CN113130792A - 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 PDFInfo
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- CN113130792A CN113130792A CN201911423155.5A CN201911423155A CN113130792A CN 113130792 A CN113130792 A CN 113130792A CN 201911423155 A CN201911423155 A CN 201911423155A CN 113130792 A CN113130792 A CN 113130792A
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- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
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- 150000003608 titanium Chemical class 0.000 description 2
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 description 2
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- YBNMDCCMCLUHBL-UHFFFAOYSA-N (2,5-dioxopyrrolidin-1-yl) 4-pyren-1-ylbutanoate Chemical compound C=1C=C(C2=C34)C=CC3=CC=CC4=CC=C2C=1CCCC(=O)ON1C(=O)CCC1=O YBNMDCCMCLUHBL-UHFFFAOYSA-N 0.000 description 1
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- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
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- 230000003287 optical effect Effects 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical class OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
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- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 description 1
- GPWILPBSXYXSMN-UHFFFAOYSA-J propane-1-sulfonate;tin(4+) Chemical compound [Sn+4].CCCS([O-])(=O)=O.CCCS([O-])(=O)=O.CCCS([O-])(=O)=O.CCCS([O-])(=O)=O GPWILPBSXYXSMN-UHFFFAOYSA-J 0.000 description 1
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- 229910052708 sodium Inorganic materials 0.000 description 1
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- TXBCHPGETQLSGV-UHFFFAOYSA-M sodium;2-(dodecylamino)propanoate Chemical compound [Na+].CCCCCCCCCCCCNC(C)C([O-])=O TXBCHPGETQLSGV-UHFFFAOYSA-M 0.000 description 1
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
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- FAKFSJNVVCGEEI-UHFFFAOYSA-J tin(4+);disulfate Chemical compound [Sn+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FAKFSJNVVCGEEI-UHFFFAOYSA-J 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- YQMWDQQWGKVOSQ-UHFFFAOYSA-N trinitrooxystannyl nitrate Chemical compound [Sn+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YQMWDQQWGKVOSQ-UHFFFAOYSA-N 0.000 description 1
- BJDDAXVXMQYXHL-UHFFFAOYSA-J tris(ethylsulfonyloxy)stannyl ethanesulfonate Chemical compound [Sn+4].CCS([O-])(=O)=O.CCS([O-])(=O)=O.CCS([O-])(=O)=O.CCS([O-])(=O)=O BJDDAXVXMQYXHL-UHFFFAOYSA-J 0.000 description 1
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Images
Classifications
-
- 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
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
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- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Electroluminescent Light Sources (AREA)
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 cation precursor, an anion precursor, a zwitterionic surfactant and a nonionic surfactant; heating a cation precursor, an anion precursor, a zwitterionic surfactant and a nonionic surfactant in an organic solvent to obtain a metal compound precursor solution; and carrying out solid-liquid separation on the metal compound precursor solution to obtain the composite material. The metal compound nano-particles prepared by the preparation method are modified with the zwitterionic surfactant and the nonionic surfactant on the surface, have small particle size and uniform size distribution, are beneficial to forming uniform and compact film layers, and improve the luminous performance of a QLED device.
Description
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 compound 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 compound 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 compound 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 cation precursor, an anion precursor, a zwitterionic surfactant and a nonionic surfactant;
heating the cation precursor, the anion precursor, the zwitterionic surfactant and the nonionic surfactant in an organic solvent to obtain a metal compound precursor solution;
and carrying out solid-liquid separation on the metal compound precursor solution to obtain the composite material.
According to the preparation method of the composite material, the zwitterionic surfactant and the nonionic surfactant are added into a reaction system of metal compound nano particles, so that newly generated metal compound precursor particles can be combined with the zwitterionic surfactant and the nonionic surfactant in time, and on one hand, the zwitterionic surfactant and the nonionic surfactant after being combined with the metal compound precursor particles have a steric hindrance effect, so that the particles are prevented from approaching each other, and the phenomenon that the particle size is overlarge due to hard agglomeration among the metal compound precursor particles is avoided; on the other hand, the amphoteric ion surfactant and the nonionic surfactant can form mixed micelles in a reaction system, and molecules of the nonionic surfactant are inserted into surface active ions of the anionic surfactant, so that the electric repulsion between the cation 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 compound precursor particles is inhibited, the morphology size of the particles is effectively improved, and the metal compound nano-particles with small size and uniform size distribution are prepared. Therefore, the metal compound nano-particles prepared by the preparation method are modified with the amphoteric ion surfactant and the nonionic surfactant on the surfaces, have small particle sizes and uniform size distribution, are beneficial to forming uniform and compact film layers, 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 surfactant is a zwitterionic surfactant and a nonionic surfactant.
The composite material provided by the invention is prepared by the preparation method, is metal compound nanoparticles 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 cation precursor, an anion precursor, a zwitterionic surfactant and a nonionic surfactant;
s02, heating the cation precursor, the anion precursor, the zwitterionic surfactant and the nonionic surfactant in an organic solvent to obtain a metal compound precursor solution;
and S03, carrying out solid-liquid separation on the metal compound precursor solution to obtain the composite material.
According to the preparation method of the composite material provided by the embodiment of the invention, the zwitterionic surfactant and the nonionic surfactant are added into a reaction system of the metal compound nanoparticles, so that newly generated metal compound precursor particles can be combined with the zwitterionic surfactant and the nonionic surfactant in time; on the other hand, the amphoteric ion surfactant and the nonionic surfactant can form mixed micelles in a reaction system, and molecules of the nonionic surfactant are inserted into surface active ions of the anionic surfactant, so that the electric repulsion between the cation 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 compound precursor particles is inhibited, the morphology size of the particles is effectively improved, and the metal compound nano-particles with small size and uniform size distribution are prepared. Therefore, the metal compound nano-particles prepared by the preparation method provided by the embodiment of the invention are modified with the zwitterionic 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 cation precursor and an anion precursor are used as raw materials for synthesizing the metal compound nanoparticles, the cation precursor is used for providing cations, and the anion precursor is used for providing anions.
The cation precursor is selected from organic or inorganic substances that can provide cations through a reaction, and as one embodiment, the cation precursor is selected from soluble organic metal salts and/or soluble inorganic metal salts, so that the cation precursor can be sufficiently dissolved in an organic solvent to improve the yield of the metal compound nanoparticles. In some embodiments, the cationic precursor is selected from cationic precursor salts corresponding to metal compounds that can act as electron transport materials. In some embodiments, the cationic precursor is selected from at least one of a zinc salt, a titanium salt, a tin salt, and a zirconium salt. In a further embodiment, the zinc salt is selected from at least one of zinc acetate, zinc nitrate, zinc chloride, zinc acetate dihydrate. In a further embodiment, the titanium salt is selected from at least one of titanium nitrate, titanium chloride, titanium sulfate, titanium bromide. In some embodiments, the tin salt is selected from at least one of tin nitrate, tin chloride, tin sulfate, tin methane sulfonate, tin ethane sulfonate, tin propane sulfonate.
The anion precursor is selected from organic or inorganic substances that can provide anions by reaction, and as an embodiment, the anion precursor is selected from at least one of a sulfur source, an organic base, and an inorganic base. In some embodiments, the anion precursor is selected from at least one of sodium sulfide, potassium sulfide, thiourea and amine sulfide, and the anion precursors can be completely dissolved in the organic solvent, have good reactivity with the cation precursor, and can greatly improve the yield of the metal sulfide nanoparticles. In some embodiments, the anionic precursor is selected from organic and/or inorganic bases including, but not limited to, ammonia, potassium hydroxide, sodium hydroxide, lithium hydroxide, ethanolamine, ethylene glycol, diethanolamine, triethanolamine, ethylenediamine, and the like, and these base sources can form metal oxide nanoparticles by reaction with the cationic precursor described above.
In step S01, a zwitterionic surfactant and a nonionic surfactant are used as surface modification raw materials of the metal compound nanoparticles.
The zwitterionic surfactant can be selected from Gemini surfactants and macromolecular surfactants. As an embodiment, the zwitterionic surfactant includes: at least one of a betaine type surfactant, an imidazoline type surfactant, an amine oxide type surfactant, and an amino acid type surfactant. Among them, the betaine type surfactant includes, but is not limited to, alkyl dimethyl sulfoethyl betaine, alkyl dimethyl sulfopropyl betaine, dodecyl ethoxy sulfobetaine, tetradecylamidopropyl hydroxypropyl sulfobetaine, etc. Imidazoline type surfactants include, but are not limited to, 2-undecyl-N-carboxymethyl-N-hydroxyethyl imidazoline, oleate sulfate type imidazoline, and the like. Amine oxide type surfactants include, but are not limited to, octadecyl dihydroxyethyl amine oxide, tetradecyl dihydroxyethyl amine oxide, lauramidopropyl amine oxide, and the like. Amino acid type surfactants include, but are not limited to, sodium dodecylaminopropionate, sodium dodecyldimethyleneaminodiformate, and the like. In some embodiments, the zwitterionic surfactant is selected from at least one of octadecyl dihydroxyethyl amine oxide, alkyl dimethyl sulfopropyl betaine, and imidazolinium oleate sulfate.
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 cation precursor, the anion precursor, the zwitterionic surfactant, and the nonionic surfactant are subjected to heat treatment in an organic solvent to prepare a metal compound precursor, thereby obtaining a metal compound precursor solution.
As an embodiment, the heating process includes: heating at 60-90 deg.C for 2-6 hr. Under the reaction condition, the method can improve the reactivity between the cation precursor and the anion precursor, promote the synthesis of the metal compound precursor, and simultaneously facilitate the adsorption of the surfactant on the surface of the synthesized metal compound precursor.
As an embodiment, as shown in fig. 2, the step of subjecting the cationic precursor, the anionic precursor, the zwitterionic surfactant, and the nonionic surfactant to a heat treatment in an organic solvent includes:
s021, dissolving the cation precursor and the anion precursor in the organic solvent, and performing first heating treatment to obtain a first solution in which metal compound precursor crystal nuclei are dispersed;
s022, dispersing the zwitterionic surfactant and the nonionic surfactant in the first solution, and further carrying out second heating treatment to obtain the metal compound precursor solution.
The method comprises the steps of firstly preparing metal compound precursor crystal nuclei, and then adding the zwitterionic surfactant and the nonionic surfactant into the first solution dispersed with the metal compound precursor crystal nuclei, so that a cation precursor and an anion precursor are fully reacted, the yield of metal compound nanoparticles is improved, and the metal compound nanoparticles with small particle size and uniform size distribution are synthesized at high yield
In step S021, the cation precursor and the anion precursor are dissolved in the organic solvent, and a first heating treatment is performed to obtain a first solution in which metal compound precursor nuclei are dispersed.
The step of dissolving the cationic precursor and the anionic precursor in the organic solvent may be referred to a conventional procedure in the art. In order to accelerate the dissolution of the cation precursor and the anion precursor in the organic solvent, ultrasonic and/or mechanical stirring methods may be used.
In some embodiments, the anionic precursor is selected from a sulfur source, and the molar ratio of the anion of the anionic precursor to the cation of the cationic precursor is (1-1.5):1, at which molar ratio range the introduction of too much sulfur or metal impurities can be avoided to promote adequate synthesis of metal compound nanoparticles.
In some embodiments, the anionic precursor is selected from an organic base and/or an inorganic base, and the molar ratio of anions of the anionic precursor to cations of the cationic precursor is (1.8-4.5): 1. Reacting the metal salt with alkali liquor in an organic solvent to form hydroxide (M (OH)x，M(OH)xBy polycondensation reaction, dehydration to form MOxThe dosage of the alkali liquor can be adjusted according to the valence state of the metal ions of the metal salt. When the metal ion is +2 (e.g. Zn)2+、Ni2+) The theoretical value of the molar ratio of the alkali liquor to the metal ions is 2:1, optimizing and screening, for example, keeping the molar ratio of alkali liquor to metal ions to be (1.8-2.5): 1, ensuring that reaction substrates can fully react to form corresponding metal oxide nano-particles; when the metal ion is +4 (Ti)4 +、Sn4+、Zr4+) The mol ratio of the alkali liquor to the metal ions is 4: 1, when the molar ratio of the alkali liquor to the metal ions is (3.5-4.5): 1, the reaction substrates can be ensured to react sufficiently to form the corresponding metal oxide nanoparticles. When the molar ratio of the alkali liquor to the metal ions is less than 1.8:1 or 3.5: 1, pH<12, alkali liquor is insufficient, metal salt is excessive, and reaction is insufficient; when the molar ratio of the alkali liquor to the metal ions is more than 2.5: 1 or 4.5: 1, pH>13, excessive pH will cause the system to dissolveThe hydrolysis and polycondensation rates of the gum will be reduced.
In some embodiments, the concentration of the cation precursor in the organic solvent is 0.2-1mol/L, so that the cation precursor and the anion precursor have good reaction activity, the synthesis of metal compound nanoparticles is promoted, and the synthesis efficiency is improved.
In some embodiments, the first heating process comprises: heating at 60-90 deg.C for 2-6 hr. Under the reaction condition, the method can improve the reactivity between the cation precursor and the anion precursor, promote the synthesis of the metal compound nano-particles and improve the yield.
In step S022, the zwitterionic surfactant and the nonionic surfactant are dispersed in the first solution, and then subjected to a second heating treatment to obtain the metal compound precursor solution.
In the second heating treatment process, the unreacted cation precursor and the unreacted anion precursor in the reaction system continue to react to synthesize the metal compound precursor crystal nucleus, meanwhile, the added zwitterionic surfactant and the nonionic surfactant are combined with the metal compound precursor crystal nucleus in the reaction system, and the size and the shape of the metal compound nano-particles prepared subsequently are controlled by modifying the particle surface.
Dispersing newly synthesized metal compound precursor crystal nuclei in a first solution, wherein the metal compound precursor crystal nuclei comprise metal sulfide precursor crystal nuclei and metal oxide precursor crystal nuclei, the metal oxide precursor crystal nuclei are positively charged in the solution, the metal sulfide precursor crystal nuclei are negatively charged in the solution, and a zwitterionic surfactant and a nonionic surfactant are dispersed in the first solution; meanwhile, the polar head of the nonionic surfactant is fixed on the surface of the metal compound nanoparticle through coordination combination with the cation of the metal compound nanoparticle, the nonpolar head of the nonionic surfactant fully extends in the solution to form a steric hindrance layer, and the particles are further hindered from approaching each other, so that the phenomenon that the particle size is overlarge due to hard agglomeration among metal compound precursor particles is avoided; on the other hand, the amphoteric ion 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 double-electric-layer micelle particles, so that the electric repulsion between ion 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 compound precursor particles is inhibited, the morphology and the size of the particles are effectively improved, and the metal compound nano-particles with small size and uniform size distribution are prepared.
In one embodiment, the molar ratio of the sum of the zwitterionic surfactant and the nonionic surfactant to the cation of the cationic precursor is (2-3): 1. The metal compound 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 cation is less than 2:1, the surfactant cannot effectively regulate and control the size of metal compound precursor particles in the system; when the molar ratio of the surfactant to the cation is more than 3:1, the yield of the metal compound precursor particles is low and surfactant residues are easily caused, thereby affecting the electrical properties of the composite material. In some embodiments, the molar ratio of the zwitterionic surfactant to the nonionic surfactant is (1.5-2): 1. The zwitterionic surfactant and the nonionic surfactant in the molar ratio range have excellent compatibility with metal compound precursor crystal nuclei synthesized in a system, and are favorable for obtaining metal compound nanoparticles with small and uniform particle sizes.
In some embodiments, the step of dispersing the zwitterionic surfactant and the nonionic surfactant in the first solution comprises:
s0221, preparing a second solution in which a zwitterionic 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 compound precursor particles is controlled to a certain extent, the surfactant is promoted to be combined with the metal compound precursor particles while metal compound precursor crystal nuclei are continuously synthesized in a reaction system, the yield of the metal compound nanoparticles is improved, the particle agglomeration is effectively prevented, and the stable metal compound 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 60-90 deg.C for 2-6 hr. Under the heating condition, the surfactant has good activity, and is favorable for adsorbing the surfactant on the surface of the synthesized metal compound precursor, so that the surface modification of the metal compound 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 zwitterionic surfactant in the solvent can be improved, and ionization is promoted to form cations; on the other hand, the synthesized metal compound precursor particles have electronegativity in a polar solvent, so that the combination of the zwitterionic surfactant and the metal compound 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 cation precursors, anion precursors, surfactants and synthesized metal compound precursor particles, and can improve the dispersibility of the synthesized metal compound precursor particles in a system, so that the system tends to be stable, thereby inhibiting the uneven growth of the metal compound 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 formation of metal compound nanoparticles with small particle size and uniform distribution is promoted.
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 compound precursor solution is subjected to solid-liquid separation to obtain a composite material.
As an embodiment, the step of subjecting the metal compound precursor solution to solid-liquid separation includes: and carrying out annealing treatment on the metal compound precursor solution at the temperature of 200-250 ℃. By carrying out annealing treatment at the temperature of 200-250 ℃, the solvent is completely removed, and meanwhile, the metal compound nano-particles have excellent crystallinity, which is beneficial to improving the electrical property of the composite material.
As an embodiment, the composite material synthesized by the above preparation method includes: the surfactant is a zwitterionic surfactant and a nonionic surfactant. In some embodiments, the metal compound nanoparticles are at least one of metal sulfide nanoparticles and metal oxide nanoparticles.
In summary, the composite material prepared by the preparation method is modified metal compound nanoparticles, the surface of the modified metal compound nanoparticles is modified with the zwitterionic surfactant and the nonionic surfactant, the particle size is small, the distribution is uniform, the crystallinity is high, and when the modified metal compound nanoparticles 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 surfactant is a zwitterionic surfactant and a nonionic surfactant.
The composite material provided by the embodiment of the invention is prepared by the preparation method, is a metal compound nanoparticle with the surface modified with a surfactant, has small particle size and uniform size distribution, is favorable for forming a uniform and compact film layer, and improves the light emitting performance of a QLED device.
Wherein the kinds of the zwitterionic surfactant and the nonionic surfactant are substantially the same as those of the zwitterionic surfactant and the nonionic surfactant described above, it is understood that the zwitterionic surfactant and the nonionic surfactant have the same properties and effects as those described above.
In embodiments of the present invention, the metal compound nanoparticles include, but are not limited to, zinc sulfide, zinc oxide, titanium oxide, tin oxide, zirconium oxide, and the like. In some embodiments, the metal compound nanoparticles are selected to be zinc oxide. In some embodiments, the metal compound nanoparticles have a particle size of 5 to 10 nanometers.
As one embodiment, the molar ratio of the sum of the zwitterionic surfactant and the nonionic surfactant to the metal compound nanoparticles is (2-3): 1.
In one embodiment, the molar ratio of the zwitterionic surfactant to the nonionic surfactant is (1.5-2): 1.
In one embodiment, the composite material is a metal compound nanoparticle and a surfactant bound to the surface of the metal compound nanoparticle, the surfactant is a zwitterionic surfactant and a nonionic surfactant, the molar ratio of the surfactant to the metal compound nanoparticle is (2-3):1, and the molar ratio of the zwitterionic 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 of nanoparticles of metal compounds such as metal sulfides or metal oxides 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 a quantum dot, the quantum dot comprising IAt least one of the group V quantum dots, the group II-VI quantum dots, the group II-V quantum dots, the group III-VI quantum dots, the group IV-VI quantum dots, the group I-III-VI quantum dots, the group II-IV-VI quantum dots and the group II-IV-V quantum dots has the quantum dot characteristic and high luminous 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 dihydroxyethyl amine oxide and sorbitol liver fatty acid ester in ethanol to form a surfactant solution (molar ratio, octadecyl dihydroxyethyl amine oxide: sorbitol liver fatty acid ester 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 250 ℃ 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 hydroxide in 10mL of propanol, and stirring for dissolving to form a potassium hydroxide solution; adding a proper amount of potassium hydroxide solution into zinc nitrate solution, and stirring for 4h at 80 ℃ to form zinc oxide crystal nucleus solution (molar ratio, OH)-：Zn2+＝2：1)。
Dissolving alkyl dimethyl sulfoethyl betaine and fatty alcohol-polyoxyethylene ether in ethanol to form a surfactant solution (the molar ratio of alkyl dimethyl sulfoethyl betaine to fatty alcohol-polyoxyethylene ether is 1.5: 1);
dripping surfactant solution into the zinc oxide crystal nucleus solution, and continuously stirring at 70 ℃ for 1h to obtain solution (molar ratio, surfactant: Zn) dispersed with composite material2+＝2.5:1)；
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 3
The preparation method of the composite material film comprises the following steps:
adding titanium sulfate into 50mL of methanol, and stirring at 60 ℃ until the titanium sulfate is dissolved to form a titanium sulfate solution with the total concentration of 0.5M; dissolving potassium hydroxide in 10mL of methanol, and stirring for dissolving to form a potassium hydroxide solution; adding a proper amount of potassium hydroxide solution into titanium sulfate solution (molar ratio, OH)-：Ti4+4: 1) stirring at 60 deg.C for 4h to form titanium oxide crystal nucleus solution.
Dissolving the oleic acid sulfate type imidazoline and the polyoxyethylene alkylamine in ethanol to form a surfactant solution (the molar ratio of the oleic acid sulfate type imidazoline to the polyoxyethylene alkylamine is 1.8: 1);
dropwise adding surfactant solution into titanium oxide crystal nucleus solution, and stirring at 70 deg.C for 1 hr to obtain solution (molar ratio, surfactant: Ti) with composite material dispersed therein4+＝3:1)；
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 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 5 in that: spinning commercial ZnO nanoparticle ethanol dispersion liquid on the quantum dot light-emitting layer, and annealing at 250 ℃ to prepare an electron transmission layer;
the same points as those in embodiment 5 are basically the same, and are not described herein.
Comparative example 3
This comparative example prepared a light emitting diode which differed from example 6 in that: spin coating commercial TiO on Quantum dot light emitting layers2Annealing 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 to 3, and the quantum dot light-emitting diodes prepared in examples 4 to 9 and comparative examples 1 to 3 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 the 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
As can be seen from table 1 above, the composite material of the composite material thin film prepared in examples 1 to 3 of the present invention is metal compound nanoparticles surface-modified with zwitterionic surfactant and nonionic surfactant, and the resistivity is significantly lower than that of the electron transport thin film in comparative examples 1 to 3, and the electron mobility is significantly higher than that in comparative examples 1 to 3.
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 to 3, 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 cation precursor, an anion precursor, a zwitterionic surfactant and a nonionic surfactant;
heating the cation precursor, the anion precursor, the zwitterionic surfactant and the nonionic surfactant in an organic solvent to obtain a metal compound precursor solution;
and carrying out solid-liquid separation on the metal compound precursor solution to obtain the composite material.
2. The production method according to claim 1, wherein the step of subjecting the cationic precursor, the anionic precursor, the zwitterionic surfactant, and the nonionic surfactant to a heat treatment in an organic solvent comprises:
dissolving the cation precursor and the anion precursor in the organic solvent, and carrying out first heating treatment to obtain a first solution dispersed with metal compound precursor crystal nuclei;
and dispersing the zwitterionic surfactant and the nonionic surfactant in the first solution, and carrying out second heating treatment to obtain the metal compound precursor solution.
3. The production method according to claim 1 or 2, characterized in that the zwitterionic surfactant comprises: at least one of a sugar beet anion precursor type surfactant, an imidazoline type surfactant, an amine oxide type surfactant, and an amino acid 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 zwitterionic surfactant is selected from at least one of octadecyl dihydroxyethyl amine oxide, alkyl dimethyl sulfopropyl betaine, and oleate sulfate type imidazoline; 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, characterized in that in the step of subjecting the cation precursor, the anion precursor, the zwitterionic surfactant and the nonionic surfactant to heat treatment in an organic solvent, the molar ratio of the sum of the zwitterionic surfactant and the nonionic surfactant to the cation of the cation precursor is (2-3): 1; and/or
And a step of subjecting the cationic precursor, the anionic precursor, the zwitterionic surfactant and the nonionic surfactant to a heat treatment in an organic solvent, wherein the molar ratio of the zwitterionic surfactant to the nonionic surfactant is (1.5-2): 1.
6. The production method according to claim 1 or 2, wherein the heating treatment includes: heating at 60-90 deg.c for 2-6 hr; and/or
The step of subjecting the metal compound precursor solution to solid-liquid separation comprises: and carrying out annealing treatment on the metal compound precursor solution at the temperature of 200-250 ℃.
7. The method according to claim 1 or 2, wherein the cationic precursor is selected from soluble organic metal salts and/or soluble inorganic metal salts; and/or
The organic solvent is at least one of methanol, ethanol, propanol, glycerol, n-butanol, n-pentanol, ethylene glycol methyl ether and ethylene glycol methyl ether acetate; and/or
And a step of subjecting the cationic precursor, the anionic precursor, the zwitterionic surfactant and the nonionic surfactant to a heat treatment in an organic solvent, wherein the concentration of the cationic precursor in the organic solvent is 0.2 to 1 mol/L.
8. The production method according to claim 1 or 2, characterized in that, in the step of subjecting the cation precursor, the anion precursor, the zwitterionic surfactant and the nonionic surfactant to a heat treatment in an organic solvent, the anion precursor is selected from a sulfur source, and a molar ratio of an anion of the anion precursor to a cation of the cation precursor is (1-1.5): 1;
or the anion precursor is selected from organic base and/or inorganic base, and the molar ratio of the anion precursor to the cation of the cation precursor is (1.8-4.5): 1.
9. A composite material, comprising: the surfactant is a zwitterionic surfactant and a nonionic surfactant.
10. The composite material of claim 9, wherein the molar ratio of the sum of the zwitterionic surfactant and the nonionic surfactant to the metal compound nanoparticles is (2-3: 1; and/or
The molar ratio of the zwitterionic 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 compound nanoparticle and a surfactant bonded to the surface of the metal compound nanoparticle, the surfactant is a zwitterionic surfactant and a nonionic surfactant, the molar ratio of the surfactant to the metal compound nanoparticle is (2-3):1, and the molar ratio of the zwitterionic 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.
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| KR20180035279A (en) * | 2016-09-28 | 2018-04-06 | 경북대학교 산학협력단 | White quantum dots based light emitting device and method of manufacturing the same |
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