CN111244296B - Quantum dot light-emitting diode and preparation method thereof - Google Patents
Quantum dot light-emitting diode and preparation method thereof Download PDFInfo
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- CN111244296B CN111244296B CN201811432581.0A CN201811432581A CN111244296B CN 111244296 B CN111244296 B CN 111244296B CN 201811432581 A CN201811432581 A CN 201811432581A CN 111244296 B CN111244296 B CN 111244296B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229920000962 poly(amidoamine) Polymers 0.000 claims abstract description 131
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- 239000000463 material Substances 0.000 claims abstract description 42
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- 239000003607 modifier Substances 0.000 claims description 8
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- 238000000151 deposition Methods 0.000 claims description 5
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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
- RKVIAZWOECXCCM-UHFFFAOYSA-N 2-carbazol-9-yl-n,n-diphenylaniline Chemical compound C1=CC=CC=C1N(C=1C(=CC=CC=1)N1C2=CC=CC=C2C2=CC=CC=C21)C1=CC=CC=C1 RKVIAZWOECXCCM-UHFFFAOYSA-N 0.000 description 1
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- 239000000395 magnesium oxide Substances 0.000 description 1
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- 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
-
- 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
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- 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
- H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
Abstract
The invention discloses a quantum dot light-emitting diode and a preparation method thereof, wherein the quantum dot light-emitting diode comprises a cathode, an anode and a quantum dot light-emitting layer arranged between the cathode and the anode, the quantum dot light-emitting layer is made of a mixed material consisting of quantum dots and oil-soluble PAMAM dendrimer, and the exciton Bohr radius of the quantum dots is larger than the diameter of the quantum dots. In the invention, the space distance between the quantum dots in the quantum dot luminescent layer can be effectively pulled open by the oil-soluble PAMAM dendrimer, thereby effectively reducing the energy transfer between the quantum dots and indirectly improving the fluorescence intensity of the quantum dot luminescent layer; in addition, the oil-soluble PAMAM dendrimer can wrap the surface of the quantum dot to bind excitons, so that the quantum yield of the quantum dot light-emitting layer can be improved, and the light-emitting efficiency of the quantum dot light-emitting diode can be improved.
Description
Technical Field
The invention relates to the field of quantum dot light-emitting diodes, in particular to a quantum dot light-emitting diode and a preparation method thereof.
Background
In the quantum dot light-emitting diode, when quantum dots with exciton Bohr radius far larger than particle size are used as light-emitting layer material, the prepared device has low light-emitting efficiency, and the major reason is that exciton energy transfer can be generated between the quantum dots in the light-emitting layer, so that the Quantum Yield (QY) is low.
For a quantum dot light-emitting diode using quantum dots with exciton Bohr radius far larger than particle size as a material of a quantum dot light-emitting layer, how to improve the quantum yield of the quantum dot light-emitting layer is a key for improving the light-emitting efficiency of the quantum dot light-emitting diode. In the prior art, a wide band gap shell layer is grown on an outer layer of the quantum dot with the exciton Bohr radius far larger than the particle size, so that the energy transfer between the quantum dot and the quantum dot can be reduced to a certain extent, but the quantum yield of the quantum dot solid-state film cannot be greatly improved, so that the prior art needs to be improved.
Disclosure of Invention
In view of the above-mentioned deficiencies of the prior art, the present invention aims to provide a quantum dot light emitting diode and a method for manufacturing the same, which aims to solve the problem of low light emitting efficiency of the quantum dot light emitting diode due to low quantum yield of the existing quantum dot material.
The technical scheme of the invention is as follows:
the quantum dot light-emitting diode comprises a cathode, an anode and a quantum dot light-emitting layer arranged between the cathode and the anode, wherein the quantum dot light-emitting layer is made of a mixed material consisting of quantum dots and oil-soluble PAMAM (polyamidoamine) dendrimer, and the exciton Bohr radius of the quantum dots is larger than the diameter of the quantum dots.
A preparation method of a quantum dot light-emitting diode comprises the following steps:
providing a substrate, and preparing a quantum dot light-emitting layer on the surface of the substrate;
the quantum dot light-emitting layer material is a mixed material consisting of quantum dots and oil-soluble PAMAM dendrimer, and the exciton Bohr radius of the quantum dots is larger than the diameter of the quantum dots.
Has the advantages that: the quantum dot light-emitting layer is prepared from the mixed material consisting of the quantum dots and the oil-soluble PAMAM dendrimer, and the spatial distance between the quantum dots in the quantum dot light-emitting layer and the quantum dots can be effectively pulled open by the oil-soluble PAMAM dendrimer, so that the energy transfer between the quantum dots and the quantum dots is effectively reduced, and the fluorescence intensity of the quantum dot light-emitting layer is indirectly improved; in addition, after the mixed material forms a quantum dot light-emitting layer, the oil-soluble PAMAM dendrimer can be wrapped on the surface of the quantum dot to further bind excitons, so that the quantum yield of the quantum dot light-emitting layer is improved, and the light-emitting efficiency of the quantum dot light-emitting diode is improved.
Drawings
Fig. 1 is a schematic structural diagram of a quantum dot light emitting diode according to a preferred embodiment of the invention.
Detailed Description
The invention provides a quantum dot light-emitting diode and a preparation method thereof, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The quantum dot light-emitting diode has various forms, is divided into a positive structure and an inversion structure, and can comprise a substrate, a cathode, an electron transmission layer, a quantum dot light-emitting layer, a hole transmission layer and an anode which are stacked from bottom to top. The embodiments of the present invention will be described mainly by taking a quantum dot light emitting diode of a positive type structure as shown in fig. 1 as an example. Specifically, as shown in fig. 1, the quantum dot light emitting diode with the positive structure comprises a substrate 10, an anode 20, a hole transport layer 30, a quantum dot light emitting layer 40, an electron transport layer 50 and a cathode 60 which are stacked from bottom to top, wherein the quantum dot light emitting layer material is a mixed material composed of quantum dots and oil-soluble PAMAM dendrimer, and the exciton bohr radius of the quantum dots is larger than the diameter of the quantum dots.
In the embodiment, the mixed material composed of the quantum dots and the oil-soluble PAMAM tree-shaped molecules is used as the material of the quantum dot light-emitting layer, so that the quantum yield of the quantum dot light-emitting layer can be effectively improved, and the light-emitting efficiency of the quantum dot light-emitting diode is improved. The mechanism for achieving the above effects is specifically as follows:
in the mixed material, because the space volume of the oil-soluble PAMAM (polyamide-amine) dendrimer is larger than the diameter of the quantum dot, after the mixed material is prepared into a solid film (a quantum dot light-emitting layer), the space distance between the quantum dot and the quantum dot in the solid film can be effectively pulled open by the oil-soluble PAMAM dendrimer, so that the energy transfer between the quantum dot and the quantum dot is effectively reduced, and the fluorescence intensity of the solid film is indirectly improved; in addition, after the mixed material forms a solid film, the oil-soluble PAMAM dendrimer can wrap the surface of the quantum dot, and similarly, a molecular shell layer wraps the surface of the quantum dot, and the oil-soluble PAMAM dendrimer can further bind excitons, so that the quantum yield of the solid film is improved, and the luminous efficiency of the quantum dot light-emitting diode is improved.
In this embodiment, the specific preparation method of the oil-soluble PAMAM dendrimer includes the steps of: providing a PAMAM dendrimer; dissolving the PAMAM dendrimer in a polar solvent to prepare a PAMAM dendrimer solution; adding an end group modifier into the PAMAM dendrimer solution in an inert atmosphere, and mixing to enable an amino functional group on the PAMAM dendrimer to react with the end group modifier to generate an oil-soluble group, thereby obtaining the oil-soluble PAMAM dendrimer.
The PAMAM dendrimer which is not modified by the terminal group is a hydrophilic organic molecule which can be stably stored and dissolved in a polar solvent to form a PAMAM dendrimer solution; adding excessive end group modifier into the PAMAM dendrimer solution under inert atmosphere, rapidly stirring, and controlling reaction conditions to enable part or all of terminal amino functional groups on the PAMAM dendrimer to react with the end group modifier, thereby preparing the oil-soluble PAMAM dendrimer. Preferably, the oil-soluble PAMAM dendrimer is a PAMAM dendrimer whose distal functional groups include a sulfonamide group, which is-NH-R, wherein R is one or more of an unsubstituted aryl group, an alkyl-substituted aryl group, and an alkylamino-substituted aryl group. The terminal group modifier is selected from one or more of p-toluenesulfonyl chloride, o-toluenesulfonyl chloride, m-toluenesulfonyl chloride, p-dimethylaminobenzenesulfonyl chloride, o-dimethylbenzenesulfonyl chloride and m-dimethylaminobenzenesulfonyl chloride, but is not limited thereto. By way of example, when p-dimethylaminobenzenesulfonyl chloride is added to a PAMAM dendrimer solution, the reaction is represented by the formula:
Dendrimer-NH2+(CH3)2-N-C10H6-SOCl 
Dendrimer-NHOS- C10H6-N-(CH3)2+
HCl；
when p-toluenesulfonyl chloride is added to the PAMAM dendrimer solution, the reaction is as follows:
Dendrimer-NH2+CH3-C6H4-SOOCl 
Dendrimer-NHSOO-C6H4-CH3(ii) a The Dendrimer-NH2The PAMAM dendrimer is a generation G1-G10, and can be effectively dispersed in an oil phase solution after being modified by an end group, so that the PAMAM dendrimer and oil phase quantum dots can be conveniently mixed to form a solid film.
In a preferred embodiment, the oil-soluble PAMAM dendrimer is selected from one or more of the first generation PAMAM dendrimer (G1), the second generation PAMAM dendrimer (G2), the third generation PAMAM dendrimer (G3), the fourth generation PAMAM dendrimer (G4), the fifth generation PAMAM dendrimer (G5), the sixth generation PAMAM dendrimer (G6), the seventh generation PAMAM dendrimer (G7), the eighth generation PAMAM dendrimer (G8), the ninth generation PAMAM dendrimer (G9), and the tenth generation PAMAM dendrimer (G10), but is not limited thereto.
In this embodiment, the PAMAM (polyamide-amine) dendrimer is obtained by reacting different molecular units a (ethylenediamine) and B (methyl acrylate), and may be synthesized by a divergent method, in the first step, ethylenediamine and methyl acrylate react to generate carboxylate, in the second step, the carboxylate obtained reacts with excess ethylenediamine, and after the above two reactions, the first generation PAMAM dendrimer may be obtained, and the above two reactions may be repeated to obtain a higher generation PAMAM dendrimer. The PAMAM dendrimer with different generations contains the molecular units A and B with the general formulas: a (2)n+2n-1+…+2n-3)+B(2n+1+2n+…+2n-1) Wherein the value of n is 3-10; in addition, the first generation PAMAMThe dendrimer contains the molecular unit A and the molecular unit B with the general formula of A +4B, and the second generation PAMAM dendrimer contains the molecular unit A and the molecular unit B with the general formula of 5A + 8B.
In a preferred embodiment, as the generation number of the PAMAM dendrimer is larger, the space volume of the PAMAM dendrimer is larger, in order to ensure that the PAMAM dendrimer can effectively enlarge the space distance between the quantum dots and the quantum dots, when the bohr radius of the selected quantum dots is relatively larger, the PAMAM dendrimer with the larger generation number is selected to be matched with the quantum dots to form a mixed material; when the Bohr radius of the selected quantum dots is relatively small, PAMAM dendrimer with small algebra is selected to be matched with the quantum dots to form the mixed material. Preferably, the phase difference between the Bohr radius of the quantum dot and the diameter of the quantum dot is controlled to be 6-100nm, and the oil-soluble PAMAM dendrimer is selected from one or more of a fifth generation PAMAM dendrimer, a sixth generation PAMAM dendrimer, a seventh generation PAMAM dendrimer, an eighth generation PAMAM dendrimer, a ninth generation PAMAM dendrimer and a tenth generation PAMAM dendrimer. The PAMAM dendrimer not only has larger space volume but also has larger viscosity coefficient along with the increase of algebra, so the PAMAM dendrimer can not only increase the distance between quantum dots after being mixed with the quantum dots, but also improve the film-forming property of the quantum dots. More preferably, in order to ensure the brightness of the whole luminescent layer, the difference between the bohr radius of the quantum dots and the diameter of the quantum dots is controlled to be 20-40nm, and the oil-soluble PAMAM dendrimer is selected from one or two of the sixth generation PAMAM dendrimer and the seventh generation PAMAM dendrimer.
In a preferred embodiment, in order to ensure that the spatial distance between the quantum dots can be pulled by the PAMAM dendrimer, thereby reducing the energy transfer between the quantum dots, the oil-soluble PAMAM dendrimer and the quantum dots are mixed according to a set ratio to form a mixed material. Because the PAMAM dendrimer of different generations has larger molecular weight difference, when the PAMAM dendrimer of different generations and the quantum dot are selected to form the mixed material, the molar mass ratio difference is larger.
Preferably, if the PAMAM dendrimer is a fifth generation PAMAM dendrimer, the ratio of the molar weight of the fifth generation PAMAM dendrimer to the mass of the quantum dots is 1-5mmol:10 mg.
Preferably, if the PAMAM dendrimer is a sixth generation PAMAM dendrimer, the ratio of the molar weight of the sixth generation PAMAM dendrimer to the mass of the quantum dots is 0.5-4mmol:10 mg.
Preferably, if the PAMAM dendrimer is a seventh generation PAMAM dendrimer, the ratio of the molar weight of the seventh generation PAMAM dendrimer to the mass of the quantum dots is 0.3-3mmol:10 mg.
Preferably, if the PAMAM dendrimer is an eighth generation PAMAM dendrimer, the ratio of the molar weight of the eighth generation PAMAM dendrimer to the mass of the quantum dots is 0.2-2mmol:10 mg.
Preferably, if the PAMAM dendrimer is a ninth generation PAMAM dendrimer, the ratio of the molar weight of the ninth generation PAMAM dendrimer to the mass of the quantum dots is 0.1-1mmol:10 mg.
Preferably, if the PAMAM dendrimer is a tenth generation PAMAM dendrimer, the ratio of the molar weight of the tenth generation PAMAM dendrimer to the mass of the quantum dots is 0.05-0.5mmol:10 mg.
In a preferred embodiment, the quantum dots are oil phase quantum dots selected from one or more of PbS, PbSe, CdTe, HgS, AgS, and InP, but not limited thereto.
In a preferred embodiment, the invention further provides a quantum dot light emitting diode with an inversion structure, which comprises a substrate, a cathode, an electron transport layer, a quantum dot light emitting layer, a hole transport layer and an anode, wherein the substrate, the cathode, the electron transport layer, the quantum dot light emitting layer, the hole transport layer and the anode are sequentially stacked from bottom to top, the quantum dot light emitting layer is made of a mixed material composed of quantum dots and oil-soluble PAMAM dendrimer, and the exciton bohr radius of the quantum dots is larger than the diameter of the quantum dots.
It should be noted that the invention is not limited to the quantum dot light emitting diode with the above structure, and may further include an interface functional layer or an interface modification layer, including but not limited to one or more of an electron blocking layer, a hole blocking layer, an electrode modification layer, and an isolation protection layer. The quantum dot light emitting diode can be partially packaged, fully packaged or not packaged.
Preferably, the material of the anode is selected from doped metal oxides; wherein the doped metal oxide includes, but is not limited to, one or more of indium-doped tin oxide (ITO), fluorine-doped tin oxide (FTO), antimony-doped tin oxide (ATO), aluminum-doped zinc oxide (AZO), gallium-doped zinc oxide (GZO), indium-doped zinc oxide (IZO), magnesium-doped zinc oxide (MZO), and aluminum-doped magnesium oxide (AMO).
Preferably, the material of the hole transport layer is selected from organic materials having good hole transport ability, such as but not limited to Poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine) (TFB), Polyvinylcarbazole (PVK), Poly (N, N 'bis (4-butylphenyl) -N, N' -bis (phenyl) benzidine) (Poly-TPD), Poly (9, 9-dioctylfluorene-CO-bis-N, N-phenyl-1, 4-Phenylenediamine) (PFB), 4', 4 "-tris (carbazol-9-yl) triphenylamine (TCTA), 4' -bis (9-Carbazole) Biphenyl (CBP), N '-diphenyl-N, N' -bis (3-methylphenyl) -1, one or more of 1 '-biphenyl-4, 4' -diamine (TPD), N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (NPB), doped graphene, undoped graphene, and C60.
Preferably, the electron transport layer material includes, but is not limited to, one or more of zinc oxide, nickel oxide, and titanium oxide.
Preferably, the material of the cathode is selected from one or more of a conductive carbon material, a conductive metal oxide material and a metal material; wherein the conductive carbon material includes, but is not limited to, one or more of doped or undoped carbon nanotubes, doped or undoped graphene oxide, C60, graphite, carbon fibers, and porous carbon; the conductive metal oxide material includes, but is not limited to, one or more of ITO, FTO, ATO, and AZO; metallic materials include, but are not limited to, Al, Ag, Cu, Mo, Au, or alloys thereof; wherein, the metal material has a form including but not limited to one or more of a compact film, a nanowire, a nanosphere, a nanorod, a nanocone and a hollow nanosphere.
Specifically, the quantum dot light emitting diode has a positive structure and an inversion structure. The positive structure comprises an anode, a cathode and a quantum dot light emitting layer, wherein the anode, the cathode and the quantum dot light emitting layer are arranged in a stacked mode, the anode of the positive structure is arranged on the substrate, hole function layers such as a hole transmission layer, a hole injection layer and an electron blocking layer can be further arranged between the anode and the quantum dot light emitting layer, and electronic function layers such as an electron transmission layer, an electron injection layer and a hole blocking layer can be further arranged between the cathode and the quantum dot light emitting layer. The reflection structure comprises an anode, a cathode and a quantum dot light emitting layer, wherein the anode and the cathode are arranged in a stacked mode, the quantum dot light emitting layer is arranged between the anode and the cathode, the cathode of the reflection structure is arranged on the substrate, hole function layers such as a hole transmission layer, a hole injection layer and an electron blocking layer can be further arranged between the anode and the quantum dot light emitting layer, and electronic function layers such as an electron transmission layer, an electron injection layer and a hole blocking layer can be further arranged between the cathode and the quantum dot light emitting layer.
For a positive type device, the bottom electrode disposed on the substrate is an anode, and in one embodiment of the present invention, the substrate may be a substrate on which the bottom electrode is disposed; in still another embodiment of the present invention, the substrate may include a substrate, a bottom electrode stacked on a surface of the substrate, and a hole transport layer stacked on the surface of the substrate; in still another embodiment of the present invention, the substrate may include a substrate, a bottom electrode stacked on a surface of the substrate, a hole injection layer stacked on the surface of the substrate, and a hole transport layer stacked on a surface of the hole injection layer; in still another embodiment of the present invention, the substrate may include a substrate, a bottom electrode stacked on a surface of the substrate, a hole injection layer stacked on the surface of the substrate, a hole transport layer stacked on a surface of the hole injection layer, and an electron blocking layer stacked on a surface of the hole transport layer.
For an inversion device, the bottom electrode disposed on the substrate is a cathode, and in one embodiment of the present invention, the substrate may be a substrate on which the bottom electrode is disposed; in still another embodiment of the present invention, the base plate may include a substrate, a bottom electrode stacked on a surface of the substrate, and an electron transport layer stacked on the surface of the substrate; in still another embodiment of the present invention, the substrate may include a substrate, a bottom electrode stacked on a surface of the substrate, an electron injection layer stacked on the surface of the substrate, and a hole transport layer stacked on a surface of the electron injection layer; in still another embodiment of the present invention, the substrate may include a substrate, a bottom electrode stacked on a surface of the substrate, an electron injection layer stacked on a surface of the substrate, an electron transport layer stacked on a surface of the electron injection layer, and a hole blocking layer stacked on a surface of the electron transport layer.
Further, the present invention also provides an embodiment of a method for preparing a quantum dot light emitting diode with a positive structure as shown in fig. 1, which specifically includes the following steps:
providing a substrate, and preparing an anode on the substrate;
preparing a hole transport layer on the anode;
preparing a quantum dot light emitting layer on the hole transport layer;
preparing an electron transport layer on the quantum dot light emitting layer;
preparing a cathode on the electron transport layer to obtain the quantum dot light-emitting diode;
the quantum dot light-emitting layer material is a mixed material consisting of quantum dots and oil-soluble PAMAM dendrimer, and the exciton Bohr radius of the quantum dots is larger than the diameter of the quantum dots.
In the present invention, the preparation method of each layer may be a chemical method or a physical method, wherein the chemical method includes, but is not limited to, one or more of a chemical vapor deposition method, a continuous ionic layer adsorption and reaction method, an anodic oxidation method, an electrolytic deposition method, and a coprecipitation method; the physical method includes, but is not limited to, one or more of solution method (such as spin coating, printing, knife coating, dip-coating, dipping, spraying, roll coating, casting, slit coating, or bar coating), evaporation method (such as thermal evaporation, electron beam evaporation, magnetron sputtering, or multi-arc ion plating), deposition method (such as physical vapor deposition, atomic layer deposition, pulsed laser deposition, etc.).
In a preferred embodiment, the step of preparing a quantum dot light emitting layer on the hole transport layer comprises:
dissolving the mixed material in a non-polar solvent to generate a colloidal solution;
depositing the colloidal solution on the surface of the hole transport layer to form a film, and annealing at the temperature for min to obtain the quantum dot light-emitting layer.
The quantum dot light-emitting layer is prepared from the mixed material consisting of the quantum dots and the oil-soluble PAMAM dendrimer, and the spatial distance between the quantum dots in the quantum dot light-emitting layer and the quantum dots can be effectively pulled open by the oil-soluble PAMAM dendrimer, so that the energy transfer between the quantum dots and the quantum dots is effectively reduced, and the fluorescence intensity of the quantum dot light-emitting layer is indirectly improved; in addition, after the mixed material forms a quantum dot light-emitting layer, the oil-soluble PAMAM dendrimer can be wrapped on the surface of the quantum dot to further bind excitons, so that the quantum yield of the quantum dot light-emitting layer is improved, and the light-emitting efficiency of the quantum dot light-emitting diode is improved.
The invention also provides a preparation method of the QLED with the hole transport layer in the inversion structure, which comprises the following steps:
providing a substrate;
preparing a cathode on the substrate;
preparing an electron transport layer on the cathode;
preparing a quantum dot light-emitting layer on the electron transport layer, wherein the quantum dot light-emitting layer is made of a mixed material consisting of quantum dots and oil-soluble PAMAM dendrimer, and the exciton Bohr radius of the quantum dots is larger than the diameter of the quantum dots;
preparing a hole transport layer on the quantum dot light emitting layer;
and preparing an anode on the hole transport layer to obtain the QLED.
The preparation method of each layer can be a chemical method or a physical method, wherein the chemical method comprises one or more of but not limited to a chemical vapor deposition method, a continuous ion layer adsorption and reaction method, an anodic oxidation method, an electrolytic deposition method and a coprecipitation method; physical methods include, but are not limited to, physical coating methods or solution methods, wherein solution methods include, but are not limited to, spin coating, printing, knife coating, dip-coating, dipping, spraying, roll coating, casting, slot coating, bar coating; physical coating methods include, but are not limited to, one or more of thermal evaporation coating, electron beam evaporation coating, magnetron sputtering, multi-arc ion coating, physical vapor deposition, atomic layer deposition, pulsed laser deposition.
In conclusion, the quantum dot light-emitting layer is prepared by adopting the mixed material consisting of the quantum dots and the oil-soluble PAMAM dendrimer, and the spatial distance between the quantum dots in the quantum dot light-emitting layer and the quantum dots can be effectively pulled open by the oil-soluble PAMAM dendrimer, so that the energy transfer between the quantum dots and the quantum dots is effectively reduced, and the fluorescence intensity of the quantum dot light-emitting layer is indirectly improved; in addition, after the mixed material forms a quantum dot light-emitting layer, the oil-soluble PAMAM dendrimer can be wrapped on the surface of the quantum dot to further bind excitons, so that the quantum yield of the quantum dot light-emitting layer is improved, and the light-emitting efficiency of the quantum dot light-emitting diode is improved.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (8)
1. The quantum dot light-emitting diode comprises a cathode, an anode and a quantum dot light-emitting layer arranged between the cathode and the anode, and is characterized in that the material of the quantum dot light-emitting layer is a mixed material consisting of quantum dots and oil-soluble PAMAM dendrimer, the oil-soluble PAMAM dendrimer is a PAMAM dendrimer of which the terminal functional group comprises sulfonamide group, and the sulfonamide group is-NH-R, wherein R is one or more of unsubstituted aryl, alkyl substituted aryl and alkylamino substituted aryl, the PAMAM dendrimer is one or more selected from the PAMAM dendrimer of fifth generation to tenth generation, and the exciton Bohr radius of the quantum dots is larger than the diameter of the quantum dots.
2. The quantum dot light-emitting diode of claim 1, wherein the PAMAM dendrimer is selected from one or more of a sixth generation or seventh generation PAMAM dendrimer.
3. The quantum dot light-emitting diode of claim 1, wherein in the mixed material, if the PAMAM dendrimer is a fifth generation PAMAM dendrimer, the ratio of the molar weight of the fifth generation PAMAM dendrimer to the mass of the quantum dot is 1-5mmol:10 mg;
and/or if the PAMAM dendrimer is a sixth generation PAMAM dendrimer, the ratio of the molar weight of the sixth generation PAMAM dendrimer to the mass of the quantum dots is 0.5-4mmol:10 mg;
and/or if the PAMAM dendrimer is a seventh generation PAMAM dendrimer, the ratio of the molar weight of the seventh generation PAMAM dendrimer to the mass of the quantum dots is 0.3-3mmol:10 mg;
and/or if the PAMAM dendrimer is an eighth generation PAMAM dendrimer, the ratio of the molar weight of the eighth generation PAMAM dendrimer to the mass of the quantum dots is 0.2-2mmol:10 mg;
and/or if the PAMAM dendrimer is a ninth generation PAMAM dendrimer, the ratio of the molar weight of the ninth generation PAMAM dendrimer to the mass of the quantum dots is 0.1-1mmol:10 mg;
and/or if the PAMAM dendrimer is a tenth generation PAMAM dendrimer, the ratio of the molar weight of the tenth generation PAMAM dendrimer to the mass of the quantum dots is 0.05-0.5mmol:10 mg.
4. A preparation method of a quantum dot light-emitting diode is characterized by comprising the following steps:
providing a substrate, and preparing a quantum dot light-emitting layer on the surface of the substrate;
the quantum dot light-emitting layer material is a mixed material consisting of quantum dots and oil-soluble PAMAM dendrimer, the oil-soluble PAMAM dendrimer is a PAMAM dendrimer of which the peripheral functional group comprises sulfonamide groups, the sulfonamide groups are-NH-R, R is one or more of unsubstituted aryl, alkyl substituted aryl and alkylamino substituted aryl, the PAMAM dendrimer is selected from one or more of the PAMAM dendrimer from the fifth generation to the tenth generation, and the exciton Bohr radius of the quantum dots is larger than the diameter of the quantum dots.
5. The method for preparing the quantum dot light-emitting diode of claim 4, wherein the method for preparing the oil-soluble PAMAM dendrimer comprises the following steps:
dissolving the PAMAM dendrimer in a polar solvent, adding an end group modifier, and mixing to enable all or part of amine functional groups at the tail end of the PAMAM dendrimer to react with the end group modifier to obtain the oil-soluble PAMAM dendrimer.
6. The method for preparing the quantum dot light-emitting diode according to claim 5, wherein the end group modifier is selected from one or more of p-toluenesulfonyl chloride, o-toluenesulfonyl chloride, m-toluenesulfonyl chloride, p-dimethylaminobenzenesulfonyl chloride, o-dimethylbenzenesulfonyl chloride and m-dimethylaminobenzenesulfonyl chloride.
7. The method for preparing a quantum dot light-emitting diode according to claim 6, wherein the step of preparing a quantum dot light-emitting layer on the surface of the substrate comprises:
and adopting a solution method to deposit the mixed material on the substrate and then annealing to prepare the quantum dot light-emitting layer.
8. The method for preparing a quantum dot light-emitting diode according to claim 7, wherein the step of preparing the quantum dot light-emitting layer on the surface of the substrate comprises:
and depositing the mixed material on the substrate by a solution method, and annealing for 15-60min at the temperature of 80-150 ℃ to obtain the quantum dot light-emitting layer.
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