WO2022016822A1 - 量子点发光二极管及其制备方法 - Google Patents

量子点发光二极管及其制备方法 Download PDF

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WO2022016822A1
WO2022016822A1 PCT/CN2020/141768 CN2020141768W WO2022016822A1 WO 2022016822 A1 WO2022016822 A1 WO 2022016822A1 CN 2020141768 W CN2020141768 W CN 2020141768W WO 2022016822 A1 WO2022016822 A1 WO 2022016822A1
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quantum dot
dot light
poly
emitting diode
diyl
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PCT/CN2020/141768
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French (fr)
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周礼宽
邹文鑫
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Tcl科技集团股份有限公司
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
    • 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
    • H10K50/15—Hole 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
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • 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
    • 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
    • H10K71/421—Thermal treatment, e.g. annealing in the presence of a solvent vapour using coherent electromagnetic radiation, e.g. laser annealing
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers

Definitions

  • the present application relates to the technical field of display devices, in particular to a quantum dot light-emitting diode and a preparation method thereof.
  • quantum dot materials with extremely high fluorescence quantum yield can be developed.
  • quantum dots with fluorescence quantum yield close to 100% can be prepared.
  • the full width at Half Maximum (FWHM ⁇ 30 nm) of the luminescence peak of quantum dots is very narrow, indicating that quantum dots can emit light with a purer color spectrum and a wider color gamut. Therefore, the electroluminescent device of quantum dot light-emitting diode (Quantum Dot Light Emitting Diode, QLED) based on quantum dots has a larger color gamut coverage, and the unique core-shell structure of quantum dots makes it more powerful than organic quantum dot light-emitting diodes.
  • OLED Organic Dot Light Emitting Diode
  • OLED Organic Dot Light Emitting Diode
  • the emission color of the quantum dots can be completely covered from the ultraviolet to the infrared band of the visible light spectrum; by changing the type of quantum dots, not only can a variety of light-emitting devices be prepared, but also easier Achieve precise control over emission color.
  • quantum dots can be dispersed in different solvents such as organic solvents and aqueous solutions by changing the polarity of the surface ligands of quantum dots.
  • the application conditions in the environment enrich the methods for preparing quantum dot films. It is precisely because of this characteristic of quantum dots that all-solution preparation methods, such as spin coating, spray coating, inkjet printing, etc., can be perfectly used to prepare QLED devices.
  • a smooth lower layer film is the premise of preparing a smooth upper layer film.
  • the selection of the solvent for adjacent films must conform to the orthogonal principle, that is, the polarity of the solvent must be obvious. difference.
  • the solvent between the functional layers of some devices cannot choose a suitable orthogonal solvent, or the polarities of the solvents in some adjacent functional layers are significantly different, and some thin films may be mixed, especially in the hole transport layer and quantum dots.
  • aromatic hydrocarbons are good solvents for quantum dots, and quantum dot films prepared from them are better, but aromatic hydrocarbons are also good solvents for hole transport layer materials, which will damage the film formation of the hole transport layer, and will This results in obvious agglomeration and holes in the light-emitting layer of the quantum dots, resulting in roughness of the quantum dot thin film, and adversely affecting the film-forming quality of the electron transport layer.
  • the purpose of the embodiments of the present application is to provide a quantum dot light-emitting diode and a preparation method thereof, aiming at solving the technical problem of instability of the hole functional layer thin film in the existing quantum dot light-emitting diode.
  • the present application provides a method for preparing a quantum dot light-emitting diode, comprising the following steps:
  • the hole functional material is an organic material containing a benzyl group.
  • the present application provides a quantum dot light-emitting diode, comprising an anode, a cathode, and a quantum dot light-emitting layer located between the anode and the cathode, and a quantum dot light-emitting layer is disposed between the anode and the quantum dot light-emitting layer.
  • a hole functional layer, the material of the hole functional layer includes a cross-linking agent and a cross-linked product after the cross-linking of an organic material containing a benzyl group.
  • the beneficial effect of the preparation method of the quantum dot light-emitting diode provided by the embodiment of the present application is that: when the quantum dot light-emitting diode prepares the hole functional layer, the mixed solution containing the crosslinking agent and the hole functional material is deposited on the substrate. Annealing treatment, and then cross-linking reaction with UV light; during the UV light process, the cross-linking agent reacts with the benzyl hydrogen in the hole functional material to form a stable free radical, and the cross-linking reaction is carried out through free radical coupling, thereby forming a stable free radical.
  • a hole functional layer film that is insoluble in hydrocarbon organic solvents. The hole functional layer film obtained by such a preparation method has good stability.
  • the effect of the solvent can be used to make the device have a smooth and complete thin film morphology, so as to improve the luminescence performance and lifetime of the device.
  • the beneficial effect of the quantum dot light-emitting diode is that: in the quantum dot light-emitting diode, the hole functional layer includes a cross-linking agent and a cross-linked product obtained by cross-linking an organic material containing a benzyl group.
  • the benzyl hydrogen in the hole functional material reacts to form a stable free radical, and the crosslinking reaction is carried out through the free radical coupling, thereby forming a hole functional layer that is insoluble in hydrocarbon organic solvents, with good stability, so the device has Smooth and complete film morphology with good luminous performance and longevity.
  • Fig. 1 is the flow chart of the preparation method of the quantum dot light-emitting diode of the present application
  • FIG. 2 is a schematic structural diagram of a quantum dot light-emitting diode of the present application
  • Fig. 3 is the electroluminescence spectrogram of Example 1 of the present application and Comparative Example 1;
  • Fig. 4 is the device current efficiency diagram of Example 1 and Comparative Example 1 of the present application;
  • FIG. 5 is a graph showing the device life test curve of Example 1 and Comparative Example 1 of the present application.
  • Some embodiments of the present application provide a preparation method of a quantum dot light-emitting diode, as shown in FIG. 1 , the preparation method includes the following steps:
  • S02 depositing a mixed solution containing a crosslinking agent and a hole functional material on the substrate, performing annealing treatment, and then performing a crosslinking reaction with ultraviolet light to obtain a hole functional layer;
  • the hole functional material is an organic material containing a benzyl group.
  • the method for preparing a quantum dot light-emitting diode comprises depositing a mixed solution containing a crosslinking agent and a hole functional material on a substrate for annealing treatment, and then performing a crosslinking reaction with ultraviolet light to obtain a hole functional layer.
  • the crosslinking agent reacts with the benzyl hydrogen in the hole functional material to form stable free radicals, and the crosslinking reaction is carried out through free radical coupling, thereby forming a hole functional layer film that is insoluble in hydrocarbon organic solvents , the hole functional layer film obtained by such a preparation method has good stability, and is not easily affected by the solvent used in the preparation of the quantum dot light-emitting layer when it is used in a quantum dot light-emitting diode, so that the device has a smooth and complete film. morphology to improve the luminescence performance and lifetime of the device.
  • the cross-linking agent is selected from at least one of benzophenone and benzophenone derivatives, specifically, the cross-linking agent may be benzophenone or benzophenone Derivatives, also combinations of benzophenone and benzophenone derivatives.
  • the cross-linking agent may be benzophenone or benzophenone Derivatives, also combinations of benzophenone and benzophenone derivatives.
  • a certain proportion of benzophenone and benzophenone derivatives are doped in the hole transport material.
  • the highly active benzyl hydrogen on the hole functional layer material reacts, and stable free radicals can be formed after the reaction, and the free radicals are coupled and cross-linked to form a hole functional layer film that is insoluble in hydrocarbon organic solvents.
  • the hole functional layer can be prevented from being damaged by the hydrocarbon organic solvent, thereby maintaining a smooth and complete thin film shape.
  • the benzophenone derivative is selected from 2,4-dinitrobenzophenone, 2-hydroxy-4-methoxybenzophenone and 2-hydroxy-4-n-octyloxydiphenone At least one of benzophenones. Specifically, it can be 2,4-dinitrobenzophenone, or 2-hydroxy-4-methoxybenzophenone, or 2-hydroxy-4-n-octyloxybenzophenone, Or two or three of the above-mentioned 2,4-dinitrobenzophenone, 2-hydroxy-4-methoxybenzophenone and 2-hydroxy-4-n-octyloxybenzophenone combination.
  • the benzyl-containing organic material is selected from poly(9-vinylcarbazole), poly[(9,9-di-n-octylfluorenyl-2,7-diyl)-alt- (4,4′-(N-(4-n-butyl)phenyl)-diphenylamine)], poly[(9,9-di-n-octylfluorenyl-2,7-phenylethylene)- alt-(2-methoxy-5-(2-ethylhexyloxy)-1,4diyl)], poly(9,9-dioctylfluorene-2,7-diyl)-alt- (N,N'-diphenylbenzidine-N,N'-diyl), poly(9,9-di-n-octylfluorenyl-2,7-diyl), poly[(N,N'-diyl) (4-n-butyl) (4-
  • the above hole functional material not only contains a benzyl group and can be cross-linked with benzophenone or a benzophenone derivative, but also has good hole transport performance.
  • the mixed solution containing the cross-linking agent and the hole-functional material is prepared by dissolving the above-mentioned cross-linking agent and the hole-functional material in a solvent.
  • the concentration of the hole functional material in the mixed solution is 8-50mg/ml, 40mg/ml, 50mg/ml, etc., the dispersion effect of the cavity functional material is better at this concentration;
  • the mass ratio of the crosslinking agent and the cavity functional material in the mixed solution is (0.5-10): 100 , specifically, the mass ratio of the crosslinking agent and the hole functional material can be 0.5:100, 1:100, 2:100, 4:100, 5:100, etc.; if the proportion of the crosslinking agent is too low, the hole function
  • the material is not sufficiently cross-linked, and may be destroyed during the subsequent preparation of the quantum dot light-emitting layer; when the proportion of the cross-linking agent is too high, since benzophenone or benzophenone derivatives are non-conductive cross-linking agents,
  • the solvent in the mixed solution is selected from non-polar solvents such as hydrocarbon solvents.
  • the hydrocarbon solvent is selected from at least one of saturated or unsaturated alkanes and saturated or unsaturated aromatic hydrocarbons.
  • the method of depositing the mixed solution containing the crosslinking agent and the hole functional material on the substrate includes spin coating, blade coating, printing, spray coating, and the like.
  • the subsequent annealing process can be performed in an anhydrous and oxygen-free environment.
  • the temperature of the annealing treatment is 80-150°C, for example, the temperature of the annealing treatment may be 80°C, 100°C, 120°C, 140°C, 150°C, etc.; the temperature of the annealing treatment is 10°C -30min, for example, the time of annealing treatment can be 10min, 15min, 20min, 25min, 30min, etc.
  • the film-forming effect is better under the above annealing conditions.
  • the wavelength of the ultraviolet light is 200-410nm, such as 200nm, 250nm, 300nm, 400nm, etc.; the time of the ultraviolet light is 5-15min, such as 5min, 10min, 15min; the above-mentioned ultraviolet light conditions The effect of cross-linking reaction is better.
  • the substrate is an anode substrate
  • the method further includes preparing a quantum dot light-emitting layer on the surface of the hole functional layer, and preparing a cathode on the quantum dot light-emitting layer.
  • the cross-linking agent reacts with benzyl-containing organic materials, and the cross-linking agent reacts with benzyl hydrogen to form stable free radicals, and the cross-linking reaction is carried out through free radical coupling, so as to stabilize the quantum dot light-emitting layer and hole functional layer In this way, the non-radiative recombination caused by interface defects can be reduced, and the electro-optical efficiency and lifespan of quantum dot light-emitting diodes can be further improved.
  • the quantum dot light-emitting layer is obtained by annealing a quantum dot solution containing a high molecular polymer to form a film, and the temperature of the quantum dot solution annealing is greater than or equal to the glass transition temperature of the high molecular polymer.
  • the quantum dot solution containing the crosslinking agent is deposited on the substrate for annealing treatment to obtain the quantum dot light-emitting layer, because the annealing temperature of the quantum dot solution is greater than or equal to the glass transition temperature of the polymer, specifically, when the annealing temperature is equal to high When the glass transition temperature of the molecular polymer is high, the high molecular polymer is in a high elastic state.
  • the annealing temperature is greater than the glass transition temperature of the high molecular polymer
  • the high molecular polymer is in a viscous fluid state.
  • the molecular structure of the molecular polymer is more relaxed, so that the positions of the quantum dots in the light-emitting layer of the quantum dots are rearranged, and they are tightly packed and regularly arranged in the polymer to form a flat quantum dot film.
  • the point light-emitting layer can significantly improve the electro-optical efficiency and lifetime of the device.
  • the high molecular polymer is selected from at least one of vinyl-based polymers, acryl-based polymers, amide-based polymers, phenyl-based polymers and carbonate-based polymers, for example , which can be vinyl-based polymers, or propylene-based polymers, or amide-based polymers, or phenyl-based polymers, or carbonate-based polymers, or one or both of the above-mentioned polymers etc combination. From the above macromolecular polymers, select a suitable glass transition temperature ( ⁇ quantum dot solution annealing temperature) and mix with quantum dot materials to prepare a quantum dot light-emitting layer.
  • ⁇ quantum dot solution annealing temperature a suitable glass transition temperature
  • the vinyl-based polymer is selected from at least one of polyvinyl alcohol, polyvinyl carbazole, polyvinyl acetate, polytetrafluoroethylene, polyvinylidene fluoride and polyvinyl chloride;
  • the base polymer is selected from at least one of polyacrylic acid, polymethyl methacrylate, poly( ⁇ -butyl nitrile acrylate), polyacrylamide and polyacrylonitrile;
  • the amide polymer is selected from polyamide At least one of decyl formamide and polyethylene sebacate;
  • the phenyl-based polymer is selected from at least one of polyphenylene sulfide and polyethylene terephthalate;
  • the quasi-polymer is selected from at least one of polycarbonate diol and brominated polycarbonate.
  • the glass transition temperature of the high-molecular polymer is 30-200° C.; the annealing temperature of the quantum dot solution is 50-250° C., and the annealing temperature of the quantum dot solution is greater than or equal to the glass of the high-molecular polymer transition temperature. Further, preferably, the glass transition temperature is selected to be in the range of 50-150° C., and the temperature of the quantum dot solution annealing is 120-180° C. The low glass transition temperature enables low-temperature annealing and has little influence on the thermal aging of the device. .
  • the glass transition temperature of polymethyl methacrylate is 105°C
  • the annealing temperature of the quantum dot solution can be selected to be ⁇ 105°C.
  • the glass transition temperature of polytetrafluoroethylene is 130°C, so the annealing temperature of quantum dot solution can be selected ⁇ 130°C; the glass transition temperature of polyacrylamide is 165°C, and the annealing temperature of quantum dot solution is ⁇ 165°C.
  • the quantum dot solution containing the high molecular polymer is formulated by dissolving the quantum dots and the high molecular polymer in a solvent.
  • the concentration of the quantum dots in the quantum dot solution is 10-50mg/ml, and specifically, the concentration of the quantum dot material can be 10mg/ml, 20mg/ml, 30mg/ml, 40mg/ml, 50mg/ml ml, etc., the quantum dot dispersion effect is better at this concentration;
  • the mass ratio of the high molecular polymer and the quantum dot in the mixed solution is (0.5-10): 100, specifically, the high molecular polymer and
  • the mass ratio of the quantum dot material can be 0.5:100, 1:100, 4:100, 5:100, 10:100, etc. Under the condition of this mass ratio, the quantum dots can be better stacked and arranged in a regular manner Quantum dot films.
  • the hole function layer is a hole transport layer
  • the hole function material is a hole transport material containing a benzyl group.
  • an embodiment of the present application further provides a quantum dot light-emitting diode, comprising an anode, a cathode, and a quantum dot light-emitting layer located between the anode and the cathode, and between the anode and the quantum dot light-emitting layer
  • a hole functional layer is provided, and the material of the hole functional layer includes a cross-linking agent and a cross-linked product obtained by cross-linking of a benzyl group-containing organic material.
  • the hole functional layer includes a cross-linking product obtained by cross-linking a cross-linking agent and a benzyl-containing organic material, and the cross-linking agent reacts with benzyl hydrogen in the hole-functional material to form Stable free radicals, and the cross-linking reaction is carried out through free radical coupling, thereby forming a hole functional layer that is insoluble in hydrocarbon organic solvents, with good stability, so the device has a smooth and complete film morphology, and has good stability. Luminous performance and longevity.
  • the above quantum dot light-emitting diodes are prepared by the preparation methods described in the examples of the present application, and the film formation of the hole functional layer has good stability, so the device has a smooth and complete film shape, and has good luminous performance and life.
  • a hole functional layer film is prepared by doping a crosslinking agent in the hole functional layer material, and after preparing the hole functional layer film by ultraviolet light, a free radical coupling crosslinking reaction occurs by means of ultraviolet light, forming a hydrocarbon-insoluble organic layer.
  • the hole functional layer film of the solvent such as the hole transport layer film, can prevent the hole transport layer from being damaged by the hydrocarbon organic solvent during the subsequent preparation of the quantum dot light-emitting layer film, thereby maintaining the smooth and complete film shape of the device.
  • the crosslinking agent is selected from at least one of benzophenone and benzophenone derivatives;
  • the benzyl group-containing organic material is selected from poly(9-vinylcarbazole), poly[(( 9,9-Di-n-octylfluorenyl-2,7-diyl)-alt-(4,4′-(N-(4-n-butyl)phenyl)-diphenylamine)], poly[(9 ,9-Di-n-octylfluorenyl-2,7-phenyleneethylene)-alt-(2-methoxy-5-(2-ethylhexyloxy)-1,4diyl)], Poly(9,9-dioctylfluorene-2,7-diyl)-alt-(N,N'-diphenylbenzidine-N,N'-diyl), poly(9,9-dinormal Octylfluorenyl-2,7-diyl
  • the material of the quantum dot light-emitting layer includes quantum dots and a high molecular polymer
  • the annealing temperature of the quantum dot light-emitting layer during annealing to form a film is greater than or equal to the glass transition temperature of the high molecular polymer.
  • the mass ratio of the high molecular polymer and the quantum dots is (0.5-10): 100; 4:100, 5:100, 10:100, etc.
  • the high molecular polymer is selected from at least one of vinyl-based polymers, acryl-based polymers, amide-based polymers, phenyl-based polymers and carbonate-based polymers.
  • the hole functional layer contains 5% of 2-hydroxy-4-methoxybenzophenone and poly[(9,9-di-n-octylfluorenyl-2,7-di] base)-alt-(4,4′-(N-(4-n-butyl)phenyl)-diphenylamine)], after the formation of the hole functional layer, use a 365nm UV curing lamp for 10min to conduct free radical coupling
  • the quantum dot light-emitting layer is formed on the hole functional layer.
  • the red quantum dot solution with 3% polyacrylic acid (accounting for the mass fraction of the quantum dots) is selected, and 100 °C is selected as the annealing temperature.
  • the EQE of the prepared device was 18.9%, and the T95@1000nit was 1294h;
  • the hole functional layer is a hole transport layer, and further, a hole injection layer is provided between the hole transport layer and the anode.
  • an electronic functional layer such as an electron transport layer, or a stacked electron injection layer and an electron transport layer is provided between the quantum dot light-emitting layer and the cathode, wherein the electron injection layer and the The cathodes are adjacent.
  • the quantum dot light-emitting diode provided by the embodiments of the present application includes an upside-down structure and an upside-down structure.
  • the upright structure quantum dot light-emitting diode comprises a stacked structure of oppositely disposed anode and cathode, a quantum dot light-emitting layer disposed between the anode and the cathode, disposed between the anode and the cathode
  • a hole transport layer between the quantum dot light-emitting layers, and the anode is disposed on the substrate.
  • a hole functional layer such as a hole injection layer and an electron blocking layer can also be arranged between the anode and the quantum dot light-emitting layer; an electron transport layer can also be arranged between the cathode and the quantum dot light-emitting layer. layer, electron injection layer and hole blocking layer and other electronic functional layers.
  • the quantum dot light-emitting diode includes a substrate, an anode disposed on the surface of the substrate, the hole injection layer disposed on the surface of the anode, and the hole injection layer disposed on the surface of the anode.
  • an inverted-structure quantum dot light-emitting diode includes a stacked structure of an anode and a cathode disposed opposite to each other, a quantum dot light-emitting layer disposed between the anode and the cathode, and disposed between the anode and the cathode.
  • a hole transport layer between the quantum dot light-emitting layers, and the cathode is disposed on the substrate.
  • a hole functional layer such as a hole injection layer and an electron blocking layer can also be arranged between the anode and the quantum dot light-emitting layer; an electron transport layer can also be arranged between the cathode and the quantum dot light-emitting layer.
  • the quantum dot light-emitting diode comprises a substrate, a cathode disposed on the surface of the substrate, the electron transport layer disposed on the surface of the cathode, and an electron transport layer disposed on the surface of the electron transport layer.
  • Substrates include rigid, flexible substrates, specifically glass, silicon wafers, polycarbonate, polymethyl methacrylate, polyethylene terephthalate, polyethylene naphthalate, polyamide, Polyethersulfone, or a combination thereof.
  • Anodes include metals or alloys thereof such as nickel, platinum, vanadium, chromium, copper, zinc, or gold; conductive metal oxides such as zinc oxide, indium oxide, tin oxide, indium tin oxide (ITO), indium zinc oxide (IZO), or fluorine-doped tin oxide; or a combination of metals and oxides such as ZnO and Al or SnO 2 and Sb, but not limited thereto, any two or more of the above may be combined.
  • metals or alloys thereof such as nickel, platinum, vanadium, chromium, copper, zinc, or gold
  • conductive metal oxides such as zinc oxide, indium oxide, tin oxide, indium tin oxide (ITO), indium zinc oxide (IZO), or fluorine-doped tin oxide
  • a combination of metals and oxides such as ZnO and Al or SnO 2 and Sb, but not limited thereto, any two or more of the above may be combined.
  • the hole injection layer includes conductive compounds, including polythiophene, polyaniline, polypyrrole, poly(p-phenylene), polyfluorene, poly(3,4-ethylenedioxythiophene), poly(3,4-ethylenediene) ethyldioxythiophene) polystyrene sulfonate (PEDOT: PSS), MoO 3 , WoO 3 , NiO, HATCN, CuO, V 2 O 5 , CuS, or a combination thereof.
  • conductive compounds including polythiophene, polyaniline, polypyrrole, poly(p-phenylene), polyfluorene, poly(3,4-ethylenedioxythiophene), poly(3,4-ethylenediene) ethyldioxythiophene) polystyrene sulfonate (PEDOT: PSS), MoO 3 , WoO 3 , NiO, HATCN, CuO, V 2 O 5 , CuS, or a combination thereof.
  • the benzyl-containing organic material of the hole transport layer is selected from poly(9-vinylcarbazole), poly[(9,9-di-n-octylfluorenyl-2,7-diyl)-alt-(4, 4′-(N-(4-n-butyl)phenyl)-diphenylamine)], poly[(9,9-di-n-octylfluorenyl-2,7-phenylethylene)-alt-( 2-methoxy-5-(2-ethylhexyloxy)-1,4diyl)], poly(9,9-dioctylfluorene-2,7-diyl)-alt-(N, N'-diphenylbenzidine-N,N'-diyl), poly(9,9-di-n-octylfluorenyl-2,7-diyl), poly[(N,N'-(4- n-butylphen
  • the quantum dots in the quantum dot light-emitting layer are group II-VI CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe, CdH
  • the material of the electron transport layer is one or more of ZnO, TiO 2 , Alq 3 , SnO 2 , ZrO, AlZnO, ZnSnO, BCP, TAZ, PBD, TPBI, Bphen, and CsCO 3 .
  • Cathodes include metals or their alloys such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, lead, cesium, or barium; multilayer construction materials include alkali metal halides, alkaline earth metals A structure of a first layer of halide, alkali metal oxide, or a combination thereof, and a metal layer, wherein the metal layer comprises an alkaline earth metal, a Group 13 metal, or a combination thereof.
  • LiF/Al, LiO 2 /Al, LiF/Ca, Liq/Al, and BaF 2 /Ca but not limited thereto.
  • the anode is selected from indium tin oxide (ITO), the hole injection layer is PEDOT:PSS, and the hole transport layer is poly[(9,9-di-n-octylfluorenyl-2,7] -diyl)-alt-(4,4′-(N-(4-n-butyl)phenyl)-diphenylamine)] and 2-hydroxy-4-methoxybenzophenone, quantum dot light-emitting layer It is a red quantum dot material, the electron transport layer is ZnO, and the cathode is Ag.
  • ITO indium tin oxide
  • the hole injection layer is PEDOT:PSS
  • the hole transport layer is poly[(9,9-di-n-octylfluorenyl-2,7] -diyl)-alt-(4,4′-(N-(4-n-butyl)phenyl)-diphenylamine)] and 2-hydroxy-4-methoxybenzophen
  • the thickness of the anode is 20-200 nm; the thickness of the hole injection layer is 20-200 nm; the thickness of the hole transport layer is 30-180 nm; the quantum dot mixed light-emitting layer The total thickness is 30 to 180 nm.
  • the thickness of the electron transport layer is 10-180 nm; the thickness of the cathode is 40-190 nm.
  • the QLED device includes a substrate 1 , an anode 2 , a hole injection layer 3 , a hole transport layer 4 , and a quantum dot light-emitting layer 5 in order from bottom to top , electron transport layer 6 , cathode 7 .
  • the material of the substrate 1 is a glass sheet
  • the material of the anode 2 is an ITO substrate
  • the material of the hole injection layer 3 is PEDOT:PSS
  • the material of the hole transport layer 4 is 2-hydroxy-4-methoxydiphenyl Methyl ketone and poly[(9,9-di-n-octylfluorenyl-2,7-diyl)-alt-(4,4′-(N-(4-n-butyl)phenyl)-diphenylamine) ]
  • the material of the quantum dot light-emitting layer 5 is CdZnSe/ZnSe/ZnS red quantum dots
  • the material of the electron transport layer 6 is ZnO
  • the material of the cathode 7 is Al.
  • the preparation method of the device includes the following steps:
  • the hole injection layer PEDOT:PSS material was spin-coated on the anode ITO, and then annealed at 100 °C for 15 min; then the hole injection layer was spin-coated with 2-hydroxy-4-methoxydibenzyl with a mass ratio of 5:100 Ketones and Poly[(9,9-Di-n-octylfluorenyl-2,7-diyl)-alt-(4,4′-(N-(4-n-butyl)phenyl)-diphenylamine)]
  • the mixed solution was annealed at 100 °C for 15 min, and irradiated under a 365 nm UV lamp for 10 min to obtain a hole transport layer; the quantum dots of CdZnSe/ZnSe/ZnS red quantum dots containing 3% polyacrylic acid were formed on the hole transport layer as the bearing part.
  • Point light-emitting layer using 100 °C annealing to rearrange the quantum dot position; spin-coating ZnO ethanol solution on the quantum dot light-emitting layer to obtain an electron transport layer; finally, by evaporating the Ag cathode electrode layer, encapsulation to form an electroluminescent device.
  • the QLED device includes a substrate 1 , an anode 2 , a hole injection layer 3 , a hole transport layer 4 , and a quantum dot light-emitting layer 5 in order from bottom to top , electron transport layer 6 , cathode 7 .
  • the material of the substrate 1 is a glass sheet
  • the material of the anode 2 is an ITO substrate
  • the material of the hole injection layer 3 is PEDOT:PSS
  • the material of the hole transport layer 4 is 2-hydroxy-4-n-octyloxydi Benzophenone and poly(9-vinylcarbazole)
  • the material of quantum dot light-emitting layer 5 is CdZnSe/ZnSe/ZnS red quantum dots
  • the material of electron transport layer 6 is ZnO
  • the material of cathode 7 is Al.
  • the preparation method of the device includes the following steps:
  • the hole injection layer PEDOT:PSS material was spin-coated on the anode ITO, and then annealed at 100 °C for 15 min; then the hole injection layer was spin-coated with 2-hydroxy-4-n-octyloxydiphenyl with a mass ratio of 4:100
  • the mixed solution of methyl ketone and poly(9-vinylcarbazole) was annealed at 100 °C for 15 min, and irradiated under a 365 nm UV lamp for 10 min to obtain a hole transport layer; CdZnSe/ZnSe/ZnS was formed on the hole transport layer as a carrier
  • the quantum dot light-emitting layer of the red quantum dots; the ethanol solution of ZnO is spin-coated on the quantum dot light-emitting layer to obtain an electron transport layer; finally, an electroluminescent device is formed by encapsulating the Ag cathode electrode layer by evaporation.
  • the QLED device includes a substrate 1 , an anode 2 , a hole injection layer 3 , a hole transport layer 4 , and a quantum dot light-emitting layer 5 in order from bottom to top , electron transport layer 6 , cathode 7 .
  • the material of the substrate 1 is a glass sheet
  • the material of the anode 2 is an ITO substrate
  • the material of the hole injection layer 3 is PEDOT:PSS
  • the material of the hole transport layer 4 is benzophenone and poly[(9,9 -Di-n-octylfluorenyl-2,7-phenyleneethylene)-alt-(2-methoxy-5-(2-ethylhexyloxy)-1,4diyl)], quantum dots
  • the material of the light-emitting layer 5 is CdZnSe/ZnSe/ZnS red quantum dots
  • the material of the electron transport layer 6 is ZnO
  • the material of the cathode 7 is Al.
  • the preparation method of the device includes the following steps:
  • the hole injection layer PEDOT:PSS material was spin-coated on the anode ITO, and then annealed at 100 °C for 15 min; then the hole injection layer was spin-coated with benzophenone and poly[(9,9- A mixed solution of di-n-octylfluorenyl-2,7-phenyleneethylene)-alt-(2-methoxy-5-(2-ethylhexyloxy)-1,4diyl)], Annealed at 100°C for 15min, irradiated under a 365nm UV lamp for 10min to obtain a hole transport layer; a quantum dot light-emitting layer of CdZnSe/ZnSe/ZnS red quantum dots was formed on the hole transport layer as a carrier; spin on the quantum dot light-emitting layer An ethanol solution of ZnO is coated to obtain an electron transport layer; finally, an electroluminescent device is formed by encapsulating the Ag cathode electrode layer by vapor deposition
  • the quantum dot light-emitting diode device of this comparative example is only poly[(9,9-di-n-octylfluorenyl-2,7-diyl)-alt-(4,4′-(N- (4-n-butyl)phenyl)-diphenylamine)], other is the same as Example 1.
  • the quantum dot light-emitting diode device of this comparative example is the same as that of Example 2 except that the material of the hole transport layer is only poly(9-vinylcarbazole).
  • the quantum dot light-emitting diode device of this comparative example is only poly[(9,9-di-n-octylfluorenyl-2,7-phenyleneethylene)-alt-(2-methoxyl) -5-(2-ethylhexyloxy)-1,4diyl)], other are the same as in Example 3.
  • the life test of the device adopts the 128-channel life test system customized by Guangzhou New Vision Company.
  • the system architecture is to drive the QLED with a constant voltage and constant current source, and test the change of voltage or current; the photodiode detector and test system test the change of the brightness (photocurrent) of the QLED; the luminance meter tests and calibrates the brightness (photocurrent) of the QLED.
  • the hole functional layer film formed by the crosslinkable hole transport material is used, and the positions of the quantum dots in the light emitting layer are rearranged, so that the light emitting performance and life of the device can be improved.
  • the current efficiency and lifetime of the quantum dot light-emitting diode obtained in Example 1 are 2.7 times and 5 times that of the non-crosslinked hole transport layer device, respectively.
  • the crosslinked hole transport layer obtained in the embodiment of the present application can avoid the formation of quantum dots to emit light Therefore, the use of cross-linkable hole transport materials can not only improve the film formation of the functional layer, but also improve the optoelectronic properties of the device.

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Abstract

一种量子点发光二极管及其制备方法。该量子点发光二极管的制备方法包括如下步骤：提供基板（2）（S01）；将含有交联剂和空穴功能材料的混合溶液沉积在所述基板（2）上，进行退火处理，然后紫外光照进行交联反应，得到空穴功能层；其中，所述空穴功能材料为含苄基的有机材料（S02）。该制备方法得到量子点发光二极管中，形成的空穴功能层薄膜具有很好的稳定性，不易受量子点发光层（5）制备使用的溶剂的影响，从而使器件具有平滑完整的薄膜形态，可以提高器件的发光性能和寿命。

Description

量子点发光二极管及其制备方法
本申请要求于2020年07月22日在中国专利局提交的、申请号为202010711460.0、发明名称为“量子点发光二极管及其制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本申请涉及显示器件技术领域，具体涉及一种量子点发光二极管及其制备方法。
 背景技术
利用量子点（Quantum Dot，QD）的量子限域效应，可以开发出荧光量子产率极高的量子点材料，目前已经可以制备出荧光量子产率接近100%的量子点。另外，量子点发光峰的半高峰宽（Full Width at Half Maximum，FWHM<30 nm）很窄，表明量子点可以发出色谱更纯的光，且色域更广。因此，基于量子点制备的量子点发光二极管（Quantum Dot Light Emitting Diode，QLED）的电致发光器件具有更大色域覆盖率，量子点独特的核壳结构，使其具有比有机量子点发光二极管（Organic Dot Light Emitting Diode，OLED）更好的光、热、水氧稳定性。通过量子点的化学组成成分和颗粒大小进行调节，从而实现量子点的发光颜色从紫外到红外波段的可见光光谱完全覆盖；通过量子点种类的改变，不仅能够制备丰富多彩的发光器件，而且更容易实现对发光颜色的精确控制。量子点因其表面配体可调控，因此可以通过改变量子点的表面配体的极性实现在不同溶剂如有机溶剂和水溶液中进行分散，可调控的表面配体极大地扩展了量子点在不同环境下的应用条件，丰富制备量子点薄膜的方法。正是由于量子点的这一特性，全溶液的制备方法，例如旋涂、喷涂、喷墨印刷等可以完美地用来制备QLED器件。
在多层薄膜的QLED器件结构中，相邻层薄膜的形貌质量有着紧密的相互关系，各功能层的薄膜质量会严重地影响电子和空穴在器件中的注入和传输，从而影响辐射复合的几率。在薄膜制备的过程中，平滑的下层薄膜是制备平整的上层薄膜的前提。要实现全溶液技术制备符合应用要求的QLED器件，首先要防止在制备上层薄膜时下层薄膜被上层溶液溶解破坏，因此相邻薄膜溶剂的选择必须符合正交原则，即溶剂的极性要有明显的差距。然而，有些器件功能层间的溶剂无法选择合适的正交溶剂，或者有些相邻功能层溶剂极性相差明显，也会有部分薄膜相混的现象，尤其是在空穴传输层和量子点发光层之间，芳香烃作为量子点的良溶剂，由其制备的量子点薄膜较佳，但是芳香烃同样是空穴传输层材料的良溶剂，会对空穴传输层成膜造成破坏，同时会造成量子点发光层出现明显的团聚和孔洞，导致量子点薄膜变得粗糙，对电子传输层成膜质量也会产生不利影响。
因此，相关技术有待改进。
 技术问题
本申请实施例的目的在于：提供一种量子点发光二极管及其制备方法，旨在解决现有量子点发光二极管中空穴功能层薄膜不稳定的技术问题。
 技术解决方案
为解决上述技术问题，本申请实施例采用的技术方案是：
第一方面，本申请提供了一种量子点发光二极管的制备方法，包括如下步骤：
提供基板；
将含有交联剂和空穴功能材料的混合溶液沉积在所述基板上，进行退火处理，然后紫外光照进行交联反应，得到空穴功能层；
其中，所述空穴功能材料为含苄基的有机材料。
第二方面，本申请提供了一种量子点发光二极管，包括阳极、阴极以及位于所述阳极和所述阴极之间的量子点发光层，所述阳极和所述量子点发光层之间设置有空穴功能层，所述空穴功能层的材料包括交联剂和含苄基的有机材料交联后的交联产物。
 有益效果
本申请实施例提供的量子点发光二极管的制备方法的有益效果在于：该量子点发光二极管在制备空穴功能层时，是将含有交联剂和空穴功能材料的混合溶液沉积在基板上进行退火处理，然后紫外光照进行交联反应得到；该紫外光照过程中，交联剂与空穴功能材料中的苄基氢反应形成稳定的自由基，并且通过自由基耦合进行交联反应，从而形成不溶于烃类有机溶剂的空穴功能层薄膜，这样的制备方法得到的空穴功能层薄膜具有很好的稳定性，将其用于量子点发光二极管中，不易受量子点发光层制备使用的溶剂的影响，从而使器件具有平滑完整的薄膜形态，以提高器件的发光性能和寿命。
本申请实施例提供的量子点发光二极管的有益效果在于：该量子点发光二极管中，空穴功能层包括交联剂和含苄基的有机材料交联后的交联产物，交联剂与空穴功能材料中的苄基氢反应形成稳定的自由基，并且通过自由基耦合进行交联反应，从而形成不溶于烃类有机溶剂的空穴功能层，具有很好的稳定性，因此该器件具有平滑完整的薄膜形态，具有很好的发光性能和寿命。
 附图说明
为了更清楚地说明本申请实施例中的技术方案，下面将对实施例或示范性技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本申请的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其它的附图。
图1是本申请的量子点发光二极管的制备方法流程图；
图2是本申请的量子点发光二极管的结构示意图；
图3是本申请实施例1和对比例1的电致发光光谱图；
图4是本申请实施例1和对比例1的器件电流效率图；
图5是本申请实施例1和对比例1的器件寿命测试曲线图。
 本发明的实施方式
为了使本申请的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本申请进行进一步详细说明。应当理解，此处所描述的具体实施例仅用以解释本申请，并不用于限定本申请。
本申请一些实施例提供了一种量子点发光二极管的制备方法，如图1所示，该制备方法包括如下步骤：
S01：提供基板；
S02：将含有交联剂和空穴功能材料的混合溶液沉积在所述基板上，进行退火处理，然后紫外光照进行交联反应，得到空穴功能层；
其中，所述空穴功能材料为含苄基的有机材料。
本申请实施例提供的量子点发光二极管的制备方法，通过将含有交联剂和空穴功能材料的混合溶液沉积在基板上进行退火处理，然后紫外光照进行交联反应得到空穴功能层。该紫外光照过程中，交联剂与空穴功能材料中的苄基氢反应形成稳定的自由基，并且通过自由基耦合进行交联反应，从而形成不溶于烃类有机溶剂的空穴功能层薄膜，这样的制备方法得到的空穴功能层薄膜具有很好的稳定性，将其用于量子点发光二极管中，不易受量子点发光层制备使用的溶剂的影响，从而使器件具有平滑完整的薄膜形态，以提高器件的发光性能和寿命。
在一些实施例中，所述交联剂选自二苯甲酮和二苯甲酮衍生物中的至少一种，具体地，交联剂可以是二苯甲酮，也可以是二苯甲酮衍生物，也可以是二苯甲酮和二苯甲酮衍生物的组合。本申请实施例通过在空穴传输材料中掺杂一定比例的二苯甲酮和二苯甲酮衍生物，上述二苯甲酮和二苯甲酮衍生物在紫外光照条件下，其羰基跟空穴功能层材料上的高活性的苄基氢反应，反应后可以形成稳定的自由基，自由基耦合交联反应，形成不溶于烃类有机溶剂的空穴功能层薄膜，当在其表面制备量子点发光层薄膜时，可以使空穴功能层避免被烃类有机溶剂破坏，从而保持平滑完整的薄膜形态。
进一步地，所述二苯甲酮衍生物选自2，4-二硝基二苯甲酮、2-羟基-4-甲氧基二苯甲酮和2-羟基-4-正辛氧基二苯甲酮中的至少一种。具体地，可以是2，4-二硝基二苯甲酮，或者是2-羟基-4-甲氧基二苯甲酮，或者是2-羟基-4-正辛氧基二苯甲酮，或者是上述2，4-二硝基二苯甲酮、2-羟基-4-甲氧基二苯甲酮和2-羟基-4-正辛氧基二苯甲酮中两种或三种的组合。
在一些实施例中，所述含苄基的有机材料选自聚(9-乙烯基咔唑)、聚[(9,9-二正辛基芴基-2,7-二基) -alt- (4,4′-(N-(4-正丁基)苯基)-二苯胺)]、聚[(9,9-二正辛基芴基-2,7-亚苯基乙撑)-alt-(2-甲氧基-5-(2-乙基己氧基)-1,4二基)]、聚(9,9-二辛基芴-2,7-二基)-alt-(N,N’-二苯基联苯胺-N,N’-二基)、聚(9,9-二正辛基芴基-2,7-二基)、聚[(N,N’-(4-正丁基苯基)-N,N’-二苯基-1,4-苯二胺)-alt-(9,9-二正辛基芴基-2,7-二基)]、聚[9-(1-辛基壬基)-9H-咔唑]、聚[2-甲氧基-5-(2-乙基己氧基)-1,4-苯乙炔]、聚[2-甲氧基-5-(2-乙基己氧基)-1,4-苯乙炔]、聚[(9,9-二辛基芴基-2,7-二基)-co-并噻吩]和聚[(9,9-二辛基芴基-2,7-二基)-alt-(苯并[2,1,3]噻二唑-4,8-二基)]中的至少一种。例如，可以是上述含苄基的有机材料中的一种，或者是其中的两种或三种的组合。上述空穴功能材料不仅含有苄基，可以与二苯甲酮或二苯甲酮衍生物进行交联反应，而且具有很好的空穴传输性能。
在一些实施例中，含有交联剂和空穴功能材料的混合溶液通过上述交联剂和空穴功能材料溶解在溶剂中配制。其中，所述混合溶液中的所述空穴功能材料的浓度为8-50mg/ml，具体地，空穴功能材料的浓度可以为8mg/ml、10mg/ml、20mg/ml、30mg/ml、40mg/ml、50mg/ml等，该浓度下空穴功能材料分散效果更佳；所述混合溶液中的所述交联剂和所述空穴功能材料的质量比为（0.5-10）：100，具体地，交联剂和空穴功能材料的质量比可以为0.5：100、1：100、2：100、4：100、5：100等；如果交联剂成分比例过低，空穴功能材料交联不充分，后续制备量子点发光层时可能还会被破坏；当交联剂成分比例过高时，由于二苯甲酮或二苯甲酮衍生物属于不导电交联剂，过量的交联剂虽对交联有利，但会降低空穴功能层的空穴的注入和传输能力，从而影响器件整体性能。因此，上述比例范围的交联剂和空穴功能层材料，不仅保证良好的薄膜形态，而且有利于提升器件的电流效率和寿命性能。
进一步地，所述混合溶液中的溶剂选自非极性溶剂如烃类溶剂。具体地，所述烃类溶剂选自饱和或者不饱和的烷烃、饱和或者不饱和的芳香烃中的至少一种。将分散有交联剂和空穴功能材料的混合溶液沉积在基板上，并进行退火去除溶剂，然后紫外光照进行交联反应得到空穴功能层薄膜，退火过程不影响述空穴功能材料的稳定性。
在一个实施例中，将含交联剂和空穴功能材料的混合溶液沉积在基板上的方式包括旋涂，刮涂、印刷，喷涂等。后续退火过程可以在无水无氧环境下进行。
在一个实施例中，所述退火处理的温度为80-150℃，例如，退火处理的温度可以为80℃、100℃、120℃、140℃、150℃等；所述退火处理的温度为 10-30min，例如，退火处理的时间可以是10min、15min、20min、25min、30min等；上述退火条件下成膜效果更佳。
在一个实施例中，所述紫外光照的波长为200-410nm，例如200nm、250nm、300nm、400nm等；所述紫外光照的时间为5-15min，例如5 min、10min、15min；上述紫外光照条件下，交联反应的效果更佳。
进一步地，所述基板为阳极基板，在所述基板上得到所述空穴功能层后，还包括在所述空穴功能层表面制备量子点发光层，在所述量子点发光层上制备阴极。
交联剂与含苄基的有机材料发生交联反应，交联剂与苄基氢反应形成稳定的自由基，并且通过自由基耦合进行交联反应，从而稳固量子点发光层和空穴功能层的界面接触，这样可以减少界面缺陷产生的非辐射复合，进一步地提高量子点发光二极管的电光效率和寿命。
在一些实施例中，所述量子点发光层由含有高分子聚合物的量子点溶液退火得到成膜得到，所述量子点溶液退火的温度≥所述高分子聚合物的玻璃化转变温度。将含有交联剂的量子点溶液沉积在基板上进行退火处理得到量子点发光层，因该量子点溶液退火的温度≥高分子聚合物的玻璃化转变温度，具体地，当退火的温度等于高分子聚合物的玻璃化转变温度时，高分子聚合物呈高弹态，当退火的温度大于高分子聚合物的玻璃化转变温度时，高分子聚合物呈粘流态，上述情况均可以使高分子聚合物的分子结构更加松弛，从而使量子点发光层中的量子点位置重排，在高分子聚合物中堆积紧密、排布规整，形成平整的量子点薄膜，这样的制备方法得到的量子点发光层可以显著提高器件的电光效率和寿命。
在一些实施例中，所述高分子聚合物选自乙烯基类聚合物、丙烯基类聚合物、酰胺类聚合物、苯基类聚合物和碳酸酯基类聚合物中的至少一种，例如，可以是乙烯基类聚合物，或者丙烯基类聚合物，或者酰胺类聚合物，或者苯基类聚合物，或者碳酸酯基类聚合物，或者上述高分子聚合物中的一种、两种等的组合。从上述高分子聚合物中，选择合适的玻璃化转变温度（≤量子点溶液退火温度）与量子点材料混合，制备得到量子点发光层。
具体地，所述乙烯基类聚合物选自聚乙烯醇、聚乙烯基咔唑、聚醋酸乙烯酯、聚四氟乙烯、聚偏二氟乙烯和聚氯乙烯中的至少一种；所述丙烯基类聚合物选自聚丙烯酸、聚甲基丙烯酸甲酯、聚(α-腈基丙烯酸丁酯)、聚丙烯酰胺和聚丙烯腈中的至少一种；所述酰胺类聚合物选自聚亚癸基甲酰胺和聚癸二酰乙二胺中的至少一种；所述苯基类聚合物选自聚苯硫醚和聚对苯二甲酸乙二酯中的至少一种；所述碳酸酯类聚合物选自聚碳酸酯二醇、溴化聚碳酸酯中的至少一种。
在一个实施例中，所述高分子聚合物的玻璃化转变温度为30-200℃；所述量子点溶液退火的温度为50-250℃，且量子点溶液退火温度≥高分子聚合物的玻璃化转变温度。进一步地，优选的，选择玻璃化转变温度范围在50-150℃，量子点溶液退火的温度为120-180℃，低的玻璃化转变温度从而可以进行低温退火，从而对器件的热老化影响小。例如，聚甲基丙烯酸甲酯的玻璃化转变温度为105℃，此时量子点溶液退火温度可以选择≥105℃。聚四氟乙烯的的玻璃化转变温度为130℃，故量子点溶液退火温度可以选择≥130℃；聚丙烯酰胺的玻璃化转变温度为165℃，量子点溶液选择的退火温度为≥165℃。
在一些实施例中，含有高分子聚合物的量子点溶液通过量子点和高分子聚合物溶解在溶剂中配制。其中，所述量子点溶液中的所述量子点的浓度为10-50mg/ml，具体地，量子点材料的浓度可以为10mg/ml、20mg/ml、30mg/ml、40mg/ml、50mg/ml等，该浓度下量子点分散效果更佳；所述混合溶液中的所述高分子聚合物和所述量子点的质量比为（0.5-10）：100，具体地，高分子聚合物和量子点材料的质量比可以为0.5：100、1：100、4：100、5：100、10：100等，该质量比条件下，可以是量子点更好地进行堆积、排布成规整的量子点薄膜。
进一步地，上述空穴功能层为空穴传输层，上述空穴功能材料为含苄基的空穴传输材料。
另一方面，本申请实施例还提供一种量子点发光二极管，包括阳极、阴极以及位于所述阳极和所述阴极之间的量子点发光层，所述阳极和所述量子点发光层之间设置有空穴功能层，所述空穴功能层的材料包括交联剂和含苄基的有机材料交联后的交联产物。
本申请实施例提供的量子点发光二极管中，空穴功能层包括交联剂和含苄基的有机材料交联后的交联产物，交联剂与空穴功能材料中的苄基氢反应形成稳定的自由基，并且通过自由基耦合进行交联反应，从而形成不溶于烃类有机溶剂的空穴功能层，具有很好的稳定性，因此该器件具有平滑完整的薄膜形态，具有很好的发光性能和寿命。
具体地，上述量子点发光二极管由本申请实施例所述的制备方法制备得到，空穴功能层成膜具有很好的稳定性，因此该器件具有平滑完整的薄膜形态，具有很好的发光性能和寿命。
在QLED制备工作中发现，量子点发光层材料溶液通过旋涂，刮涂、印刷，喷涂等现有成膜工艺条件在空穴功能层上进行沉积时，为制备较好的量子点薄膜，烃类有机溶剂作为量子点良溶剂是最佳选择，但是芳香烃同样是空穴功能层材料的良溶剂，在量子点发光层成膜过程中会对空穴功能层成膜造成破坏，同时会造成量子点发光层出现明显的团聚和孔洞，导致量子点薄膜变得粗糙，对下一层成膜质量也会产生不利影响。薄膜上的缺陷会增加激子的非辐射复合，对QLED器件的电流效率和寿命影响甚大。因此，本申请实施例通过在空穴功能层材料中掺杂交联剂，紫外光照制备得到空穴功能层薄膜后，通过紫外光照的方式发生自由基耦合交联反应，形成不溶于烃类有机溶剂的空穴功能层薄膜如空穴传输层薄膜，后续制备量子点发光层薄膜时，可以避免空穴传输层被烃类有机溶剂破坏，从而保持器件平滑完整的薄膜形态。
具体地，所述交联剂选自二苯甲酮和二苯甲酮衍生物中的至少一种；所述含苄基的有机材料选自聚(9-乙烯基咔唑)、聚[(9,9-二正辛基芴基-2,7-二基) -alt- (4,4′-(N-(4-正丁基)苯基)-二苯胺)]、聚[(9,9-二正辛基芴基-2,7-亚苯基乙撑)-alt-(2-甲氧基-5-(2-乙基己氧基)-1,4二基)]、聚(9,9-二辛基芴-2,7-二基)-alt-(N,N’-二苯基联苯胺-N,N’-二基)、聚(9,9-二正辛基芴基-2,7-二基)、聚[(N,N’-(4-正丁基苯基)-N,N’-二苯基-1,4-苯二胺)-alt-(9,9-二正辛基芴基-2,7-二基)]、聚[9-(1-辛基壬基)-9H-咔唑]、聚[2-甲氧基-5-(2-乙基己氧基)-1,4-苯乙炔]、聚[2-甲氧基-5-(2-乙基己氧基)-1,4-苯乙炔]、聚[(9,9-二辛基芴基-2,7-二基)-co-并噻吩]和聚[(9,9-二辛基芴基-2,7-二基)-alt-(苯并[2,1,3]噻二唑-4,8-二基)]中的至少一种；所述交联剂与所述含苄基的有机材料的质量比为（0.5-5）:100。具体地，交联剂和含苄基的有机材料含苄基的有机材料的质量比可以为0.5：100、1：100、2：100、4：100、5：100等。
进一步地，所述量子点发光层的材料包括量子点和高分子聚合物，且所述量子点发光层退火成膜时的退火温度≥所述高分子聚合物的玻璃化转变温度。具体地，所述高分子聚合物和所述量子点的质量比为（0.5-10）：100；具体地，高分子聚合物和量子点材料的质量比可以为0.5：100、1：100、4：100、5：100、10：100等。所述高分子聚合物选自乙烯基类聚合物、丙烯基类聚合物、酰胺类聚合物、苯基类聚合物和碳酸酯基类聚合物中的至少一种。
在一个优选的实施例中，空穴功能层为包含5%的2-羟基-4-甲氧基二苯甲酮和聚[(9,9-二正辛基芴基-2,7-二基)-alt-(4,4′-(N-(4-正丁基)苯基)-二苯胺)]，在空穴功能层形成后，使用365nm紫外固化灯照射10min进行自由基耦合交联反应以获得稳定的膜层，在该空穴功能层上进行量子点发光层成膜，选用添加3%聚丙烯酸（占量子点的质量分数）的红色量子点溶液，选择100℃作为退火温度，并进行量子点发光层中量子点位置重排，制备的器件EQE为18.9%，T95@1000nit为1294h；
在一些实施例中，上述量子点发光二极管器件中，空穴功能层为空穴传输层，进一步地，空穴传输层与阳极之间设置有空穴注入层。在另一实施例中，上述量子点发光二极管器件中，量子点发光层与阴极之间设置有电子功能层，如电子传输层，或层叠的电子注入层和电子传输层，其中电子注入层与阴极相邻。
本申请实施例提供的量子点发光二极管包括正置结构和倒置结构。
在一种实施方式中，正置结构量子点发光二极管包括相对设置的阳极和阴极的层叠结构，设置在所述阳极和所述阴极之间的量子点发光层，设置在所述阳极和所述量子点发光层之间的空穴传输层，且所述阳极设置在衬底上。进一步的，所述阳极和所述量子点发光层之间还可以设置空穴注入层、电子阻挡层等空穴功能层；在所述阴极和所述量子点发光层之间还可以设置电子传输层、电子注入层和空穴阻挡层等电子功能层。在一些正置结构器件的实施例中，所述量子点发光二极管包括衬底，设置在所述衬底表面的阳极，设置在阳极表面的所述空穴注入层，设置在所述空穴注入层表面的空穴传输层，设置在所述空穴传输层表面的量子点发光层，设置在量子点发光层表面的电子传输层和设置在电子传输层表面的阴极。
在一种实施方式中，倒置结构量子点发光二极管包括相对设置的阳极和阴极的叠层结构，设置在所述阳极和所述阴极之间的量子点发光层，设置在所述阳极和所述量子点发光层之间的空穴传输层，且所述阴极设置在衬底上。进一步的，所述阳极和所述量子点发光层之间还可以设置空穴注入层、电子阻挡层等空穴功能层；在所述阴极和所述量子点发光层之间还可以设置电子传输层、电子注入层和空穴阻挡层等电子功能层。在一些倒置结构器件的实施例中，所述量子点发光二极管包括衬底，设置在所述衬底表面的阴极，设置在阴极表面的所述电子传输层，设置在所述电子传输层表面的量子点发光层，设置在所述量子点发光层表面的空穴传输层，设置在空穴传输层表面的空穴注入层和设置在空穴注入层表面的阳极。
衬底包括钢性、柔性衬底，具体包括玻璃、硅晶片、聚碳酸酯、聚甲基丙烯酸甲酯、聚对苯二甲酸乙二醇酯、聚萘二甲酸乙二醇酯、聚酰胺、聚醚砜、或其组合。
阳极包括金属或其合金例如镍、铂、钒、铬、铜、锌、或金；导电金属氧化物例如氧化锌、氧化铟、氧化锡、氧化铟锡(ITO)、氧化铟锌(IZO)、或氟掺杂的氧化锡；或者金属和氧化物的组合例如ZnO和Al或者SnO 2和Sb，但是不限于此，可以为以上任意两种或两种以上组合。
空穴注入层包括导电化合物，包括聚噻吩、聚苯胺、聚吡咯、聚(对亚苯基)、聚芴、聚(3 ,4-亚乙基二氧噻吩)、聚(3 ,4-亚乙基二氧噻吩)聚磺苯乙烯(PEDOT：PSS)、MoO 3、WoO 3、NiO、HATCN、CuO、V 2O 5、CuS、或其组合。
空穴传输层的含苄基的有机材料选自聚(9-乙烯基咔唑)、聚[(9,9-二正辛基芴基-2,7-二基) -alt- (4,4′-(N-(4-正丁基)苯基)-二苯胺)]、聚[(9,9-二正辛基芴基-2,7-亚苯基乙撑)-alt-(2-甲氧基-5-(2-乙基己氧基)-1,4二基)]、聚(9,9-二辛基芴-2,7-二基)-alt-(N,N’-二苯基联苯胺-N,N’-二基)、聚(9,9-二正辛基芴基-2,7-二基)、聚[(N,N’-(4-正丁基苯基)-N,N’-二苯基-1,4-苯二胺)-alt-(9,9-二正辛基芴基-2,7-二基)]、聚[9-(1-辛基壬基)-9H-咔唑]、聚[2-甲氧基-5-(2-乙基己氧基)-1,4-苯乙炔]、聚[2-甲氧基-5-(2-乙基己氧基)-1,4-苯乙炔]、聚[(9,9-二辛基芴基-2,7-二基)-co-并噻吩]和聚[(9,9-二辛基芴基-2,7-二基)-alt-(苯并[2,1,3]噻二唑-4,8-二基)]中的至少一种。
量子点发光层中的量子点为II-VI族的CdS、CdSe、CdTe、ZnS、ZnSe、ZnTe、ZnO、HgS、HgSe、HgTe、CdSeS、CdSeTe、CdSTe、ZnSeS、ZnSeTe、ZnSTe、HgSeS、HgSeTe、HgSTe、CdZnS、CdZnSe、CdZnTe、CdHgS、CdHgSe、CdHgTe、HgZnS、HgZnSe、HgZnTe、CdZnSeS、CdZnSeTe、CdZnSTe、CdHgSeS、CdHgSeTe、CdHgSTe、HgZnSeS、HgZnSeTe、HgZnSTe；或III-V族的GaN、GaP、GaAs、GaSb、AlN、AlP、AlAs、AlSb、InN、InP、InAs、InSb、GaNP、GaNAs、GaNSb、GaPAs、GaPSb、AlNP、AlNAs、AlNSb、AlPAs、AlPSb、InNP、InNAs、InNSb、InPAs、InPSb、GaAlNP、GaAlNAs、GaAlNSb、GaAlPAs、GaAlPSb、GaInNP、GaInNAs、GaInNSb、GaInPAs、GaInPSb、InAlNP、InAlNAs、InAlNSb、InAlPAs、InAlPSb；或IV-VI族的SnS、SnSe、SnTe、PbS、PbSe、PbTe、SnSeS、SnSeTe、SnSTe、PbSeS、PbSeTe、PbSTe、SnPbS、SnPbSe、SnPbTe、SnPbSSe、SnPbSeTe、SnPbSTe；或者以上任意一种或多种的组合。量子点发光层中的高分子聚合物选自乙烯基类聚合物、丙烯基类聚合物、酰胺类聚合物、苯基类聚合物和碳酸酯基类聚合物中的至少一种
电子传输层材料为ZnO、TiO 2、Alq 3、SnO 2、ZrO、AlZnO、ZnSnO、BCP、TAZ、PBD、TPBI、Bphen、CsCO 3中的一种或多种。
阴极包括金属或其合金例如镁、钙、钠、钾、钛、铟、钇、锂、钆、铝、银、锡、铅、铯、或钡；多层结构材料包括碱金属卤化物、碱土金属卤化物、碱金属氧化物、或其组合的第一层、和金属层的结构，其中所述金属层包括碱土金属、13族金属、或其组合。例如LiF/Al、LiO 2/Al、LiF/Ca、Liq/Al、和BaF 2/Ca，但是不限于此。
在一个具体的实施方式中，阳极选自铟锡氧化物(ITO)，空穴注入层为PEDOT：PSS，空穴传输层为聚[(9,9-二正辛基芴基-2,7-二基) -alt- (4,4′-(N-(4-正丁基)苯基)-二苯胺)]和2-羟基-4-甲氧基二苯甲酮，量子点发光层为红色量子点材料，电子传输层为ZnO，阴极为Ag。
在一个具体的实施例中，阳极的厚度为20 ~ 200 nm；所述空穴注入层的厚度为20 ~ 200 nm；空穴传输层的厚度为30 ~ 180 nm；所述量子点混合发光层的总厚度为30 ~ 180 nm。所述电子传输层的厚度为10 ~ 180 nm；阴极的厚度为40 ~ 190 nm。
本申请先后进行过多次试验，现举一部分试验结果作为参考对申请进行进一步详细描述，下面结合具体实施例进行详细说明。
实施例1
本实施例提供一种QLED器件，其结构如图2所示，该QLED器件从下而上依次包括衬底1、阳极2、空穴注入层3、空穴传输层4、量子点发光层5、电子传输层6、阴极7。其中，衬底1的材料为玻璃片，阳极2的材料为ITO基板，空穴注入层3的材料为PEDOT：PSS，空穴传输层4的材料为2-羟基-4-甲氧基二苯甲酮和聚[(9,9-二正辛基芴基-2,7-二基)-alt-(4,4′-(N-(4-正丁基)苯基)-二苯胺)]，量子点发光层5的材料为CdZnSe/ZnSe/ZnS红色量子点，电子传输层6的材料为ZnO，阴极7的材料为Al。
该器件的制备方法包括如下步骤：
在阳极ITO上旋涂空穴注入层PEDOT：PSS材料，然后100℃退火15min；然后在空穴注入层上旋涂含质量比为5：100的2-羟基-4-甲氧基二苯甲酮和聚[(9,9-二正辛基芴基-2,7-二基) -alt- (4,4′-(N-(4-正丁基)苯基)-二苯胺)]的混合溶液，100℃退火15min，在365nm紫外灯下照射10min，得到空穴传输层；在作为承载部的空穴传输层上形成含3%聚丙烯酸的CdZnSe/ZnSe/ZnS红色量子点的量子点发光层，使用100℃退火进行量子点位置重排；在量子点发光层上旋涂ZnO的乙醇溶液，得到电子传输层；最后通过蒸镀Ag阴极电极层，封装形成电致发光器件。
实施例2
本实施例提供一种QLED器件，其结构如图2所示，该QLED器件从下而上依次包括衬底1、阳极2、空穴注入层3、空穴传输层4、量子点发光层5、电子传输层6、阴极7。其中，衬底1的材料为玻璃片，阳极2的材料为ITO基板，空穴注入层3的材料为PEDOT：PSS，空穴传输层4的材料为2-羟基-4-正辛氧基二苯甲酮和聚(9-乙烯基咔唑)，量子点发光层5的材料为CdZnSe/ZnSe/ZnS红色量子点，电子传输层6的材料为ZnO，阴极7的材料为Al。
该器件的制备方法包括如下步骤：
在阳极ITO上旋涂空穴注入层PEDOT：PSS材料，然后100℃退火15min；然后在空穴注入层上旋涂含质量比为4：100的2-羟基-4-正辛氧基二苯甲酮和聚(9-乙烯基咔唑)的混合溶液，100℃退火15min，在365nm紫外灯下照射10min，得到空穴传输层；在作为承载的空穴传输层上形成CdZnSe/ZnSe/ZnS红色量子点的量子点发光层；在量子点发光层上旋涂ZnO的乙醇溶液，得到电子传输层；最后通过蒸镀Ag阴极电极层，封装形成电致发光器件。
实施例3
本实施例提供一种QLED器件，其结构如图2所示，该QLED器件从下而上依次包括衬底1、阳极2、空穴注入层3、空穴传输层4、量子点发光层5、电子传输层6、阴极7。其中，衬底1的材料为玻璃片，阳极2的材料为ITO基板，空穴注入层3的材料为PEDOT：PSS，空穴传输层4的材料为二苯甲酮和聚[(9,9-二正辛基芴基-2,7-亚苯基乙撑)-alt-(2-甲氧基-5-(2-乙基己氧基)-1,4二基)]，量子点发光层5的材料为CdZnSe/ZnSe/ZnS红色量子点，电子传输层6的材料为ZnO，阴极7的材料为Al。
该器件的制备方法包括如下步骤：
在阳极ITO上旋涂空穴注入层PEDOT：PSS材料，然后100℃退火15min；然后在空穴注入层上旋涂含质量比为10：100的二苯甲酮和聚[(9,9-二正辛基芴基-2,7-亚苯基乙撑)-alt-(2-甲氧基-5-(2-乙基己氧基)-1,4二基)]的混合溶液，100℃退火15min，在365nm紫外灯下照射10min，得到空穴传输层；在作为承载的空穴传输层上形成CdZnSe/ZnSe/ZnS红色量子点的量子点发光层；在量子点发光层上旋涂ZnO的乙醇溶液，得到电子传输层；最后通过蒸镀Ag阴极电极层，封装形成电致发光器件。
对比例1
本对比例的量子点发光二极管器件除了空穴传输层材料仅为聚[(9,9-二正辛基芴基-2,7-二基)-alt- (4,4′-(N-(4-正丁基)苯基)-二苯胺)]外，其他均与实施例1相同。
对比例2
本对比例的量子点发光二极管器件除了空穴传输层材料仅为聚(9-乙烯基咔唑)外，其他均与实施例2相同。
对比例3
本对比例的量子点发光二极管器件除了空穴传输层材料仅为聚[(9,9-二正辛基芴基-2,7-亚苯基乙撑)-alt-(2-甲氧基-5-(2-乙基己氧基)-1,4二基)]，其他均与实施例3相同。
性能测试
对上述实施例和对比例的量子点发光二极管器件的光电性能和寿命进行了测试，测试结果如表1所述，其中实施例1和对比例1的结果如图3-5所示。
器件的寿命测试采用广州新视界公司定制的128路寿命测试系统。系统架构为恒压恒流源驱动QLED，测试电压或电流的变化；光电二极管探测器和测试系统，测试QLED的亮度(光电流)变化；亮度计测试校准QLED的亮度(光电流)。
表1
EL(nm) FWHM (nm) EQE(%) CE (cd/A) T95@1000nit (h)
实施例 1 623 22 16.3 24 1270
对比例 1 623 22 6 9 248
实施例 2 623 22 17 25 1200
对比例2 623 22 5.5 8.1 198
实施例 3 623 22 15.5 21 1380
对比例 3 623 22 4.5 6.6 109
由上表1的数据可知：本申请实施例使用可交联的空穴传输材料形成的空穴功能层薄膜，并且对发光层量子点位置进行重排，从而可以提高器件的发光性能和寿命。例如实施例1得到的量子点发光二极管的电流效率和寿命分别是非交联空穴传输层器件的2.7倍和5倍，因本申请实施例交联得空穴传输层可以避免在形成量子点发光层的时候被量子点材料溶剂破坏，所以使用可交联的空穴传输材料，不仅可以改善功能层成膜，也可以提升器件的光电性能。
以上仅为本申请的可选实施例而已，并不用于限制本申请。对于本领域的技术人员来说，本申请可以有各种更改和变化。凡在本申请的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本申请的权利要求范围之内。

Claims (20)

  1. 一种量子点发光二极管的制备方法，其特征在于，包括如下步骤：
    提供基板；
    将含有交联剂和空穴功能材料的混合溶液沉积在所述基板上，进行退火处理，然后紫外光照进行交联反应，得到空穴功能层；
    其中，所述空穴功能材料为含苄基的有机材料。
  2. 如权利要求1所述的量子点发光二极管的制备方法，其特征在于，所述交联剂选自二苯甲酮和二苯甲酮衍生物中的至少一种。
  3. 如权利要求1所述的量子点发光二极管的制备方法，其特征在于，所述含苄基的有机材料选自聚(9-乙烯基咔唑)、聚[(9,9-二正辛基芴基-2,7-二基) -alt- (4,4′-(N-(4-正丁基)苯基)-二苯胺)]、聚[(9,9-二正辛基芴基-2,7-亚苯基乙撑)-alt-(2-甲氧基-5-(2-乙基己氧基)-1,4二基)]、聚(9,9-二辛基芴-2,7-二基)-alt-(N,N’-二苯基联苯胺-N,N’-二基)、聚(9,9-二正辛基芴基-2,7-二基)、聚[(N,N’-(4-正丁基苯基)-N,N’-二苯基-1,4-苯二胺)-alt-(9,9-二正辛基芴基-2,7-二基)]、聚[9-(1-辛基壬基)-9H-咔唑]、聚[2-甲氧基-5-(2-乙基己氧基)-1,4-苯乙炔]、聚[2-甲氧基-5-(2-乙基己氧基)-1,4-苯乙炔]、聚[(9,9-二辛基芴基-2,7-二基)-co-并噻吩]和聚[(9,9-二辛基芴基-2,7-二基)-alt-(苯并[2,1,3]噻二唑-4,8-二基)]中的至少一种。
  4. 如权利要求1所述的量子点发光二极管的制备方法，其特征在于，所述混合溶液中，空穴功能材料的浓度为8-50mg/ml；和/或，
    所述混合溶液中，所述交联剂与所述空穴功能材料的质量比为（0.5-10）:100。
  5. 如权利要求1所述的量子点发光二极管的制备方法，其特征在于，所述退火处理的温度为80-150℃；和/或，
    所述退火处理的温度为 10-30min。
  6. 如权利要求1所述的量子点发光二极管的制备方法，其特征在于，所述紫外光照的波长为200-410nm；和/或，
    所述紫外光照的时间为5-15min。
  7. 如权利要求1所述的量子点发光二极管的制备方法，其特征在于，所述基板为阳极基板，在所述基板上得到所述空穴功能层后，还包括在所述空穴功能层表面制备量子点发光层，在所述量子点发光层上制备阴极。
  8. 如权利要求7所述的量子点发光二极管的制备方法，其特征在于，所述量子点发光层由含有高分子聚合物的量子点溶液退火成膜得到，所述量子点溶液退火的温度≥所述高分子聚合物的玻璃化转变温度。
  9. 如权利要求8所述的量子点发光二极管的制备方法，其特征在于，所述高分子聚合物和所述量子点溶液中的量子点的质量比为（0.5-10）：100。
  10. 如权利要求8所述的量子点发光二极管的制备方法，其特征在于，所述高分子聚合物的玻璃化转变温度为50-150℃，所述量子点溶液退火的温度为120-180℃。
  11. 如权利要求8所述的量子点发光二极管的制备方法，其特征在于，所述高分子聚合物选自乙烯基类聚合物、丙烯基类聚合物、酰胺类聚合物、苯基类聚合物和碳酸酯基类聚合物中的至少一种。
  12. 如权利要求11所述的量子点发光二极管的制备方法，其特征在于，所述乙烯基类聚合物选自聚乙烯醇、聚乙烯基咔唑、聚醋酸乙烯酯、聚四氟乙烯、聚偏二氟乙烯和聚氯乙烯中的至少一种；和/或，
    所述丙烯基类聚合物选自聚丙烯酸、聚甲基丙烯酸甲酯、聚(α-腈基丙烯酸丁酯)、聚丙烯酰胺和聚丙烯腈中的至少一种；和/或，
    所述酰胺类聚合物选自聚亚癸基甲酰胺和聚癸二酰乙二胺中的至少一种；和/或，
    所述苯基类聚合物选自聚苯硫醚和聚对苯二甲酸乙二酯中的至少一种；和/或，
    所述碳酸酯类聚合物选自聚碳酸酯二醇和溴化聚碳酸酯中的至少一种。
  13. 一种量子点发光二极管，包括阳极、阴极以及位于所述阳极和所述阴极之间的量子点发光层，所述阳极和所述量子点发光层之间设置有空穴功能层，其特征在于，所述空穴功能层的材料包括交联剂和含苄基的有机材料交联后的交联产物。
  14. 如权利要求13所述的量子点发光二极管，其特征在于，所述交联剂选自二苯甲酮和二苯甲酮衍生物中的至少一种。
  15. 如权利要求13所述的量子点发光二极管，其特征在于，所述含苄基的有机材料选自聚(9-乙烯基咔唑)、聚[(9,9-二正辛基芴基-2,7-二基) -alt- (4,4′-(N-(4-正丁基)苯基)-二苯胺)]、聚[(9,9-二正辛基芴基-2,7-亚苯基乙撑)-alt-(2-甲氧基-5-(2-乙基己氧基)-1,4二基)]、聚(9,9-二辛基芴-2,7-二基)-alt-(N,N’-二苯基联苯胺-N,N’-二基)、聚(9,9-二正辛基芴基-2,7-二基)、聚[(N,N’-(4-正丁基苯基)-N,N’-二苯基-1,4-苯二胺)-alt-(9,9-二正辛基芴基-2,7-二基)]、聚[9-(1-辛基壬基)-9H-咔唑]、聚[2-甲氧基-5-(2-乙基己氧基)-1,4-苯乙炔]、聚[2-甲氧基-5-(2-乙基己氧基)-1,4-苯乙炔]、聚[(9,9-二辛基芴基-2,7-二基)-co-并噻吩]和聚[(9,9-二辛基芴基-2,7-二基)-alt-(苯并[2,1,3]噻二唑-4,8-二基)]中的至少一种。
  16. 如权利要求13所述的量子点发光二极管，其特征在于，所述交联剂与所述含苄基的有机材料的质量比为（0.5-5）:100。
  17. 如权利要求13所述的量子点发光二极管，其特征在于，所述量子点发光层的材料包括量子点和高分子聚合物，且所述量子点发光层退火成膜时的退火温度≥所述高分子聚合物的玻璃化转变温度。
  18. 如权利要求17所述的量子点发光二极管，其特征在于，所述高分子聚合物和所述量子点的质量比为（0.5-10）：100。
  19. 如权利要求17所述的量子点发光二极管，其特征在于，所述高分子聚合物选自乙烯基类聚合物、丙烯基类聚合物、酰胺类聚合物、苯基类聚合物和碳酸酯基类聚合物中的至少一种。
  20. 如权利要求19所述的量子点发光二极管，其特征在于，所述乙烯基类聚合物选自聚乙烯醇、聚乙烯基咔唑、聚醋酸乙烯酯、聚四氟乙烯、聚偏二氟乙烯和聚氯乙烯中的至少一种；和/或，
    所述丙烯基类聚合物选自聚丙烯酸、聚甲基丙烯酸甲酯、聚(α-腈基丙烯酸丁酯)、聚丙烯酰胺和聚丙烯腈中的至少一种；和/或，
    所述酰胺类聚合物选自聚亚癸基甲酰胺和聚癸二酰乙二胺中的至少一种；和/或，
    所述苯基类聚合物选自聚苯硫醚和聚对苯二甲酸乙二酯中的至少一种；和/或，
    所述碳酸酯类聚合物选自聚碳酸酯二醇和溴化聚碳酸酯中的至少一种。
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