CN116396744B - Electroluminescent microcapsule core material and preparation method thereof - Google Patents

Electroluminescent microcapsule core material and preparation method thereof Download PDF

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Publication number
CN116396744B
CN116396744B CN202310242451.5A CN202310242451A CN116396744B CN 116396744 B CN116396744 B CN 116396744B CN 202310242451 A CN202310242451 A CN 202310242451A CN 116396744 B CN116396744 B CN 116396744B
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core material
quantum dots
electroluminescent
zinc oxide
microcapsule core
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CN116396744A (en
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张爱刚
张爱斌
孙志成
刘铭
胡海清
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Yangzhou Xianghua New Material Technology Co ltd
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Yangzhou Xianghua New Material Technology Co ltd
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02Use of particular materials as binders, particle coatings or suspension media therefor
    • C09K11/025Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • H10K50/10OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • H10K50/10OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/115OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • H10K50/10OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/12OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18Metal complexes
    • C09K2211/185Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd

Abstract

The invention provides an electroluminescent microcapsule core material and a preparation method thereof, wherein the core material comprises the following components: an electrophosphorescent luminescent material, tetrapod-like zinc oxide whiskers, and quantum dots, the electrophosphorescent luminescent material: four needle-shaped zinc oxide whisker: the mass ratio of the quantum dots is 1: (1-3): (5-7), the method for producing the core material comprising: uniformly mixing the tetrapod-like zinc oxide whiskers subjected to magnetron sputtering coating treatment with quantum dots according to the mass ratio to obtain a first mixture, and mixing the first mixture with an electrophosphorescent luminescent material according to the mass ratio to obtain the electroluminescent microcapsule core material. The electroluminescent microcapsule core material has uniform luminous spectrum color gamut and can obviously reduce the intensity of blue light.

Description

Electroluminescent microcapsule core material and preparation method thereof
Technical Field
The invention relates to the field of new display materials, in particular to an electroluminescent microcapsule core material and a preparation method thereof.
Background
The organic electroluminescent device has the advantages of high efficiency, low power consumption, high color gamut and the like, and the phosphorescent luminescent material has been widely paid attention to because of high internal quantum efficiency. However, the phosphorescent light-emitting material is sensitive to moisture, oxygen and the like, so that the phosphorescent light-emitting material needs to be packaged in the prior art, and a conventional packaging mode comprises a cover plate packaging technology such as a metal cover and a glass cover.
In the prior art, the problem that the wavelength power of blue light is higher in the light-emitting spectrum of the LED is mainly caused by that the energy of the blue light is stronger, other color fluorescent materials can be excited by the blue light photons, so that different colors of light can be emitted, the blue light emitting materials and the fluorescent materials are respectively packaged in different structures, the absorption of the blue light photons by the fluorescent materials is low, the blue light spectrum energy is higher, and how to provide an electroluminescent microcapsule core material capable of reducing the blue light spectrum energy for the packaging structure of the microcapsule is a technical problem to be solved at present.
Disclosure of Invention
In view of the above, the invention provides an electroluminescent microcapsule core material and a preparation method thereof, which aim to solve the problem of high energy of a blue light spectrum in the current LED light spectrum.
The technical scheme of the invention is realized as follows: the invention provides an electroluminescent microcapsule core material, which comprises an electrophosphorescent luminescent material, tetrapod-like zinc oxide whiskers and quantum dots, wherein the electrophosphorescent luminescent material comprises: four needle-shaped zinc oxide whisker: the mass ratio of the quantum dots is 1: (1-3): (5-7).
In some embodiments, the electrophosphorescent luminescent material isWherein R is-H, -CH 3 、-C 2 H 5 One of them.
In some embodiments, the electrophosphorescent luminescent material is
In some embodiments, the tetrapod-like zinc oxide whiskers are subjected to a surface magnetron sputtering coating treatment, and the coating layer is a zinc layer.
In the embodiment, the tetrapod-shaped zinc oxide whisker after surface magnetron sputtering coating has better affinity with InP/ZnS quantum dots, and is favorable for improving the adhesion between the two quantum dots, so that the filling amount of the o-quantum dots is improved, and the tetrapod-shaped zinc oxide whisker is used for supporting, so that the space between the electrophosphorescent luminescent material and the quantum dots can be kept, and quenching caused by high local concentration of the electrophosphorescent luminescent material is avoided.
In some embodiments, the thickness of the coating layer is 3-5nm.
In some embodiments, the tetrapod-like zinc oxide whiskers are subjected to a surface plasma treatment prior to the surface magnetron sputtering coating treatment.
In some embodiments, the quantum dots are InP/ZnS quantum dots having a particle size of 2-8nm.
In some embodiments, the mass ratio of quantum dots having a particle size of less than 5nm to quantum dots having a particle size of not less than 5nm is 1:3.
In the above embodiment, the granularity of the quantum dots is controlled within a certain size proportion range, so as to solve the problems of low luminous spectrum intensity and too high blue light intensity of the region between the blue light and the green light in a sealed manner, and the quantum dots are used for absorbing the high-intensity blue light and emitting light in the region between the blue light spectrum and the green light spectrum, thereby reducing the blue light intensity and improving the smoothness of the light intensity curve.
On the other hand, the invention also provides a preparation method of the electroluminescent microcapsule core material, which comprises the following steps:
uniformly mixing the tetrapod-like zinc oxide whiskers subjected to magnetron sputtering coating treatment with quantum dots according to the mass ratio to obtain a first mixture, and mixing the first mixture with an electrophosphorescent luminescent material according to the mass ratio to obtain the electroluminescent microcapsule core material.
In some embodiments, the four needle-shaped zinc oxide whiskers treated by magnetron sputtering coating are mixed with quantum dots and simultaneously subjected to ultrasonic treatment.
Compared with the prior art, the electroluminescent microcapsule core material has the following beneficial effects:
the electroluminescent microcapsule prepared by the electroluminescent microcapsule core material can emit blue light with smoother spectrum, overcomes the serious problem of blue light of the conventional phosphorescence luminescent material, and improves the saturation of the color gamut between the blue light and the green light by adding quantum dots with a certain proportion.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a graph of normalized luminous intensity for some embodiments of the present invention;
FIG. 2 is a graph of normalized luminous intensity for some embodiments of the present invention.
Detailed Description
The following description of the embodiments of the present invention will clearly and fully describe the technical aspects of the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, are intended to fall within the scope of the present invention.
Unless defined otherwise, all technical terms and science used herein have the same meaning as commonly understood by one of ordinary skill in the art to which embodiments of the present invention belong. If the definitions set forth in this section are contrary to or otherwise inconsistent with the definitions set forth in the patents, patent applications, published patent applications and other publications incorporated herein by reference, the definitions set forth in this section are preferentially set forth in the definitions set forth herein.
The preparation method of the electrophosphorescent luminescent material comprises the following steps:
compound a:and compound B: />In the atmosphere of protective gas, pd (PPh 3) 4 or Pd (PPh 3) 2Cl2 is used as a catalyst for catalysis, alkali solution Na2CO3 or K2CO3 and organic solvent AReflux stirring for 6-12h at 85-95 ℃ in the presence of benzene or tetrahydrofuran, performing suzuki reaction, separating and purifying to obtain a compound C:wherein R is-H, -CH 3 or-C 2 H 5
Under the atmosphere of protective gas, the compound C and IrCl3.3H2O are mixed according to the molar ratio of (2-3): 1 is dissolved in a mixed solution composed of 2-ethoxyethanol and water in a volume ratio of 3:1, the concentration of C in the mixed solution is 0.05-0.125mol/L, stirring treatment is carried out for 22-25h in a reflux state, and a compound D is obtained after separation and purification:
dissolving the compound D in dichloromethane, dropwise adding an organic solution of an organic salt of Ag at room temperature, filtering after the reaction is completed, removing a solvent after the filtrate is reserved to obtain a solid residue, and reacting the solid residue with the compound E under the atmosphere of protective gas:dissolving in acetonitrile, refluxing for 22-25h, separating and purifying to obtain the electrophosphorescent material:
example 1
The present embodiment provides a microcapsule core material, including: electrophosphorescent luminescent material:the preparation method comprises the steps of mixing tetrapod-like zinc oxide whiskers and InP/ZnS quantum dots with the particle size of 3nm according to the mass ratio of 1:5 to obtain a first mixture, and mixing the first mixture with an electrophosphorescent luminescent material according to the mass ratio of 6:1 to obtain the electroluminescent microcapsule core material.
Example 2
The embodiment providesA microcapsule core material comprising: electrophosphorescent luminescent material:the preparation method comprises the steps of mixing tetrapod-like zinc oxide whiskers and InP/ZnS quantum dots with diameters of 3nm according to a mass ratio of 1:5 to obtain a first mixture, and mixing the first mixture with an electrophosphorescent luminescent material according to a mass ratio of 6:1 to obtain the electroluminescent microcapsule core material.
Example 3
The present embodiment provides a microcapsule core material, including: electrophosphorescent luminescent material:the preparation method comprises the steps of mixing tetrapod-like zinc oxide whiskers and InP/ZnS quantum dots with diameters of 3nm according to a mass ratio of 1:5 to obtain a first mixture, and mixing the first mixture with an electrophosphorescent luminescent material according to a mass ratio of 6:1 to obtain the electroluminescent microcapsule core material.
Example 4
The present embodiment provides a microcapsule core material, including: electrophosphorescent luminescent material:the preparation method comprises the steps of mixing tetrapod-like zinc oxide whiskers and InP/ZnS quantum dots with diameters of 3nm according to a mass ratio of 1:7 to obtain a first mixture, and mixing the first mixture with an electrophosphorescent luminescent material according to a mass ratio of 8:1 to obtain the electroluminescent microcapsule core material.
Example 5
The present embodiment provides a microcapsule core material, including: electrophosphorescent luminescent material:the four-needle zinc oxide whisker and InP/ZnS quantum dot with the diameter of 3nm are mixed according to the mass ratio3:5 to obtain a first mixture, and mixing the first mixture with an electrophosphorescent luminescent material according to a mass ratio of 8:1 to obtain the electroluminescent microcapsule core material.
Example 6
The present embodiment provides a microcapsule core material, including: electrophosphorescent luminescent material:four needle-shaped zinc oxide whiskers and InP/ZnS quantum dots, wherein the particle size distribution of the InP/ZnS quantum dots is as follows: quantum dots with particle size greater than 2nm and less than 5 nm: the ratio of the quantum dots with the particle size of 5-8nm is 1:1, the tetrapod-like zinc oxide whisker and the InP/ZnS quantum dots are mixed according to the mass ratio of 1:5 to obtain a first mixture, and the first mixture is mixed with the electrophosphorescent luminescent material according to the mass ratio of 6:1 to obtain the electroluminescent microcapsule core material.
Example 7
The present embodiment provides a microcapsule core material, including: electrophosphorescent luminescent material:four needle-shaped zinc oxide whiskers and InP/ZnS quantum dots, wherein the particle size distribution of the InP/ZnS quantum dots is as follows: quantum dots with particle size greater than 2nm and less than 5 nm: the ratio of the quantum dots with the particle size of 5-8nm is 1:3, the tetrapod-like zinc oxide whisker and the InP/ZnS quantum dots are mixed according to the mass ratio of 1:5 to obtain a first mixture, and the first mixture is mixed with the electrophosphorescent luminescent material according to the mass ratio of 6:1 to obtain the electroluminescent microcapsule core material.
Example 8
The present embodiment provides a microcapsule core material, including: electrophosphorescent luminescent material:the zinc plating layer comprises four needle-shaped zinc oxide whiskers and InP/ZnS quantum dots with the particle size of 3nm, wherein the four needle-shaped zinc oxide whiskers are subjected to surface magnetron sputtering zinc plating treatment, and the thickness of the zinc plating layer is 3-5nm. Amount of tetrapod-like zinc oxide whisker and InP/ZnSMixing the sub-points according to the mass ratio of 1:5 to obtain a first mixture, and mixing the first mixture with an electrophosphorescent luminescent material according to the mass ratio of 6:1 to obtain the electroluminescent microcapsule core material.
Example 9
The present embodiment provides a microcapsule core material, including: electrophosphorescent luminescent material:the zinc oxide crystal whisker comprises four needle-shaped zinc oxide crystal whiskers and InP/ZnS quantum dots with the particle size of 3nm, wherein the four needle-shaped zinc oxide crystal whiskers are subjected to argon plasma surface treatment firstly and then surface magnetron sputtering zinc plating treatment, and the thickness of a zinc plating layer is 3-5nm. Mixing tetrapod-like zinc oxide whiskers and InP/ZnS quantum dots according to the mass ratio of 1:5, simultaneously assisting in ultrasonic treatment to obtain a first mixture, and mixing the first mixture with an electrophosphorescent luminescent material according to the mass ratio of 6:1 to obtain the electroluminescent microcapsule core material.
Comparative example
Directly combining the electrophosphorescent luminescent material:as a core material.
The core material is respectively prepared into microcapsules, and the preparation method of the microcapsules comprises the following steps:
dissolving gelatin in n-hexane to obtain 5% gelatin solution, adding the core material into gelatin solution, stirring to form emulsified dispersion system, regulating pH to 3.5 with 10% acetic acid, maintaining the emulsion temperature at 50deg.C, adding 20% sodium sulfate solution into the dispersion system, and reducing the emulsion temperature to 15deg.C to obtain microcapsule with particle diameter of 200 μm.
The microcapsule prepared by the method is mixed with a red light material and a green light phosphorescence material to be doped in the same luminescent layer, the luminescent layer is used in an LED luminescent display structure, and the luminescent spectrum is detected under the same power, and the obtained result is shown in figures 1 and 2.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.

Claims (7)

1. An electroluminescent microcapsule core material comprising: an electrophosphorescent luminescent material, tetrapod-like zinc oxide whiskers, and quantum dots, the electrophosphorescent luminescent material: four needle-shaped zinc oxide whisker: the mass ratio of the quantum dots is 1: (1-3): (5-7) the electrophosphorescent luminescent material isWherein R is-H, -CH 3 、-C 2 H 5 The quantum dots are InP/ZnS quantum dots, and the granularity of the quantum dots is 2-8nm.
2. The electroluminescent microcapsule core material of claim 1, wherein the tetrapod-like zinc oxide whiskers are subjected to surface magnetron sputtering coating treatment, and the coating layer is a zinc layer.
3. The electroluminescent microcapsule core of claim 2, wherein the thickness of the coating layer is 3-5nm.
4. The electroluminescent microcapsule core material of claim 2, wherein the tetrapod-like zinc oxide whiskers are subjected to a surface plasma treatment prior to the surface magnetron sputtering coating treatment.
5. The electroluminescent microcapsule core material of claim 1, wherein the mass ratio of quantum dots having a particle size of less than 5nm to quantum dots having a particle size of not less than 5nm is 1:3.
6. The method for preparing an electroluminescent microcapsule core material according to any one of claims 1 to 5, comprising the steps of:
uniformly mixing the tetrapod-like zinc oxide whiskers subjected to magnetron sputtering coating treatment with quantum dots according to the mass ratio to obtain a first mixture, and mixing the first mixture with an electrophosphorescent luminescent material according to the mass ratio to obtain the electroluminescent microcapsule core material.
7. The method for preparing an electroluminescent microcapsule core material as claimed in claim 6, characterized in that the tetrapod-like zinc oxide whiskers treated by magnetron sputtering coating are mixed with quantum dots and simultaneously subjected to ultrasonic treatment.
CN202310242451.5A 2023-03-14 2023-03-14 Electroluminescent microcapsule core material and preparation method thereof Active CN116396744B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0358078A1 (en) * 1988-08-29 1990-03-14 Matsushita Electric Industrial Co., Ltd. Fluorescent materials comprising zinc oxide whiskers
CN101638216A (en) * 2001-03-30 2010-02-03 加利福尼亚大学董事会 Methods of fabricating nanostructures and nanowires and devices fabricated therefrom
CN104170113A (en) * 2012-01-27 2014-11-26 韦克森林大学 Electroluminescent devices and applications thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0358078A1 (en) * 1988-08-29 1990-03-14 Matsushita Electric Industrial Co., Ltd. Fluorescent materials comprising zinc oxide whiskers
CN101638216A (en) * 2001-03-30 2010-02-03 加利福尼亚大学董事会 Methods of fabricating nanostructures and nanowires and devices fabricated therefrom
CN104170113A (en) * 2012-01-27 2014-11-26 韦克森林大学 Electroluminescent devices and applications thereof

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