oxide, sodium bromide.
The first embodiment is as follows: the embodiment provides green light low-melting-point composite quantum dot glass
Will analyze pure Na2CO3、ZnO、B2O3、SiO2、BaCO3、Cs2CO3PbO, NaBr, ZnS in an amount of 10 mol% Na based on the base glass raw material2O,10mol%ZnO,50mol%B2O3,20mol%SiO210 mol% BaO; 10 wt% of quantum dot raw material, wherein each component of the quantum dot raw material is 10 mol% of Cs2CO3: 22 mol% PbO: 66 mol% NaBr: accurately weighing the molar fraction ratio of 2 mol% ZnS, placing the ZnS in an agate mortar, uniformly grinding the ZnS in the agate mortar, placing the ZnS in a corundum crucible, placing the corundum crucible in a muffle furnace at 1150 ℃ for heat preservation for 10min, taking out a glass solution, quickly casting the glass solution in a mold with the preheating temperature of 250 ℃ for molding to obtain transparent glass, preserving the heat for 2h, and eliminating internal stress; and then transferring the glass to a muffle furnace for annealing at 430 ℃ for 5h, and naturally cooling to obtain the composite quantum dot glass.
The obtained composite quantum dot glass is measured by a fluorescence spectrometer (FLS920, Edinburgh Instruments, England) to obtain a spectrogram as shown in figure 1, under the excitation of 400nm wavelength, the emission wavelength is 525nm, the peak width at half height is 20nm, and the corresponding perovskite quantum dot CsPbBr is obtained3The composite quantum dot glass is coupled with a 400nm chip by using a Hangzhou remote STC4000 rapid spectrometer to emit bright green light, as shown in figure 2.
Example two: the embodiment provides a green light low-melting point composite quantum dot glass
Will analyze pure Na2CO3、ZnO、B2O3、SiO2、BaCO3、Cs2CO3PbO, NaBr, ZnS in an amount of 15 mol% Na based on the base glass raw material2O,10mol%ZnO,50mol%B2O3,20mol%SiO25 mol% BaO; 10 wt% of quantum dot raw material, wherein each component of the quantum dot raw material is 10 mol% of Cs2CO3: 20 mol% PbO: 64 mol% NaBr: accurately weighing the molar fraction ratio of 6 mol% ZnS, placing the ZnS in an agate mortar, grinding the ZnS in the agate mortar uniformly, placing the ZnS in a corundum crucible, placing the corundum crucible in a muffle furnace at 1150 ℃ for heat preservation for 10min, taking out a glass solution, quickly casting the glass solution in a mold with the preheating temperature of 250 ℃ for molding to obtain transparent glass, preserving the heat for 2h, and eliminating internal stress; then transferring the glass to a muffle furnace for annealing at 430 ℃ for 5h, and naturally cooling to obtain the composite quantum dot glass;
the obtained composite quantum dot glass is measured by a fluorescence spectrometer (FLS920, Edinburgh Instruments, England), the obtained spectrogram is shown in figure 3, under the excitation of 400nm wavelength, emission spectra show two peaks which are positioned at 510nm and 470nm and respectively correspond to perovskite quantum dots CsPbBr3And fluorescence emission of semiconductor quantum dots ZnS, coupling the composite quantum dot glass with a 400nm blue light chip by using a Hangzhou remote STC4000 rapid spectrometer, and emitting bright cyan-green light, as shown in figure 4.
The foregoing is a further description of the invention with reference to preferred embodiments, and the examples described are some, but not all, examples of the invention. It will be apparent to those skilled in the art that various modifications, additions, substitutions, and other embodiments can be made without departing from the spirit and scope of the invention.

Claims (8)

1. A composite quantum dot glass is characterized in that: comprises a glass matrix and a quantum dot matrix, wherein the glass matrix is B2O3-SiO2-ZnO system, said quantum dot matrix molar ratio being between 10% and 20% of said glass matrix; what is needed isThe quantum dot matrix is an inorganic perovskite-binary semiconductor composite quantum dot; the molar ratio of the binary semiconductor in the quantum dot matrix is 5 to 10 percent of that of the inorganic perovskite;
the inorganic perovskite-binary semiconductor composite quantum dots are cesium halide lead perovskite-zinc sulfide composite quantum dots;
the glass substrate comprises 10-15 mol% of sodium oxide, 10 mol% of zinc oxide, 50 mol% of boron oxide, 20 mol% of silicon oxide and 5-10 mol% of barium oxide.
2. A composite quantum dot glass according to claim 1, wherein: the thickness of the composite quantum dot glass is 0.05mm-1.05 mm.
3. A composite quantum dot glass according to claim 1, wherein: the emission wavelength of the inorganic perovskite is 500mm-550nm, and the emission wavelength of the zinc sulfide is 430mm-500 nm.
4. A method for preparing the composite quantum dot glass according to any one of claims 1 to 3, characterized in that: including S1: adding the quantum dot matrix into the glass matrix and sintering to obtain a molten mass; s2: casting and molding the molten mass to obtain transparent glass; s3: and annealing and cooling the transparent glass to obtain the composite quantum dot glass.
5. A method for preparing the composite quantum dot glass according to claim 4, which is characterized in that: the sintering temperature in the S1 is 1000-1350 ℃, and the sintering time is 5-30 min.
6. A method for preparing the composite quantum dot glass according to claim 4, which is characterized in that: and S2, specifically, casting the molten mass in a mold with a preheating temperature of 200-300 ℃ for molding, and keeping the temperature for 1-3 hours.
7. A method for preparing the composite quantum dot glass according to claim 4, which is characterized in that: the annealing temperature of S3 is 400-450 ℃, and the annealing time is 3-10 h.
8. A method for preparing the composite quantum dot glass according to claim 6, characterized in that: the die is an iron plate, a copper plate or a stainless steel plate.
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TR202101278A1 (en) * 2021-01-27 2022-08-22 Univ Yildiz Teknik A solid-state illumination device containing CdSe and CsPbBr3 quantum dot-doped glass nanocomposite layers and its fabrication method.
CN112759267A (en) * 2021-02-04 2021-05-07 中国科学院福建物质结构研究所 Perovskite nanocrystalline glass ceramic membrane laminated composite material
CN114213004B (en) * 2021-12-31 2022-08-02 云南大学 White light quantum dot luminescent glass and preparation method and application thereof
CN114716142B (en) * 2022-04-12 2023-09-05 中国计量大学上虞高等研究院有限公司 ZnS-doped quantum dot luminescent glass and preparation method and application thereof
CN114920460B (en) * 2022-05-02 2024-03-26 哈尔滨工程大学 Diphase quantum dot microcrystalline glass and preparation method and application thereof
CN115161026B (en) * 2022-07-29 2024-07-30 厦门大学 Core-shell quantum dot luminescent material and preparation method thereof
CN115259663A (en) * 2022-08-15 2022-11-01 上海应用技术大学 All-inorganic perovskite quantum dot composite glass and preparation method thereof
CN116282927A (en) * 2023-04-07 2023-06-23 上海应用技术大学 Double-emission color-adjustable composite glass ceramic and preparation method and application thereof

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