CN113120953A - Composite material and preparation method thereof, light-emitting diode and preparation method - Google Patents

Composite material and preparation method thereof, light-emitting diode and preparation method Download PDF

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Publication number
CN113120953A
CN113120953A CN201911416603.9A CN201911416603A CN113120953A CN 113120953 A CN113120953 A CN 113120953A CN 201911416603 A CN201911416603 A CN 201911416603A CN 113120953 A CN113120953 A CN 113120953A
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precursor
surfactant
metal
composite material
metal sulfide
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何斯纳
吴龙佳
吴劲衡
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TCL Corp
TCL Research America Inc
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TCL Research America Inc
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00—Compounds of zinc
    • C01G9/08—Sulfides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G15/00—Compounds of gallium, indium or thallium
    • 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
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots

Abstract

The invention belongs to the technical field of display, and particularly relates to a composite material and a preparation method thereof, a light emitting diode and a preparation method thereof. The preparation method of the composite material provided by the invention comprises the following steps: providing a metal precursor, a sulfur precursor, a cationic surfactant and a nonionic surfactant; heating a metal precursor, a sulfur precursor, a cationic surfactant and a nonionic surfactant in an organic solvent to obtain a metal sulfide precursor solution; and carrying out solid-liquid separation on the metal sulfide precursor solution to obtain the composite material. The metal sulfide nano-particles prepared by the preparation method are modified with the cationic surfactant and the nonionic surfactant on the surface, have small particle size and uniform size distribution, are beneficial to forming a uniform and compact film layer, and improve the luminous performance of a QLED device.

Description

Composite material and preparation method thereof, light-emitting diode and preparation method
Technical Field
The invention belongs to the technical field of display, and particularly relates to a composite material and a preparation method thereof, a light emitting diode and a preparation method thereof.
Background
With the continuous progress of technology, Quantum Dot light emitting diodes (QDs) have been gradually emerging as unique advantages of extremely thin appearance, wider color gamut, high purity, high brightness, low starting voltage, and better stability, and may become a new generation of display products to replace Organic Light Emitting Diodes (OLEDs). The semiconductor quantum dots have quantum size effect, and people can realize the required light emission with specific wavelength by regulating the size of the quantum dots, for example, the size of CdSe QDs can be regulated to make the light emission wavelength tuning range from blue light to red light. The device structure of the QLED generally includes an anode layer, a hole transport layer, a quantum dot light emitting layer, an electron transport layer, and a cathode, where electrons and holes are injected from the cathode and the anode, respectively, and then recombined in the light emitting layer to form excitons for light emission.
The metal sulfide has good carrier transmission efficiency, and is often applied to the preparation of a carrier transmission layer of a QLED (quantum dot light emitting diode) so as to improve the luminous efficiency of a QLED device. However, the metal sulfide nanoparticles prepared by the existing process generally have the problems of large size and wide particle size distribution, so that the quality of the formed film layer is poor, and the light emitting performance of the QLED is reduced.
Disclosure of Invention
The invention mainly aims to solve the problems of large size and wide distribution of metal sulfide nano particles prepared by the prior art.
The technical scheme adopted by the invention is as follows:
a preparation method of a composite material comprises the following steps:
providing a metal precursor, a sulfur precursor, a cationic surfactant and a nonionic surfactant;
heating the metal precursor, the sulfur precursor, the cationic surfactant and the nonionic surfactant in an organic solvent to obtain a metal sulfide precursor solution;
and carrying out solid-liquid separation on the metal sulfide precursor solution to obtain the composite material.
According to the preparation method of the composite material, the cationic surfactant and the nonionic surfactant are added into a reaction system of the metal sulfide nanoparticles, so that newly generated metal sulfide precursor particles can be combined with the cationic surfactant and the nonionic surfactant in time, and on one hand, the cationic surfactant and the nonionic surfactant combined with the metal sulfide precursor particles have a steric hindrance effect and prevent the particles from approaching each other, so that the phenomenon that the particle size is overlarge due to hard agglomeration among the metal sulfide precursor particles is avoided; on the other hand, the cationic surfactant and the nonionic surfactant can form mixed micelles in a reaction system, and molecules of the nonionic surfactant are inserted between surface active ions of the anionic surfactant, so that the electric repulsion between the 'cationic heads' of the original double-electric-layer micelle particles is weakened, the surface activity of the solution is improved, the reaction system tends to be stable, the collision chance among particles is further reduced, the uneven growth of metal sulfide precursor particles is inhibited, the morphology and the size of the particles are effectively improved, and the metal sulfide nano particles with small size and uniform size distribution are prepared. Therefore, the metal sulfide nano-particles prepared by the preparation method are modified with the cationic surfactant and the nonionic surfactant on the surface, have small particle size and uniform size distribution, are beneficial to forming a uniform and compact film layer, and improve the luminous performance of the QLED device.
Correspondingly, the composite material is prepared by the preparation method and comprises the following steps: the metal sulfide nano-particle comprises a metal sulfide nano-particle and a surfactant bound on the surface of the metal sulfide nano-particle, wherein the surfactant is a cationic surfactant and a nonionic surfactant.
The composite material provided by the invention is prepared by the preparation method, is metal sulfide nano-particles with the surface modified with the surfactant, has small particle size and uniform size distribution, is favorable for forming a uniform and compact film layer, and improves the luminous performance of a QLED device.
Correspondingly, the light-emitting diode comprises a carrier transport layer, wherein the material of the carrier transport layer comprises: the composite material prepared by the preparation method or the composite material.
According to the light-emitting diode provided by the invention, the material of the carrier transmission layer is the composite material prepared by the preparation method or the composite material, and the composite material has the advantages of small particle size and uniform size distribution, so that the carrier transmission layer is uniform and compact, the film layer has excellent quality, and the light-emitting diode has good light-emitting performance.
Correspondingly, the preparation method of the light-emitting diode is characterized by comprising the following steps of preparing a carrier transmission layer:
providing a composite material, wherein the composite material is prepared by the preparation method or the composite material
Providing a substrate, and depositing the composite material on the substrate to obtain the carrier transport layer.
According to the preparation method of the light-emitting diode, the carrier transmission layer is prepared by adopting the composite material, so that the carrier transmission layer is uniform and compact, the quality of the film layer is excellent, and the light-emitting performance of the light-emitting diode is improved.
Drawings
FIG. 1 is a flow chart of a method for preparing a composite material according to an embodiment of the present invention;
FIG. 2 is a flow chart illustrating a step of performing a heating process in a method for manufacturing a composite material according to an embodiment of the present invention;
fig. 3 is a schematic structural diagram of a light emitting diode according to an embodiment of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the description of the present invention, it is to be understood that the terms "first", "second" and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
A method for preparing a composite material, as shown in fig. 1, comprising the steps of:
s01, providing a metal precursor, a sulfur precursor, a cationic surfactant and a nonionic surfactant;
s02, heating the metal precursor, the sulfur precursor, the cationic surfactant and the nonionic surfactant in an organic solvent to obtain a metal sulfide precursor solution;
and S03, carrying out solid-liquid separation on the metal sulfide precursor solution to obtain the composite material.
According to the preparation method of the composite material provided by the embodiment of the invention, the cationic surfactant and the nonionic surfactant are added into a reaction system of the metal sulfide nanoparticles, so that the newly generated metal sulfide precursor particles can be timely combined with the cationic surfactant and the nonionic surfactant, and on one hand, the cationic surfactant and the nonionic surfactant combined with the metal sulfide precursor particles have a steric hindrance effect and prevent the particles from approaching each other, so that the phenomenon that the particle size is overlarge due to hard agglomeration among the metal sulfide precursor particles is avoided; on the other hand, the cationic surfactant and the nonionic surfactant can form mixed micelles in a reaction system, and molecules of the nonionic surfactant are inserted between surface active ions of the anionic surfactant, so that the electric repulsion between the 'cationic heads' of the original double-electric-layer micelle particles is weakened, the surface activity of the solution is improved, the reaction system tends to be stable, the collision chance among particles is further reduced, the uneven growth of metal sulfide precursor particles is inhibited, the morphology and the size of the particles are effectively improved, and the metal sulfide nano particles with small size and uniform size distribution are prepared. Therefore, the metal sulfide nano-particles prepared by the preparation method provided by the embodiment of the invention are modified with the cationic surfactant and the nonionic surfactant on the surface, have small particle size and uniform size distribution, are beneficial to forming a uniform and compact film layer, and improve the light emitting performance of the QLED device.
Specifically, in step S01, a metal precursor and a sulfur precursor are raw materials for synthesizing metal sulfide nanoparticles, the metal precursor is used for providing metal atoms, and the sulfur precursor is used for providing sulfur atoms.
The metal precursor is selected from organic or inorganic substances which can provide metal atoms through reaction, and as one embodiment, the metal precursor is selected from at least one of soluble organic zinc salt, soluble inorganic zinc salt, soluble organic indium salt and soluble inorganic indium salt, so that the metal precursor can be fully dissolved in an organic solvent to improve the yield of the metal sulfide nanoparticles. In some embodiments, the metal precursor is selected from metal precursor salts corresponding to metal sulfides that can act as electron transport materials. In some embodiments, the zinc salt is selected from at least one of zinc acetate, zinc nitrate, zinc chloride, zinc acetate dihydrate. In some embodiments, the indium salt is selected from at least one of indium acetate, indium nitrate, indium chloride, and indium sulfate.
The sulfur precursor is selected from organic matters or inorganic matters which can provide sulfur atoms through reaction, as an implementation mode, the sulfur precursor is selected from at least one of sodium sulfide, potassium sulfide, thiourea and amine sulfide, the sulfur precursors can be completely dissolved in an organic solvent, and have good reaction activity with the metal precursor, so that the yield of the metal sulfide nanoparticles can be greatly improved.
In step S01, a cationic surfactant and a nonionic surfactant are used as the surface modification raw material of the metal sulfide nanoparticles.
The cationic surfactant can be selected from cationic Gemini surfactants and cationic high molecular surfactants. As an embodiment, the cationic surfactant includes: amine salt type surfactants and/or quaternary ammonium salt type surfactants. The amine salt type surfactant is an organic substance containing amine groups, and includes but is not limited to primary amine salts, secondary amine salts, tertiary amine salts and the like. The quaternary ammonium salt surfactant contains ammonium ions, and is preferably alkyltrimethylammonium salt, dialkyldimethylammonium salt, benzyl quaternary ammonium salt, imidazole quaternary ammonium salt, pyridine quaternary ammonium salt, or the like. In some embodiments, the cationic surfactant is selected from at least one of octadecyl trimethyl ammonium chloride, dodecyl dimethyl benzyl ammonium chloride, and didodecyl dimethyl ammonium chloride.
The nonionic surfactant can be selected from nonionic Gemini surfactants and nonionic polymer surfactants. As an embodiment, the nonionic surfactant includes: at least one of a polyoxyethylene-type surfactant and/or a fatty acid polyol ester. Among them, polyoxyethylene type surfactants include, but are not limited to, fatty alcohol polyoxyethylene ethers, polyoxyethylene alkylphenol ethers, polyoxyethylene fatty acid esters, polyoxyethylene alkylamines, alkanolamide polyoxyethylene, polyoxyethylene alkylamides, and the like. Fatty acid polyol esters include, but are not limited to, fatty acid glycerides, pentaerythritol esters, fatty acid sorbitol esters, fatty acid polyoxyethylene sorbitan esters, glycolipids, alkyl glycosides, block polyethers, and the like. In some embodiments, the nonionic surfactant is selected from at least one of fatty alcohol polyoxyethylene ethers, polyoxyethylene alkylphenol ethers, and sorbitan fatty acid esters.
In step S02, the metal precursor, the sulfur precursor, the cationic surfactant, and the nonionic surfactant are heated in an organic solvent to prepare a metal sulfide precursor, thereby obtaining a metal sulfide precursor solution.
As an embodiment, the heating process includes: heating at 60-80 deg.C for 2-4 hr. Under the reaction condition, the reaction activity between the metal precursor and the sulfur precursor can be improved, the synthesis of the metal sulfide precursor is promoted, and meanwhile, the surfactant can be favorably adsorbed on the surface of the synthesized metal sulfide precursor.
As one embodiment, as shown in fig. 2, the step of heat-treating the metal precursor, the sulfur precursor, the cationic surfactant, and the nonionic surfactant in an organic solvent includes:
s021, dissolving the metal precursor and the sulfur precursor in the organic solvent, and performing first heating treatment to obtain a first solution in which metal sulfide precursor crystal nuclei are dispersed;
s022, dispersing the cationic surfactant and the nonionic surfactant in the first solution, and further performing second heating treatment to obtain the metal sulfide precursor solution.
By preparing the metal sulfide precursor crystal nucleus and adding the cationic surfactant and the nonionic surfactant into the first solution in which the metal sulfide precursor crystal nucleus is dispersed, the metal precursor and the sulfur precursor are fully reacted, the yield of the metal sulfide nanoparticles is improved, and the metal sulfide nanoparticles with small particle size and uniform size distribution are synthesized with high yield.
In step S021, the metal precursor and the sulfur precursor are dissolved in the organic solvent, and a first heating treatment is performed to obtain a first solution in which metal sulfide precursor nuclei are dispersed.
The step of dissolving the metal precursor and the sulfur precursor in the organic solvent may refer to a conventional procedure in the art. In order to accelerate the dissolution of the metal precursor and the sulfur precursor in the organic solvent, ultrasonic and/or mechanical stirring methods and the like may be employed.
In some embodiments, the molar ratio of sulfur atoms of the sulfur precursor to metal atoms of the metal precursor is (1-1.5):1, promoting adequate synthesis of metal sulfide nanoparticles while avoiding the introduction of excessive sulfur or metal impurities. In a further embodiment, the concentration of the metal precursor in the organic solvent is 0.2-1mol/L, so that the metal precursor and the sulfur precursor have good reaction activity, the synthesis of metal sulfide nanoparticles is promoted, and the synthesis efficiency is improved.
In some embodiments, the first heating process comprises: heating at 60-80 deg.C for 2-4 hr. Under the reaction condition, the reaction activity between the metal precursor and the sulfur precursor can be improved, the synthesis of metal sulfide nano-particles is promoted, and the yield is improved.
In step S022, the cationic surfactant and the nonionic surfactant are dispersed in the first solution, and then subjected to a second heat treatment to obtain the metal sulfide precursor solution.
And in the second heating treatment process, the unreacted metal precursor and the sulfur precursor in the reaction system continue to react to synthesize a metal sulfide precursor crystal nucleus, meanwhile, the added cationic surfactant and the nonionic surfactant are combined with the metal sulfide precursor crystal nucleus in the reaction system, and the size and the shape of the metal sulfide nano-particles prepared subsequently are controlled by modifying the particle surface.
Dispersing newly synthesized metal sulfide precursor crystal nuclei in the first solution, wherein the metal sulfide precursor crystal nuclei are negatively charged in the solution, and dispersing a cationic surfactant and a nonionic surfactant in the first solution, wherein on one hand, the cationic surfactant is ionized to form cations, and tends to approach negatively charged metal sulfide precursor particles to form double-electric-layer micelle particles, so that the distance between the particles is increased; meanwhile, the polar head of the nonionic surfactant is coordinated and combined with the metal atoms of the metal sulfide nanoparticles and fixed on the surfaces of the metal sulfide nanoparticles, the nonpolar head of the nonionic surfactant is fully extended in the solution to form a potential barrier layer, and the particles are further prevented from approaching each other, so that hard agglomeration among metal sulfide precursor particles is avoided, and overlarge particle size caused by hard agglomeration among the metal sulfide precursor particles is avoided; on the other hand, the cationic surfactant and the nonionic surfactant can form mixed micelles in a reaction system, and molecules of the nonionic surfactant are inserted between surface active ions of the anionic surfactant, so that the electric repulsion between the 'cationic heads' of the original double-electric-layer micelle particles is weakened, the surface activity of the solution is improved, the reaction system tends to be stable, the collision chance among particles is further reduced, the uneven growth of metal sulfide precursor particles is inhibited, the morphology and the size of the particles are effectively improved, and the metal sulfide nano particles with small size and uniform size distribution are prepared.
In one embodiment, the molar ratio of the sum of the cationic surfactant and the nonionic surfactant to the metal atom of the metal precursor is (2-3): 1. The metal sulfide precursor particles synthesized in the molar ratio range have small and uniform sizes and highest yield. When the molar ratio of the surfactant to the metal atoms is less than 2:1, the surfactant cannot effectively regulate and control the size of metal sulfide precursor particles in the system; when the molar ratio of the surfactant to the metal atom is more than 3:1, the yield of the metal sulfide precursor particles is low, and surfactant residue is easily caused, thereby affecting the electrical properties of the composite material. In some embodiments, the molar ratio of the cationic surfactant to the nonionic surfactant is (1.5-2): 1. The cationic surfactant and the nonionic surfactant in the molar ratio range have excellent compatibility with metal sulfide precursor crystal nuclei synthesized in a system, and are favorable for obtaining metal sulfide nanoparticles with small and uniform particle sizes.
In some embodiments, the step of dispersing the cationic surfactant and the nonionic surfactant in the first solution comprises:
s0221, preparing a second solution in which a cationic surfactant and a nonionic surfactant are dissolved;
s0222, dispersing the second solution into the first solution in a dropwise manner.
The second solution is dispersed in the first solution by a dropwise adding method, so that the speed of the surfactant adsorbed on the surface of the metal sulfide precursor particles is controlled to a certain extent, the surfactant is promoted to be combined with the metal sulfide precursor particles while the metal sulfide precursor crystal nuclei in the reaction system are continuously synthesized, the yield of the metal sulfide nanoparticles is improved, the particle agglomeration is effectively prevented, and the stable metal sulfide nanoparticle sol is obtained.
The conditions of the second heating treatment are the same as or different from those of the first heating treatment, and can be flexibly adjusted according to the actual conditions of the product. As an embodiment, the second heating process includes: heating at 60-80 deg.C for 2-4 hr. Under the heating condition, the surfactant has good activity, and is favorable for adsorbing the surfactant on the surface of the synthesized metal sulfide precursor, so that the surface modification of the metal sulfide precursor is realized.
The organic solvent is a reaction medium, in the embodiment of the invention, the organic solvent is preferably a polar solvent or a medium polar solvent, on one hand, the solubility of the cationic surfactant in the solvent can be improved, and the ionization can be promoted to form cations; on the other hand, the synthesized metal sulfide precursor particles have electronegativity in a polar solvent, so that the combination of the cationic surfactant and the metal sulfide precursor particles is promoted, and the modification effect is improved.
The organic solvent is preferably alcohol with 4-18 carbon atoms and/or derivatives of the alcohol, and the organic solvent has good compatibility with metal precursors, sulfur precursors, surfactants and synthesized metal sulfide precursor particles, and can improve the dispersibility of the synthesized metal sulfide precursor particles in a system, so that the system tends to be stable, thereby inhibiting the uneven growth of the metal sulfide precursor particles and improving the morphology and size of the particles.
In the present specification, "derivatives of alcohols" refer to derivatives formed by reacting alcohols and other compounds, such as alcohols, ethers, esters, etc., and the hydrocarbon molecular weight of alcohols and derivatives thereof may be a saturated molecular chain or an unsaturated molecular chain.
As an embodiment, the boiling point of the organic solvent is 50-250 ℃ to ensure that the organic solvent can be completely removed in the subsequent solid-liquid separation process, and the organic solvent is prevented from remaining in the prepared composite material and even influencing the electrical properties of the film layer.
As an embodiment, the organic solvent has a surface tension of 25 to 50mN/m at 20 to 35 degrees Celsius and a viscosity of 2 to 10 centipoise (the unit may be expressed as: cP). Under the surface tension range and the viscosity range, the reaction system has excellent stability, and the metal sulfide nano-particles with small particle size and uniform distribution are promoted to be formed.
In some embodiments, the organic solvent is selected from at least one of methanol, ethanol, propanol, glycerol, n-butanol, n-pentanol, ethylene glycol methyl ether, and ethylene glycol methyl ether acetate.
In step S03, the metal sulfide precursor solution is subjected to solid-liquid separation to obtain a composite material.
As an embodiment, the step of subjecting the metal sulfide precursor solution to solid-liquid separation comprises: and annealing the metal sulfide precursor solution at the temperature of 200-250 ℃. By carrying out annealing treatment at the temperature of 200-250 ℃, the metal sulfide nano-particles can have excellent crystallinity while completely removing the solvent, thereby being beneficial to improving the electrical property of the composite material.
In summary, the composite material prepared by the preparation method is modified metal sulfide nano-particles, the surface of the modified metal sulfide nano-particles is modified with a cationic surfactant and a nonionic surfactant, the particle size is small, the distribution is uniform, the crystallinity is high, and when the modified metal sulfide nano-particles are applied to the preparation of a current carrier transmission layer of a light-emitting diode, the film quality of the current carrier transmission layer is favorably improved, so that the light-emitting performance of a QLED device is improved.
Based on the technical scheme, the embodiment of the invention also provides the composite material, the light-emitting diode and the preparation method thereof.
Correspondingly, the composite material is prepared by the preparation method and comprises the following steps: the metal sulfide nano-particle comprises a metal sulfide nano-particle and a surfactant bound on the surface of the metal sulfide nano-particle, wherein the surfactant is a cationic surfactant and a nonionic surfactant.
The composite material provided by the embodiment of the invention is prepared by the preparation method, is metal sulfide nano-particles with the surface modified with the surfactant, has small particle size and uniform size distribution, is favorable for forming a uniform and compact film layer, and improves the luminous performance of a QLED device.
Wherein the cationic surfactant and the nonionic surfactant are substantially the same as those described above, it is understood that they have the same properties and effects as those described above.
In embodiments of the present invention, metal sulfide nanoparticles include, but are not limited to, zinc sulfide, indium sulfide, and the like. In some embodiments, the metal sulfide nanoparticles are selected to be zinc sulfide. In some embodiments, the metal sulfide nanoparticles have a particle size of 5 to 10 nanometers.
As an embodiment, the molar ratio of the sum of the cationic surfactant and the nonionic surfactant to the metal sulfide nanoparticles is (2-3): 1.
In one embodiment, the molar ratio of the cationic surfactant to the nonionic surfactant is (1.5-2): 1.
The composite material is a metal sulfide nanoparticle and a surfactant bound to the surface of the metal sulfide nanoparticle, wherein the surfactant is a cationic surfactant and a nonionic surfactant, the molar ratio of the surfactant to the metal sulfide nanoparticle is (2-3):1, and the molar ratio of the cationic surfactant to the nonionic surfactant is (1.5-2): 1.
Correspondingly, the light-emitting diode comprises a carrier transport layer, wherein the material of the carrier transport layer comprises: the composite material prepared by the preparation method or the composite material.
According to the light-emitting diode provided by the embodiment of the invention, the material of the carrier transmission layer is the composite material prepared by the preparation method or the composite material, and the composite material has the advantages of small particle size and uniform size distribution, so that the carrier transmission layer is uniform and compact, the film layer has excellent quality, and the light-emitting diode has good light-emitting performance.
In the embodiment of the present invention, the carrier transport layer is an electron transport layer or a hole transport layer, which is specifically referred to the kind of the light emitting diode to be manufactured.
The light-emitting diode mainly comprises an anode, a light-emitting layer, a carrier transport layer and a cathode, and the specific structure can refer to the conventional technology in the field. In some embodiments, the light emitting diode is a positive type structure, and the anode is connected with the substrate as a bottom electrode. In some embodiments, the light emitting diode is an inverted structure, and the cathode is connected to the substrate as a bottom electrode.
In some embodiments, the carrier transport layer is an electron transport layer comprising a composite material made from the metal sulfide nanoparticles described above.
The materials of the cathode, the anode and the light emitting layer can refer to the conventional techniques in the art, and the embodiment of the present invention is not limited thereto. In some embodiments, the material of the light emitting layer is quantum dots, and the quantum dots comprise at least one of group IV quantum dots, group II-VI quantum dots, group II-V quantum dots, group III-VI quantum dots, group IV-VI quantum dots, group I-III-VI quantum dots, group II-IV-VI quantum dots, and group II-IV-V quantum dots, have quantum dot characteristics, and have high light emitting efficiency. The quantum dots include, but are not limited to, binary phase, ternary phase, quaternary phase quantum dots, and the like, and may be selected from blue quantum dots, green quantum dots, red quantum dots, or yellow quantum dots, and may be specifically based on the requirements of an actual QLED device. In some embodiments, the quantum dots are selected as binary phase quantum dots, preferably at least one of CdS, CdSe, CdTe, InP, AgS, PbS, PbSe, and HgS. In some embodiments, the quantum dots are selected to be ternary phase quantum dots, preferably ZnXCd1-XS、CuXIn1-XS、ZnXCd1-XSe、ZnXSe1-XS、ZnXCd1-XTe and PbSeXS1-XAt least one of (1). In some embodiments, the quantum dots are selected to be quaternary phase quantum dots, preferably ZnXCd1-XS/ZnSe、CuXIn1-XS/ZnS、ZnXCd1-XTe/ZnS、PbSeXS1-X/ZnS、ZnXCd1-XAt least one of Se/ZnS and CuInSeS.
Furthermore, the light emitting diode includes a carrier function layer such as a carrier injection layer and a carrier blocking layer in addition to the function film layers such as the cathode, the anode, the light emitting layer, and the carrier transport layer.
In one embodiment, as shown in fig. 3, the light emitting diode is a front-mount light emitting diode, and includes a substrate 1, an anode 2, a hole transport layer 3, a light emitting layer 4, an electron transport layer 5, and a cathode 6, which are sequentially disposed. Wherein, the substrate 1 is made of glass sheet, the anode 2 is made of ITO matrix, the hole transport layer 3 is made of TFB, and the luminescent layer 4 is made of blue CdXZn1-XThe S/ZnS quantum dots and the electron transport layer 5 are made of modified zinc sulfide prepared by the preparation method provided by the embodiment of the invention, and the cathode 6 is made of Al.
Correspondingly, the preparation method of the light-emitting diode is characterized by comprising the following steps of preparing a carrier transmission layer:
s01', providing a composite material, wherein the composite material is prepared by the preparation method or the composite material
S02', providing a substrate, and depositing the composite material on the substrate to obtain the carrier transport layer.
According to the preparation method of the light-emitting diode provided by the embodiment of the invention, the carrier transmission layer is prepared by adopting the composite material, so that the carrier transmission layer is uniform and compact, the quality of the film layer is excellent, and the light-emitting performance of the light-emitting diode is improved.
The composite material in step S01' is the same as the composite material described above, and should have the same properties and functions, and the details of the embodiment of the present invention are not repeated here.
In step S02', the substrate serves as a carrier for depositing the composite material, and the structure thereof can be determined according to the conventional techniques in the art, and the suitable substrate can be selected according to the actual preparation process of the carrier transport layer and the type of the light emitting diode. In some embodiments, the light emitting diode is a positive type light emitting diode, the anode is a bottom electrode, the substrate includes an anode, and when the carrier transport layer formed by deposition is an electron transport layer, a light emitting layer is further formed on the anode. It is understood that functional film layers such as a hole blocking layer, a hole injection layer, a hole transport layer, etc. may be further disposed between the anode and the light emitting layer.
In one embodiment, the substrate has a light emitting layer formed thereon, and the step of depositing the composite material on the substrate includes: depositing the composite material on the light emitting layer; or
As an embodiment, the substrate comprises a first electrode, and the step of depositing the composite material on the substrate comprises: depositing the composite material on the first electrode.
The deposition method can refer to the conventional technology in the field, for example, the inkjet printing, the magnetron sputtering method and the like are adopted, so that the composite material is deposited on the substrate and forms a uniform film layer.
In order that the details of the above-described implementation and operation of the present invention will be clearly understood by those skilled in the art, and the advanced performance of the composite material, the method of manufacturing the same, the light emitting diode and the method of manufacturing the same according to the embodiments of the present invention will be apparent, the implementation of the present invention will be illustrated by the following examples.
Example 1
The preparation method of the composite material film comprises the following steps:
adding 50mL of ethanol into zinc chloride, and stirring and dissolving at 70 ℃ to form a zinc chloride solution with the total concentration of 0.5M; dissolving sodium sulfide in 10mL of ethanol, and stirring for dissolving to form a sodium sulfide solution; adding a proper amount of sodium sulfide solution into zinc chloride solution, and stirring for 4h at 70 ℃ to form zinc sulfide crystal nucleus solution (molar ratio, S)2-：Zn2+＝1.2：1)。
Dissolving octadecyl trimethyl ammonium chloride and fatty alcohol-polyoxyethylene ether in ethanol to form a surfactant solution (molar ratio, octadecyl trimethyl ammonium chloride: fatty alcohol-polyoxyethylene ether is 2: 1);
dripping surfactant solution into zinc sulfide crystal nucleus solution, and stirring at 70 deg.C for 1 hr to obtain composite material dispersed solution (molar ratio, surfactant: Zn)2+＝2:1)；
And after the solution is cooled, spin-coating the treated ITO by using a spin coater and annealing at 200 ℃ to obtain the composite material film.
Example 2
The preparation method of the composite material film comprises the following steps:
adding zinc nitrate into 50mL of propanol, and stirring at 80 ℃ until the zinc nitrate is dissolved to form a zinc nitrate solution with the total concentration of 0.5M; dissolving potassium sulfide in 10mL of propanol, and stirring for dissolving to form a potassium sulfide solution; adding a proper amount of potassium sulfide solution into zinc nitrate solution, and stirring for 4 hours at 80 ℃ to form zinc sulfide crystal nucleus solution (molar ratio, S)2-：Zn2+＝1.5：1)。
Dissolving dodecyl dimethyl benzyl ammonium chloride and polyoxyethylene alkylphenol ether in ethanol to form a surfactant solution (the molar ratio of dodecyl dimethyl benzyl ammonium chloride to alkylphenol polyoxyethylene ether is 1.5: 1);
dripping surfactant solution into zinc sulfide crystal nucleus solution, and stirring at 70 deg.C for 1 hr to obtain composite material dispersed solution (molar ratio, surfactant: Zn)2+＝2.5:1)；
And after the solution is cooled, spin-coating the treated ITO by using a spin coater and annealing at 250 ℃ to obtain the composite material film.
Example 3
The preparation method of the composite material film comprises the following steps:
adding indium sulfate into 50mL of methanol, and stirring at 60 ℃ until the indium sulfate is dissolved to form an indium sulfate solution with the total concentration of 0.5M; dissolving thiourea in 10mL of methanol, and stirring for dissolving to form a thiourea solution; adding a proper amount of thiourea solution into the indium sulfate solution, and stirring for 4 hours at 60 ℃ to form an indium sulfide crystal nucleus solution (molar ratio, S)2-：In3+＝3：2)。
Dissolving didodecyldimethylammonium chloride and sorbitan fatty acid ester in ethanol to form a surfactant solution (molar ratio, didodecyldimethylammonium chloride and sorbitan fatty acid ester is 1.8: 1);
in a solution of indium sulfide nucleiDropwise adding surfactant solution, and stirring at 70 deg.C for 1 hr to obtain solution dispersed with composite material (molar ratio, surfactant: In)3+＝3:1)；
And after the solution is cooled, spin-coating the treated ITO by using a spin coater and annealing at 250 ℃ to obtain the composite material film.
Example 4
The embodiment prepares the light emitting diode, and specifically comprises the following steps:
preparing an ITO anode on a glass substrate;
preparing a TFB hole transport layer on the ITO anode;
preparation of blue Cd on TFB hole transport layerXZn1-XAn S/ZnS quantum dot light emitting layer;
spin-coating the solution prepared in step (1) of example 1 on a quantum dot light-emitting layer, and annealing at 250 ℃ to prepare an electron transport layer;
and preparing an Al cathode on the electron transport layer.
Example 5
This example prepared a light emitting diode which differed from example 4 in that: spin-coating the solution prepared in step (1) of example 2 on a quantum dot light-emitting layer, and annealing at 250 ℃ to prepare an electron transport layer;
the same parts as those in embodiment 4 are basically the same, and are not described herein again.
Example 6
This example prepared a light emitting diode which differed from example 4 in that: spin-coating the solution prepared in step (1) of example 3 on a quantum dot light-emitting layer, and annealing at 250 ℃ to prepare an electron transport layer;
the same parts as those in embodiment 4 are basically the same, and are not described herein again.
Example 7
The embodiment prepares the light emitting diode, and specifically comprises the following steps:
preparing an ITO cathode on a glass substrate;
spin-coating the solution prepared in step (1) of example 1 on an ITO cathode, and annealing at 250 ℃ to prepare an electron transport layer;
preparing a quantum dot light-emitting layer on the electron transport layer;
preparing a TFB hole transport layer on the quantum dot light emitting layer;
an Al anode was prepared on the TFB hole transport layer.
Example 8
This example prepared a light emitting diode which differed from example 7 in that: spin-coating the solution prepared in step (1) of example 2 on an ITO cathode, annealing at 250 ℃ to prepare an electron transport layer;
the same points as those in embodiment 7 are basically the same, and the description thereof is omitted here.
Example 9
This example prepared a light emitting diode which differed from example 7 in that: spin-coating the solution prepared in step (1) of example 3 on an ITO cathode, annealing at 250 ℃ to prepare an electron transport layer;
the same points as those in embodiment 7 are basically the same, and the description thereof is omitted here.
Comparative example 1
This comparative example prepared a light emitting diode which differed from example 4 in that: spin-coating commercial ZnS nanoparticle ethanol dispersion on the quantum dot light-emitting layer, and annealing at 250 ℃ to prepare an electron transport layer;
the same parts as those in embodiment 4 are basically the same, and are not described herein again.
Comparative example 2
This comparative example prepared a light emitting diode which differed from example 6 in that: spin coating commercial In over quantum dot light emitting layer2S3Annealing the nano-particle ethanol dispersion liquid at 250 ℃ to prepare an electron transport layer;
the same points as those in embodiment 6 are basically the same, and are not described herein.
The composite material films prepared in examples 1 to 3, the electron transport layer films in comparative examples 1 and 2, and the quantum dot light emitting diodes prepared in examples 4 to 9 and comparative examples 1 and 2 were subjected to performance tests, and the test indexes and the test methods were as follows:
(1) electron mobility: testing the current density (J) -voltage (V) of the quantum dot light-emitting diode, drawing a curve relation diagram, fitting a Space Charge Limited Current (SCLC) region in the relation diagram, and then calculating the electron mobility according to a well-known Child's law formula:
J＝(9/8)εrε0μeV2/d3；
wherein J represents current density in mAcm-2；εrDenotes the relative dielectric constant,. epsilon0Represents the vacuum dielectric constant; mu.seDenotes the electron mobility in cm2V-1s-1(ii) a V represents the drive voltage, in units of V; d represents the film thickness in m.
(2) Resistivity: the resistivity of the electron transport film is measured by the same resistivity measuring instrument.
(3) External Quantum Efficiency (EQE): measured using an EQE optical test instrument.
Note: the electron mobility and resistivity were tested as single layer thin film structure devices, namely: cathode/electron transport film/anode. The external quantum efficiency test is the QLED device, namely: anode/hole transport film/quantum dot/electron transport film/cathode, or cathode/electron transport film/quantum dot/hole transport film/anode.
Table 1 shows the results of the tests, as shown in the results:
TABLE 1
Figure BDA0002351344340000171
As can be seen from table 1 above, the composite materials of the composite material films prepared in examples 1 to 3 of the present invention are zinc sulfide nanoparticles surface-modified with cationic surfactant and nonionic surfactant, and the resistivity is significantly lower than that of the electron transport films of comparative examples 1 and 2, and the electron mobility is significantly higher than that of comparative examples 1 and 2.
The electron transport layers in the quantum dot light-emitting diodes provided in examples 4 to 9 of the present invention are all made of the composite materials prepared in examples 1 to 3, and the external quantum efficiency of the quantum dot light-emitting diodes of examples 4 to 9 is significantly higher than that of comparative examples 1 and 2, which shows that the light-emitting efficiency of the quantum dot light-emitting diodes can be significantly improved by the technical scheme provided in the examples of the present invention.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (13)

1. The preparation method of the composite material is characterized by comprising the following steps:
providing a metal precursor, a sulfur precursor, a cationic surfactant and a nonionic surfactant;
heating the metal precursor, the sulfur precursor, the cationic surfactant and the nonionic surfactant in an organic solvent to obtain a metal sulfide precursor solution;
and carrying out solid-liquid separation on the metal sulfide precursor solution to obtain the composite material.
2. The production method according to claim 1, wherein the step of subjecting the metal precursor, the sulfur precursor, the cationic surfactant, and the nonionic surfactant to a heat treatment in an organic solvent comprises:
dissolving the metal precursor and the sulfur precursor in the organic solvent, and carrying out first heating treatment to obtain a first solution dispersed with metal sulfide precursor crystal nuclei;
and dispersing the cationic surfactant and the nonionic surfactant in the first solution, and carrying out second heating treatment to obtain the metal sulfide precursor solution.
3. The method according to claim 1 or 2, wherein the cationic surfactant comprises: an amine salt type surfactant and/or a quaternary ammonium salt type surfactant; and/or
The nonionic surfactant includes: polyoxyethylene type surfactants and/or fatty acid polyol esters.
4. The production method according to claim 1 or 2, characterized in that the cationic surfactant is selected from at least one of octadecyl trimethyl ammonium chloride, dodecyl dimethyl benzyl ammonium chloride, and didodecyl dimethyl ammonium chloride; and/or
The nonionic surfactant is at least one selected from fatty alcohol-polyoxyethylene ether, polyoxyethylene alkylphenol ether and sorbitan fatty acid ester.
5. The production method according to claim 1 or 2, wherein the heating treatment includes: heating at 60-80 deg.c for 2-4 hr; and/or
The step of performing solid-liquid separation on the metal sulfide precursor solution comprises the following steps: and annealing the metal sulfide precursor solution at the temperature of 200-250 ℃.
6. The production method according to claim 1 or 2, characterized in that the metal precursor is selected from at least one of soluble organic zinc salt, soluble inorganic zinc salt, soluble organic indium salt, soluble inorganic indium salt; and/or the presence of a gas in the gas,
the sulfur precursor is selected from at least one of sodium sulfide, potassium sulfide, thiourea and amine sulfide; and/or the presence of a gas in the gas,
the organic solvent is at least one selected from methanol, ethanol, propanol, glycerol, n-butanol, n-pentanol, ethylene glycol methyl ether and ethylene glycol methyl ether acetate.
7. The production method according to claim 1 or 2, characterized in that, in the step of subjecting the metal precursor, the sulfur precursor, the cationic surfactant, and the nonionic surfactant to a heating treatment in an organic solvent, the molar ratio of the sum of the cationic surfactant and the nonionic surfactant to the metal atom of the metal precursor is (2-3: 1; and/or
And a step of subjecting the metal precursor, the sulfur precursor, the cationic surfactant and the nonionic surfactant to a heat treatment in an organic solvent, wherein the molar ratio of the cationic surfactant to the nonionic surfactant is (1.5-2): 1.
8. The production method according to claim 1 or 2, characterized in that, in the step of subjecting the metal precursor, the sulfur precursor, the cationic surfactant, and the nonionic surfactant to a heating treatment in an organic solvent, the molar ratio of the sulfur atom of the sulfur precursor to the metal atom of the metal precursor is (1-1.5): 1; and/or
And heating the metal precursor, the sulfur precursor, the cationic surfactant and the nonionic surfactant in an organic solvent, wherein the concentration of the metal precursor in the organic solvent is 0.2-1 mol/L.
9. A composite material, comprising: the metal sulfide nano-particle comprises a metal sulfide nano-particle and a surfactant bound on the surface of the metal sulfide nano-particle, wherein the surfactant is a cationic surfactant and a nonionic surfactant.
10. The composite material of claim 9, wherein the molar ratio of the sum of the cationic surfactant and the nonionic surfactant to the metal sulfide nanoparticles is (2-3): 1; and/or
The molar ratio of the cationic surfactant to the nonionic surfactant is (1.5-2): 1.
11. The composite material according to claim 9 or 10, wherein the composite material is a metal sulfide nanoparticle and a surfactant bonded to the surface of the metal sulfide nanoparticle, the surfactant is a cationic surfactant and a nonionic surfactant, the molar ratio of the surfactant to the metal sulfide nanoparticle is (2-3):1, and the molar ratio of the cationic surfactant to the nonionic surfactant is (1.5-2): 1.
12. A light emitting diode comprising a carrier transport layer, wherein the material of the carrier transport layer comprises: a composite material produced by the production method described in any one of claims 1 to 8, or a composite material described in any one of claims 9 to 11.
13. A preparation method of a light-emitting diode is characterized by comprising the following steps of preparing a carrier transport layer:
providing a composite material comprising: a composite material produced by the production method according to any one of claims 1 to 8 or the composite material according to any one of claims 9 to 11;
providing a substrate, and depositing the composite material on the substrate to obtain the carrier transport layer.
CN201911416603.9A 2019-12-31 2019-12-31 Composite material and preparation method thereof, light-emitting diode and preparation method Pending CN113120953A (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10105687B1 (en) * 2017-08-24 2018-10-23 Imam Abdulrahman Bin Faisal University Heterostructured Bi2S3—ZnS photocatalysts and methods thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10105687B1 (en) * 2017-08-24 2018-10-23 Imam Abdulrahman Bin Faisal University Heterostructured Bi2S3—ZnS photocatalysts and methods thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
MOHSEN MOHSENNIA ET AL.: ""Low driving voltage in polymer light emitting diodes with CdS nanoparticles as an electron transport layer"", 《JOURNAL OF NANOPHOTONICS》 *

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