WO2022016821A1 - 量子点薄膜及其制备方法和量子点发光二极管 - Google Patents

量子点薄膜及其制备方法和量子点发光二极管 Download PDF

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WO2022016821A1
WO2022016821A1 PCT/CN2020/141767 CN2020141767W WO2022016821A1 WO 2022016821 A1 WO2022016821 A1 WO 2022016821A1 CN 2020141767 W CN2020141767 W CN 2020141767W WO 2022016821 A1 WO2022016821 A1 WO 2022016821A1
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quantum dot
polymer
dot light
high molecular
quantum
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French (fr)
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周礼宽
邹文鑫
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TCL Technology Group Co Ltd
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TCL Technology Group Co Ltd
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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
    • 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
    • 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
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • 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
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/114—Poly-phenylenevinylene; Derivatives thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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

Definitions

  • the application belongs to the technical field of display devices, and in particular relates to a quantum dot film, a preparation method thereof, and a quantum dot light-emitting diode.
  • Quantum Dot Light Emitting Diodes has the advantages of high luminous efficiency, narrow luminescence spectrum, high chemical and optical stability, and can become a high-performance, low-cost electroluminescent device, thus becoming the next generation of light-emitting display devices.
  • quantum dot light-emitting diodes the external quantum efficiency of red, green and blue devices has been close to 20%, and has good repeatability, but the working life of the device is not very ideal.
  • the quantum dot light-emitting layer material of the device is made of spherical quantum dot (Quantum Dot, QD) nanomaterials, the size is generally between 5-15 nanometers, the quantum dot light-emitting layer obtained by spin coating or printing processes has quantum dots.
  • QD quantum dot
  • the problem of loose material accumulation and irregular arrangement makes it easy to form an uneven quantum dot film with "holes", which leads to the movement of carriers in the recombination area of the device, which adversely affects the optoelectronic properties and life of the device. , thereby affecting the efficiency and lifetime of the device.
  • One of the purposes of the embodiments of the present application is to provide a quantum dot film and a preparation method thereof, aiming at solving the technical problem of unevenness of the existing quantum dot film.
  • Another object of the embodiments of the present application is to provide a quantum dot light emitting diode, which aims to solve the technical problem of unevenness of the quantum dot light emitting layer of the quantum dot light emitting diode.
  • the present application provides a method for preparing a quantum dot film, comprising the following steps:
  • the temperature of the annealing treatment is greater than or equal to the glass transition temperature of the high molecular polymer.
  • the present application provides a quantum dot film
  • the material of the quantum dot light-emitting film includes quantum dots and a polymer
  • the annealing temperature of the quantum dot film during annealing to form a film is greater than or equal to the polymer polymerization glass transition temperature of the substance.
  • 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 the quantum dot light-emitting layer is the quantum dot film described in this application.
  • the beneficial effect of the preparation method of the quantum dot film is that: in the preparation method of the quantum dot film, a mixed solution containing quantum dots and a high molecular polymer is deposited on a substrate for annealing treatment to obtain the quantum dot film, During the annealing treatment, the temperature of the annealing treatment is greater than or equal to the glass transition temperature of the high molecular polymer. Specifically, when the temperature of the annealing treatment is equal to the glass transition temperature of the high molecular polymer, the high molecular polymer exhibits high elasticity. When the temperature of the annealing treatment is higher than the glass transition temperature of the polymer, the polymer is in a viscous fluid state.
  • All of the above conditions can make the molecular structure of the polymer more relaxed, thereby making the quantum dot film in the quantum dot film.
  • the position of the quantum dots is rearranged, and they are tightly packed and regularly arranged in the polymer to form a flat quantum dot film.
  • the quantum dot film obtained by this preparation method can be used in quantum dot light-emitting devices, which can significantly improve the electro-optical efficiency and life of the device. .
  • the beneficial effect of the quantum dot film provided by the embodiment of the present application is that the material of the quantum dot film includes quantum dots and high molecular polymers, because the annealing temperature of the quantum dot film during annealing to form a film is greater than or equal to the glass transition of the high molecular polymer. Under these conditions, when the quantum dot film is formed into a film, the positions of the quantum dots are rearranged, and they are densely packed and regularly arranged in the polymer to form a flat quantum dot film. Therefore, the quantum dot film can be used in quantum dot light-emitting devices. Significantly improve the electro-optical efficiency and lifetime of the device.
  • the beneficial effect of the quantum dot light-emitting diode provided by the embodiment of the present application is that the quantum dot light-emitting layer in the quantum dot light-emitting diode is a unique quantum dot film of the present application, so the quantum dot film can improve the electro-optical efficiency of the quantum dot light-emitting diode. life.
  • Fig. 1 is the flow chart of the preparation method of the quantum dot film of the embodiment of the present application.
  • FIG. 2 is a schematic structural diagram of a quantum dot light-emitting diode according to an embodiment 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 method for preparing a quantum dot film, as shown in FIG. 1 , the preparation method includes the following steps:
  • S02 depositing a mixed solution containing quantum dots and a high molecular polymer on the substrate, and then performing annealing treatment to obtain a quantum dot film;
  • the temperature of the annealing treatment is greater than or equal to the glass transition temperature of the high molecular polymer.
  • a mixed solution containing quantum dots and a high molecular polymer is deposited on a substrate and subjected to annealing treatment to obtain a quantum dot film.
  • the glass transition temperature of the polymer specifically, when the annealing temperature is equal to the glass transition temperature of the polymer, the polymer is in a highly elastic state, and when the annealing temperature is greater than the polymer
  • the glass transition temperature is 100%, the polymer is in a viscous fluid state, and the above conditions can make the molecular structure of the polymer more relaxed, so that the positions of the quantum dots in the quantum dot film are rearranged.
  • the quantum dot film obtained by this preparation method is used in a quantum dot light-emitting device, which can significantly improve the electro-optical efficiency and life of the device.
  • the quantum dots include at least one of II-VI, IV-VI, III-V, I-VI compound single-structure and composite-structure quantum dots.
  • the composite structure quantum dots include core-shell structure quantum dots, and the cores constituting the core-shell structure quantum dots include CdSe, CdS, CdTe, CdSeTe, CdZnS, PbSe, ZnTe, CdSeS, PbS, PbTe, HgS, HgSe , at least one of HgTe, GaN, GaP, GaAs, InP, InAs, InZnP, InGaP and InGaN; the shell constituting the core-shell structure quantum dot contains at least one of ZnSe, ZnS and ZnSeS.
  • 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.
  • it can be a vinyl-based polymer, or acryl-based polymer, or an amide-based polymer, or a phenyl-based polymer, or a carbonate-based polymer, or one or two of the above-mentioned high molecular polymers. combinations of species.
  • a suitable glass transition temperature ⁇ annealing 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 class of polymers is at least one selected from polycarbonate diols and brominated polycarbonates.
  • the glass transition temperature of the high-molecular polymer is 30-200° C.; the temperature of the annealing treatment is 50-250° C., and the temperature of the annealing treatment is greater than or equal to the glass transition temperature of the high-molecular polymer .
  • the difference between the temperature of the annealing treatment and the glass transition temperature of the high molecular polymer is in the range of 30°C-220°C, at most 220°C, and the specific difference can also be 50°C-130°C between.
  • the glass transition temperature is selected to be in the range of 50-150°C, and the temperature of the annealing treatment is 120-180°C.
  • the low glass transition temperature enables low-temperature annealing and has little effect on the thermal aging of the device.
  • the glass transition temperature of polymethyl methacrylate is 105°C
  • the annealing temperature can be selected to be ⁇ 105°C.
  • the glass transition temperature of polytetrafluoroethylene is 130°C, so the annealing temperature can be selected to be ⁇ 130°C; the glass transition temperature of polyacrylamide is 165°C, and the annealing temperature to be selected is ⁇ 165°C.
  • the mixed solution containing quantum dots and high molecular polymer is prepared by dissolving the above quantum dots and high molecular polymer in a solvent.
  • the concentration of the quantum dots in the mixed 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 etc., the dispersion effect of quantum dots is better at this concentration;
  • the mass ratio of the high molecular polymer and the quantum dots in the mixed solution is (0.5-10): 100, specifically, the high molecular polymer and quantum
  • the mass ratio of the dot material can be 0.5:100, 1:100, 2:100, 4:100, 5:100, 8:100, 10:100, etc.
  • the solvent in the mixed solution is selected from non-polar solvents.
  • the non-polar solvent is selected from at least one of chloroform, toluene, n-hexane, cyclohexane, n-heptane, n-octane, cycloheptane and dioxane.
  • the mixed solution in which the quantum dots and the macromolecular polymer are dispersed is deposited on the substrate, and the solvent is removed by annealing to obtain a quantum dot film.
  • the annealing process does not affect the stability of the quantum dots.
  • the method of depositing the mixed solution containing the quantum dots and the high molecular polymer 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 present application also provides a quantum dot film
  • the material of the quantum dot light-emitting film includes quantum dots and a polymer
  • the annealing temperature of the quantum dot film during annealing to form a film is greater than or equal to the polymer polymer glass transition temperature of the substance.
  • the materials of the quantum dot film provided by the present application include quantum dots and high molecular polymers. Since the annealing temperature of the quantum dot film during annealing is ⁇ the glass transition temperature of the high molecular polymer, under this condition, the quantum dot film is formed into a film. When the quantum dots are rearranged, they are tightly packed and regularly arranged in the polymer to form a flat quantum dot film. Therefore, the quantum dot film used in quantum dot light-emitting devices can significantly improve the electro-optical efficiency and life of the device.
  • the quantum dot film is prepared by the preparation method of the quantum dot film described in the embodiments of the present application.
  • the quantum dot films provided in the examples of the present application are obtained by the unique preparation method of the present application.
  • the positions of the quantum dots are rearranged, and the high molecular polymers are densely packed and regularly arranged to form a flat quantum dot film. Therefore, the use of the quantum dot film in a quantum dot light-emitting device can significantly improve the electro-optical efficiency and lifetime of the device.
  • the mass ratio of the high molecular polymer and the quantum dot material is (0.5-10):100; specifically, the mass ratio of the high molecular polymer and the quantum dot material may be 0.5:100, 1 : 100, 2: 100, 4: 100, 5: 100, 8: 100, 10: 100, etc.; the high molecular polymer is selected from vinyl polymers, acryl polymers, amide polymers, benzene At least one of a base-based polymer and a carbonate-based polymer.
  • 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 class of polymers is selected from at least one of polycarbonate diols and brominated polycarbonates.
  • an annealing temperature of less than 180°C can be selected to avoid the thermal aging effect of the higher annealing temperature on the functional layer of the device.
  • 1% polymethyl methacrylate (glass transition temperature of 105°C) is selected to be mixed with red quantum dots, thermally annealed at 150°C, and the current efficiency of the prepared device is 29Cd/A , T95@1000nit is 2500h; in another preferred embodiment, 10% polydecylidene formamide (glass transition temperature of 46°C) is selected to be mixed with green quantum dots, and thermally annealed at 60°C for 30min to prepare The obtained device current efficiency is 75Cd/A, and T95@1000nit is 3500h.
  • an embodiment of the present application further provides a quantum dot light-emitting diode, including an anode, a cathode, and a quantum dot light-emitting layer located between the anode and the cathode, and the quantum dot light-emitting layer is the one described in the embodiment of the present application.
  • Quantum dot films including an anode, a cathode, and a quantum dot light-emitting layer located between the anode and the cathode, and the quantum dot light-emitting layer is the one described in the embodiment of the present application. Quantum dot films.
  • the quantum dot light-emitting layer is the quantum dot thin film obtained by the above-mentioned preparation method of the quantum dot thin film.
  • the quantum dot light-emitting layer is the quantum dot film obtained by the specific preparation method of the embodiment of the present application, so the quantum dot film can improve the electro-optical efficiency and lifespan of the quantum dot light-emitting diode.
  • a hole functional layer is provided between the anode and the quantum dot light-emitting layer; the material of the hole functional layer is an organic benzyl group-containing organic layer.
  • the material, the quantum dot light-emitting layer contains quantum dots, a high molecular polymer and a cross-linking agent, and the quantum dot light-emitting layer and the hole functional layer interface are cross-linked.
  • a hole functional layer (the material is an organic material containing benzyl groups) on the anode substrate, and then depositing a mixed solution containing a crosslinking agent, quantum dots and high molecular polymers on the hole functional layer for annealing treatment.
  • the quantum dot light-emitting layer is then subjected to ultraviolet light for cross-linking reaction; in the process of annealing treatment, the temperature of the annealing treatment is greater than or equal to the glass transition temperature of the polymer.
  • the material of the hole functional layer is an organic material containing a benzyl group
  • the material of the quantum dot light-emitting layer includes quantum dots, high molecular polymers and cross-linking agents.
  • the cross-linking agent reacts with benzyl-containing organic materials
  • the cross-linking agent reacts with benzyl hydrogen to form stable free radicals
  • the cross-linking reaction is carried out through free radical coupling, so as to stabilize the quantum dot light-emitting layer and the empty space.
  • the interface contact of the hole functional layer can reduce the non-radiative recombination generated by the interface defect, thereby improving the electro-optical efficiency and lifetime of the quantum dot light-emitting diode.
  • the crosslinking agent is selected from at least one of benzophenone and benzophenone derivatives.
  • a certain proportion of benzophenone and benzophenone derivatives are doped in the quantum dot light-emitting layer, and the above-mentioned benzophenone and benzophenone derivatives are combined with the hole functional layer under the condition of ultraviolet light.
  • the highly active benzyl hydrogen on the surface reacts, and after the reaction, stable free radicals can be formed, and the free radicals are coupled and cross-linked to form a stable interface contact between the quantum dot light-emitting layer and the hole functional layer, which can reduce the undesired effects of interface defects.
  • the benzophenone derivative is selected from 2,4-dinitrobenzophenone, 2-hydroxy-4-methoxybenzophenone and 2-hydroxy-4-n-octyloxydiphenone At least one of benzophenones.
  • the benzyl-containing organic material of the hole functional 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)] (TFB), 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
  • the mixed solution containing the high molecular polymer, the cross-linking agent and the quantum dots is prepared by dissolving the above-mentioned high molecular polymer, the cross-linking agent and the quantum dot material in a solvent.
  • the mass ratio of the crosslinking agent and the quantum dot material is (0.5-5): 100.
  • the mass ratio of the crosslinking agent and the quantum dot material may be 0.5:100, 1:100, 2:100, 4:100, 5:100, etc.; when the proportion of the crosslinking agent is too low, the crosslinking agent at the interface between the quantum dot light-emitting layer and the hole functional layer is too small, and it is difficult to fully crosslink with the hole functional layer material, and the interface Poor contact effect; when the proportion of cross-linking agent is too high, since benzophenone or benzophenone derivatives are non-conductive cross-linking agents, although excess cross-linking agent is beneficial to cross-linking, it will increase the number of quantum dots The difficulty of injection and transport of electrons and holes in the light-emitting layer reduces the probability of radiative recombination of carriers in the light-emitting layer of quantum dots.
  • the quantum dot light-emitting layer formed by the crosslinking agent and the quantum dot material within the above ratio range can not only obtain a good interface morphology, but also improve the electro-optical efficiency and lifetime performance of the QLEDs device.
  • 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.
  • a preparation method of a quantum dot light-emitting diode comprising the following steps:
  • E02 Prepare a quantum dot thin film on the substrate by using the preparation method described in the examples of the present application to obtain a quantum dot light-emitting layer.
  • the quantum dot materials of the quantum dot light-emitting layer have the problems of loose accumulation and irregular arrangement under the existing film-forming process conditions such as spin coating, blade coating, printing, spraying, etc., resulting in the resulting quantum dot film.
  • the existence of "holes" allows the material of the hole functional layer and the electron functional layer to have the opportunity to directly contact.
  • the quantum dot light-emitting layer thin film is obtained by adopting a unique preparation method, so that the positions of the quantum dots in the quantum dot light-emitting layer are rearranged, and the quantum dots in the high-molecular polymer are densely packed and tightly packed.
  • the arrangement is regular to form a flat quantum dot light-emitting layer, thereby significantly improving the electro-optical efficiency and lifetime of the device.
  • the substrate is an anode substrate, and after obtaining the quantum dot light-emitting layer, the method further includes preparing a cathode on the quantum dot light-emitting layer; or, the substrate is a cathode substrate, and obtaining the quantum dot light-emitting layer After the layer, the method also includes preparing an anode on the quantum dot light-emitting layer.
  • the quantum dot light-emitting diode prepared in this way includes an anode, a cathode, and a quantum dot light-emitting layer located between the anode and the cathode, and the quantum dot light-emitting layer is the quantum dot film described in this application or the quantum dot film obtained by the above-mentioned preparation method. Point film.
  • a hole functional layer (the material is an organic material containing a benzyl group) can be prepared on the anode substrate, and then the mixed solution containing the crosslinking agent, quantum dots and high molecular polymer can be deposited on the anode substrate.
  • An annealing treatment is performed on the hole functional layer to obtain a quantum dot light-emitting layer, and then ultraviolet irradiation is performed to perform a cross-linking reaction; during the annealing treatment, the temperature of the annealing treatment is greater than or equal to the glass transition temperature of the polymer.
  • the mixed solution containing the high molecular polymer, the cross-linking agent and the quantum dots is prepared by dissolving the above-mentioned high molecular polymer, the cross-linking agent and the quantum dot material in a solvent.
  • the mass ratio of the crosslinking agent and the quantum dot material is (0.5-5):100.
  • the temperature of annealing treatment is 50-250°C, and the temperature of annealing treatment is 10-30min; the film formation effect is better under the above annealing conditions.
  • the wavelength of the ultraviolet light is 200-410nm; the time of the ultraviolet light is 5-15min, and under the above-mentioned ultraviolet light conditions, the effect of the cross-linking reaction is better; under the ultraviolet light of 200-410nm , the carbonyl group on benzophenone and benzophenone derivatives reacts with the highly active benzyl hydrogen on the hole functional layer material, and a stable free radical can be formed after the reaction, and the generated free radical can be carried out by free radical coupling.
  • a cross-linking reaction is carried out to obtain a quantum dot light-emitting layer and a hole functional layer film with closely adjacent interfaces.
  • a hole functional layer is provided between the anode and the quantum dot light-emitting layer; the material of the hole functional layer includes a crosslinking agent and The cross-linked product of the benzyl group-containing organic material is cross-linked, and the quantum dot light-emitting layer contains quantum dots and a high molecular polymer.
  • the hole functional layer can be obtained by depositing a mixed solution containing a cross-linking agent and an organic material containing a benzyl group on a substrate, performing annealing treatment, and then performing a cross-linking reaction with ultraviolet light.
  • the cross-linking agent reacts with benzyl hydrogen in the organic material containing benzyl groups to form stable free radicals, and the cross-linking reaction is carried out through free radical coupling, thereby forming a hole function 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, so that the device has a smooth and complete film morphology to improve the light-emitting performance of the device. and longevity.
  • the mixed solution containing the crosslinking agent and the benzyl group-containing organic material is prepared by dissolving the above-mentioned crosslinking agent and the benzyl group-containing organic material in a solvent.
  • concentration of the benzyl group-containing organic material in the mixed solution is 8-50 mg/ml, and the dispersing effect of the benzyl group-containing organic material is better at this concentration; the cross-linking agent and the benzyl group-containing organic material in the mixed solution
  • the mass ratio of benzyl-containing organic materials is (0.5-10): 100.
  • the proportion of the cross-linking agent is too low, the benzyl-containing organic materials are not sufficiently cross-linked, and may be damaged during subsequent preparation of the quantum dot light-emitting layer;
  • the proportion of the cross-linking agent is too high, since benzophenone or benzophenone derivatives are non-conductive cross-linking agents, the excess cross-linking agent is beneficial for cross-linking, but it will reduce the voids of the void functional layer. injection and transfer capability, thus affecting the overall performance of the device. Therefore, the crosslinking agent and the benzyl group-containing organic material in the above ratio range not only ensure good film morphology, but also help to improve the current efficiency and lifetime performance of the device.
  • the degradation temperature of depositing the mixed solution containing the crosslinking agent and the benzyl group-containing organic material on the substrate for annealing treatment may be 80-150° C., for example, the temperature of the annealing treatment may be 80° C., 100° C. °C, 120 °C, 150 °C, etc;; the time is 10-30min, such as 5min, 10min, 15min; under the above annealing conditions, the film formation effect of the hole functional layer is better.
  • 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 quantum dot light emitting layer and the anode are directly provided with a hole functional layer, such as a hole transport layer, or a stacked hole injection layer and a hole transport layer. , where the hole injection layer is adjacent to the anode.
  • a hole functional layer such as a hole transport layer, or a stacked hole injection layer and a hole transport layer.
  • 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 hole transport layer may be one or more of PVK, Poly-TPD, CBP, TCTA and TFB.
  • the quantum dots of 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, Cd
  • the electron transport layer is one or more of ZnO, TiO 2 , Alq 3 , SnO 2 , ZrO, AlZnO, ZnSnO, BCP, TAZ, PBD, TPBI, Bphen, 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, the hole transport layer is TFB, 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 TFB
  • the electron transport layer is ZnO
  • the cathode is Ag.
  • 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 nm ⁇ 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 TFB
  • the material of the quantum dot light-emitting layer 5 is composed of CdZnSe/ZnSe /ZnS red quantum dots and polymethyl methacrylate
  • 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:
  • a hole injection layer PEDOT:PSS material was spin-coated on the anode ITO, and then annealed at 100 °C for 15 min; then a hole transport layer TFB was formed on the hole injection layer, and annealed at 100 °C for 15 min; Spin coating a mixed solution composed of polymethyl methacrylate (glass transition temperature: 105 °C) and CdZnSe/ZnSe/ZnS red quantum dots with a mass ratio of 1:100, and bake on a hot plate at 150 °C for 30 min to conduct quantum dots.
  • the positions are rearranged to obtain a quantum dot light-emitting layer; an ethanol solution of ZnO is deposited on the quantum dot light-emitting layer to obtain an electron transport layer; finally, an electroluminescent device is formed by evaporating an Al cathode electrode layer by encapsulation.
  • 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 TFB
  • the material of the quantum dot light-emitting layer 5 is composed of CdZnSe/CdZnS /ZnS red quantum dots and polyethylene terephthalate
  • 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:
  • a hole injection layer PEDOT:PSS material was spin-coated on the anode ITO, and then annealed at 100 °C for 15 min; then a hole transport layer TFB was formed on the hole injection layer, and annealed at 100 °C for 15 min; Spin coating a mixed solution composed of polyethylene terephthalate and quantum dots with a mass ratio of 0.5:100, bake on a hot plate at 80°C for 30 min, and rearrange the positions of quantum dots to obtain a quantum dot light-emitting layer; An ethanol solution of ZnO is deposited on the light-emitting layer to obtain an electron transport layer; finally, an electroluminescent device is formed by evaporating an Al cathode electrode layer and encapsulating it.
  • 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 TFB
  • the material of the quantum dot light-emitting layer 5 is composed of CdZnSe/ZnSe /ZnS green quantum dots and polydecylidene formamide
  • 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:
  • a hole injection layer PEDOT:PSS material was spin-coated on the anode ITO, and then annealed at 100 °C for 15 min; then a hole transport layer TFB was formed on the hole injection layer, annealed at 100 °C for 15 min; Spin coating a mixed solution composed of polydecylidene formamide and quantum dots with a mass ratio of 10:100, bake on a 60°C hot plate for 30 minutes, and rearrange the positions of quantum dots to obtain a quantum dot light-emitting layer; An ethanol solution of ZnO is deposited thereon to obtain an electron transport layer; finally, an electroluminescent device is formed by evaporating an Al cathode electrode layer by encapsulation.
  • the quantum dot light-emitting diode device of this comparative example is the same as that of Example 1 except that the material of the light-emitting layer is only quantum dots.
  • 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 light-emitting layer is only quantum dots.
  • the quantum dot light-emitting diode device of this comparative example is the same as that of Example 3 except that the material of the light-emitting layer is only quantum dots.
  • 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 to 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.
  • Example 1 twenty two 20 29 2500 Comparative Example 1 623 twenty two 14 20 580
  • Example 2 633 twenty one 19.5 twenty four 2200 Comparative Example 2 633 twenty one 12 15 340
  • the quantum dot light-emitting diodes of the embodiments of the present application are annealed to make the quantum dots in the quantum dot films Position rearrangement, forming a tightly packed and regularly arranged quantum dot film in the polymer, the electro-optical efficiency and lifespan of the quantum dot light-emitting diode device are evenly improved compared to the quantum dot light-emitting device without the polymer; According to the current efficiency-brightness curve analysis of Example 1 and Comparative Example 1, the device with the rearrangement of quantum dots has a current efficiency value of about 1.5 times, and the roll-off effect is less obvious, and the obtained life test data is 4.3 times that of the normal device.
  • the other two groups of examples and comparative examples have the same rules. It is indicated that the solution provided in this application has a certain improvement effect on the accumulation and arrangement of quantum dots in the light-emitting layer of the device, and improves the optoelectronic performance and life of the quantum dot light-emitting device.

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Abstract

本申请公开一种量子点薄膜及其制备方法和量子点发光二极管。该量子点薄膜的制备方法包括如下步骤：提供基板；将含有量子点和高分子聚合物的混合溶液沉积在所述基板上，然后进行退火处理，得到量子点薄膜；其中，所述退火处理的温度≥所述高分子聚合物的玻璃化转变温度。该制备方法可以使量子点薄膜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薄膜用于量子点发光器件可以显著提高器件的电光效率和寿命。

Description

量子点薄膜及其制备方法和量子点发光二极管
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202010709907.0、发明名称为“量子点薄膜及其制备方法和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
本申请属于显示器件技术领域，具体涉及一种量子点薄膜及其制备方法和量子点发光二极。
 背景技术
近年来，由于固态发光二极管（Light Emitting Diode，LED）在照明和显示器领域有着很多优势，科研工作者和产业界对其的关注越来越高，量子点发光二极管（Quantum Dot Light Emitting Diode，QLED）具有发光效率高、发光光谱窄、化学和光学稳定性高等优点，可成为高性能、低成本的电致发光器件，因此成为下一代的发光显示器件。随着量子点发光二极管的研究进步，红绿蓝器件的外量子效率都已经接近20%，且具有较好的重复性，但是器件的工作寿命不是很理想。
由于器件的量子点发光层材料采用的是球形量子点（Quantum Dot，QD）纳米材料，尺寸一般在5-15纳米之间，通过旋涂或者印刷等工艺得到的量子点发光层存在着量子点材料堆积松散、排布不规整的问题，容易形成带有“孔洞”的不平整的量子点薄膜，从而导致载流子在器件中的复合区域发生移动，对器件的光电性能和寿命产生不良影响，从而影响器件的效率和寿命。
因此，相关技术有待改进。
 技术问题
本申请实施例的目的之一在于：提供一种量子点薄膜及其制备方法，旨在解决现有量子点薄膜不平整的技术问题。
本申请实施例的另一目的在于：提供一种量子点发光二极管，旨在解决量子点发光二极管的量子点发光层不平整的技术问题。
 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，本申请提供了一量子点薄膜的制备方法，包括如下步骤：
提供基板；
将含有量子点和高分子聚合物的混合溶液沉积在所述基板上，然后进行退火处理，得到量子点薄膜；
其中，所述退火处理的温度≥所述高分子聚合物的玻璃化转变温度。
第二方面，本申请提供了一种量子点薄膜，所述量子点发光薄膜的材料包括量子点和高分子聚合物，且所述量子点薄膜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。
第三方面，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，所述量子点发光层为本申请所述的量子点薄膜。
 有益效果
本申请实施例提供的量子点薄膜的制备方法的有益效果在于：该量子点薄膜的制备方法中，将含有量子点和高分子聚合物的混合溶液沉积在基板上进行退火处理得到量子点薄膜，在该退火处理的过程中，退火处理的温度≥高分子聚合物的玻璃化转变温度，具体地，当退火处理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，当退火处理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，从而使量子点薄膜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薄膜用于量子点发光器件可以显著提高器件的电光效率和寿命。
本申请实施例提供的量子点薄膜的有益效果在于：量子点薄膜的材料包括量子点和高分子聚合物，因量子点薄膜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，该条件下量子点薄膜成膜时，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，因此该量子点薄膜用于量子点发光器件可以显著提高器件的电光效率和寿命。
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的量子点发光层为本申请特有的量子点薄膜，因此该量子点薄膜可以提高量子点发光二极管的电光效率和寿命。
 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是本申请实施例的量子点薄膜的制备方法流程图；
图2是本申请实施例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。
一方面，本申请一些实施例提供了一种量子点薄膜的制备方法，如图1所示，该制备方法包括如下步骤：
S01：提供基板；
S02：将含有量子点和高分子聚合物的混合溶液沉积在所述基板上，然后进行退火处理，得到量子点薄膜；
其中，所述退火处理的温度≥所述高分子聚合物的玻璃化转变温度。
本申请实施例提供的量子点薄膜的制备方法中，将含有量子点和高分子聚合物的混合溶液沉积在基板上进行退火处理得到量子点薄膜，因该退火处理的过程中，退火处理的温度≥高分子聚合物的玻璃化转变温度，具体地，当退火处理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，当退火处理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，从而使量子点薄膜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薄膜用于量子点发光器件可以显著提高器件的电光效率和寿命。
在一些实施例中，所述量子点包括II-VI、IV-VI、III-V、I-VI族化合物单一结构和复合结构量子点中的至少一种。具体地，所述复合结构量子点包括核壳结构量子点，构成所述核壳结构量子点的核包括CdSe、CdS、CdTe、CdSeTe、CdZnS、PbSe、ZnTe、CdSeS、PbS、PbTe、HgS、HgSe、HgTe、GaN、GaP、GaAs、InP、InAs、InZnP、InGaP和InGaN中的至少一种；构成所述核壳结构量子点的壳包含ZnSe、ZnS和ZnSeS中的至少一种。
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（≤退火处理的温度）与量子点材料混合，制备得到量子点薄膜。
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和溴化聚碳酸酯中得至少一种。
在一些实施例中，所述高分子聚合物的玻璃化转变温度为30-200℃；所述退火处理的温度为50-250℃，且退火处理的温度≥高分子聚合物的玻璃化转变温度。具体地，所述退火处理的温度与所述高分子聚合物的玻璃化转变温度的差值范围在30℃-220℃之间，最多为220℃，具体差值还可以是50℃-130℃之间。
进一步优选的，选择玻璃化转变温度范围在50-150℃，退火处理的温度为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℃，此时退火温度可以选择≥105℃。聚四氟乙烯的玻璃化转变温度为130℃，故退火温度可以选择≥130℃；聚丙烯酰胺的玻璃化转变温度为165℃，需选择的退火温度为≥165℃。
在一些实施例中，含有量子点和高分子聚合物的混合溶液通过上述量子点和高分子聚合物溶解在溶剂中配制。其中，所述混合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、2：100、4：100、5：100、8：100、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，所述混合溶液中的溶剂选自非极性溶剂。溶剂沸点在50-200℃的非极性溶剂，退火后可以挥发。具体地，所述非极性溶剂选自氯仿、甲苯、正己烷、环己烷、正庚烷、正辛烷、环庚烷和二氧六环中的至少一种。
将分散有量子点和高分子聚合物的混合溶液沉积在基板上，并进行退火去除溶剂，得到量子点薄膜，退火过程不影响量子点的稳定性。
在一些实施例中，将含有量子点和高分子聚合物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。
另一方面，本申请还提供一种量子点薄膜，所述量子点发光薄膜的材料包括量子点和高分子聚合物，且所述量子点薄膜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。
本申请提供的量子点薄膜的材料包括量子点和高分子聚合物，因量子点薄膜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，该条件下量子点薄膜成膜时，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，因此该量子点薄膜用于量子点发光器件可以显著提高器件的电光效率和寿命。
进一步地，所述量子点薄膜由本申请实施例所述的量子点薄膜的制备方法制备得到。本申请实施例提供的量子点薄膜由本申请特有的制备方法得到，这样的量子点薄膜中，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，因此该量子点薄膜用于量子点发光器件可以显著提高器件的电光效率和寿命。
在一个实施例中，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、2：100、4：100、5：100、8：100、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。进一步地，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和溴化聚碳酸酯中的至少一种。
优选的，高分子聚合物玻璃化转变温度小于150℃，即可选择小于180℃的退火温度，避免较高的退火温度对器件功能层产生热老化效应。在一个优选的实施例中，选择1%的聚甲基丙烯酸甲酯（玻璃化转变温度为105℃）与红色量子点混合，在150℃下热退火，制备得到的器件电流效率为29Cd/A，T95@1000nit为2500h；在另一个优选的实施例中，选择10%的聚亚癸基甲酰胺（玻璃化转变温度为46℃）与绿色量子点混合，在60℃下热退火30min，制备得到的器件电流效率为75Cd/A，T95@1000nit为3500h。
最后，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，所述量子点发光层为本申请实施例所述的量子点薄膜。
具体地，该量子点发光层为上述量子点薄膜的制备方法得到的量子点薄膜。本申请实施例提供的量子点发光二极管中，量子点发光层为本申请实施例特有的制备方法得到的量子点薄膜，因此该量子点薄膜可以提高量子点发光二极管的电光效率和寿命。
进一步地，在一些实施例中，本申请实施例提供的量子点发光二极管中，阳极与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为含苄基的有机材料，所述量子点发光层含有量子点、高分子聚合物和交联剂，且所述量子点发光层与所述空穴功能层界面交联。可以通过在阳极基板上制备空穴功能层（材料为含苄基的有机材料），然后将含有交联剂、量子点和高分子聚合物的混合溶液沉积在空穴功能层上进行退火处理得到量子点发光层，然后进行紫外光照进行交联反应；退火处理的过程中，退火处理的温度≥高分子聚合物的玻璃化转变温度。
空穴功能层的材料为含苄基的有机材料，量子点发光层的材料包括量子点、高分子聚合物和交联剂，这样紫外光照过程中，在量子点发光层和空穴功能层的界面处，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，从而提高量子点发光二极管的电光效率和寿命。
具体地，交联剂选自二苯甲酮和二苯甲酮衍生物中的至少一种。本申请实施例通过在量子点发光层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跟空穴功能层表面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，形成稳定的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，从而提高量子点发光二极管的电光效率和寿命。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。
空穴功能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)] (TFB)、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。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。
进一步地，在一些实施例中，含有高分子聚合物、交联剂和量子点的混合溶液通过上述高分子聚合物、交联剂和量子点材料溶解在溶剂中配制。其中，交联剂和所述量子点材料的质量比为（0.5-5）：100，具体地，交联剂和量子点材料的质量比可以为0.5：100、1：100、2：100、4：100、5：100等；当交联剂成分比例过低时，量子点发光层和空穴功能层的界面处交联剂成分过少，难以与空穴功能层材料充分交联，界面接触效果不佳；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，但会增加量子点发光层内电子和空穴注入和传输的难度，降低载流子在量子点发光层辐射复合的几率。因此，上述比例范围内的交联剂和量子点材料形成的量子点发光层，既可以获得良好的界面形态，又可以提升QLEDs器件的电光效率和寿命性能。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。将分散有交联剂和量子点的混合溶液沉积在空穴功能层表面，并进行退火去除溶剂，然后紫外光照条件下与空穴功能层表面的含苄基的有机材料进行交联反应形成稳定的界面接触。
以及，一种量子点发光二极管的制备方法，包括如下步骤：
E01：提供基板；
E02：利用本申请实施例所述的制备方法在所述基板上制备量子点薄膜，得到量子点发光层。
在QLED器件制备工艺中，在旋涂，刮涂、印刷，喷涂等现有成膜工艺条件下量子点发光层的量子点材料存在堆积松散、排布不规整的问题，致使得到的量子点薄膜存在着“孔洞”，使得空穴功能层与电子功能层的材料能够有机会直接接触，在器件通电工作情况下，电子和空穴在界面层上累积形成激子以及产生激子复合区，导致载流子传输材料发光，使得电致发光光谱上出现明显的杂光峰影响发光纯度，而且界面处累积的电荷会产生焦耳热，尤其在高电流密度下，热量会影响激子的形成，从而影响器件的发光效率和寿命。本发明实施例提供的上述量子点发光二极管的制备方法，因采用特有的制备方法得到量子点发光层薄膜，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，形成平的量子点发光层，从而显著提高器件的电光效率和寿命。
在一些实施例中，所述基板为阳极基板，得到所述量子点发光层后，还包括在所述量子点发光层上制备阴极；或者，所述基板为阴极基板，得到所述量子点发光层后，还包括在所述量子点发光层上制备阳极。这样制备的量子点发光二极管，包括阳极、阴极以及位于阳极和阴极之间的量子点发光层，该量子点发光层为本申请所述的量子点薄膜或上述量子点薄膜的制备方法得到的量子点薄膜。
进一步地，在一些实施例中，可以通过在阳极基板上制备空穴功能层（材料为含苄基的有机材料），然后将含有交联剂、量子点和高分子聚合物的混合溶液沉积在空穴功能层上进行退火处理得到量子点发光层，然后进行紫外光照进行交联反应；退火处理的过程中，退火处理的温度≥高分子聚合物的玻璃化转变温度。进一步地，在一些实施例中，含有高分子聚合物、交联剂和量子点的混合溶液通过上述高分子聚合物、交联剂和量子点材料溶解在溶剂中配制。其中，交联剂和所述量子点材料的质量比为（0.5-5）：100。
在一个实施例中，制备含有量子点、高分子聚合物和交联剂的量子点发光层时，退火处理的温度为50-250℃，退火处理的温度为 10-30min；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；所述紫外光照的时间为5-15min，上述紫外光照条件下，交联反应的效果更佳；在200-410nm的紫外光照下，二苯甲酮和二苯甲酮衍生物上的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，生成的自由基可以通过自由基耦合进行交联反应，从而获得界面紧密相邻的量子点发光层和空穴功能层薄膜。
进一步地，在另一个实施例中，本发明实施例提供的量子点发光二极管中，阳极与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，所述量子点发光层含有量子点和高分子聚合物。该空穴功能层可以通过将含有交联剂和含苄基的有机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，交联剂与含苄基的有机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，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。
含有交联剂和含苄基的有机材料的混合溶液通过上述交联剂和含苄基的有机材料溶解在溶剂中配制。其中，所述混合溶液中的含苄基的有机材料的浓度为8-50mg/ml，该浓度下含苄基的有机材料分散效果更佳；所述混合溶液中的所述交联剂和含苄基的有机材料的质量比为（0.5-10）：100，如果交联剂成分比例过低，含苄基的有机材料交联不充分，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含苄基的有机材料，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。
在一些实施例中，将含有交联剂、含苄基的有机材料的混合溶液沉积在基板上进行退火处理的退化温度可以为80-150℃，例如，退火处理的温度可以为80℃、100℃、120℃、150℃等；；时间为 10-30min，例如5min、10min、15min；上述退火条件下空穴功能层成膜效果更佳。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。
在一些实施例中，上述量子点发光二极管器件中，量子点发光层与阳极直接设置有空穴功能层，如设置有空穴传输层，或者设置有层叠的空穴注入层和空穴传输层，其中空穴注入层与阳极相邻。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。
空穴传输层可以是PVK、Poly-TPD、CBP、TCTA和TFB中的一种或多种。
量子点发光层的量子点为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。
电子传输层为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TFB，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TFB，量子点发光层5包括CdZnSe/ZnSe/ZnS红色量子点和聚甲基丙烯酸甲酯，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形成空穴传输层TFB，100℃退火15min；在作为承载部的空穴传输层上旋涂质量比为1:100的聚甲基丙烯酸甲酯（玻璃化转变温度为105℃）和CdZnSe/ZnSe/ZnS红色量子点组成的混合溶液，150℃热板上烘烤30min，进行量子点位置重排，得到量子点发光层；在量子点发光层上沉积ZnO的乙醇溶液，得到电子传输层；最后通过蒸镀Al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TFB，量子点发光层5包括CdZnSe/CdZnS/ZnS红色量子点和聚对苯二甲酸乙二酯，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形成空穴传输层TFB，100℃退火15min；在作为承载部的空穴传输层上旋涂质量比为0.5:100的聚对苯二甲酸乙二酯和量子点组成的混合溶液，80℃热板上烘烤30min，进行量子点位置重排，得到量子点发光层；在量子点发光层上沉积ZnO的乙醇溶液，得到电子传输层；最后通过蒸镀Al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TFB，量子点发光层5包括CdZnSe/ZnSe/ZnS绿色量子点和聚亚癸基甲酰胺，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形成空穴传输层TFB，100℃退火15min；在作为承载部的空穴传输层上旋涂质量比为10:100的聚亚癸基甲酰胺和量子点组成的混合溶液，60℃热板上烘烤30min，进行量子点位置重排，得到量子点发光层；在量子点发光层上沉积ZnO的乙醇溶液，得到电子传输层；最后通过蒸镀Al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发光层材料仅为量子点外，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发光层材料仅为量子点外，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发光层材料仅为量子点外，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 20 29 2500
对比例 1 623 22 14 20 580
实施例 2 633 21 19.5 24 2200
对比例2 633 21 12 15 340
实施例3 534 25 18 75 3500
对比例3 534 25 10 41.5 760
通过表1的数据对比可知，本申请实施例的量子点发光二极管，含有量子点和高分子聚合物的混合溶液沉积在基板上形成的量子点薄膜，通过退火处理使量子点薄膜中的量子点位置重排，在高分子聚合物中形成堆积紧密、排布规整的量子点薄膜，量子点发光二极管器件的电光效率和寿命相较于没有高分子聚合物的量子点发光器件均匀提升；从实施例1和对比例1 的电流效率-亮度曲线分析，经过量子点位置重排的器件有约1.5倍的电流效率值，且滚降效应更不明显，得到的寿命测试数据是正常器件的4.3倍，其他两组实施例和对比例有同样的规律。说明本申请提供的方案对器件中发光层内的量子点堆积和排布有一定的改善效果，提升了量子点发光器件的光电性能和寿命。
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. 一种量子点薄膜的制备方法，其特征在于，包括如下步骤：
    提供基板；
    将含有量子点和高分子聚合物的混合溶液沉积在所述基板上，然后进行退火处理，得到量子点薄膜；
    其中，所述退火处理的温度≥所述高分子聚合物的玻璃化转变温度。
  2. 如权利要求1所述的量子点薄膜的制备方法，其特征在于，所述高分子聚合物的玻璃化转变温度为30-200℃。
  3. 如权利要求1所述的量子点薄膜的制备方法，其特征在于，所述退火处理的温度为80-250℃。
  4. 如权利要求1所述的量子点薄膜的制备方法，其特征在于，所述高分子聚合物的玻璃化转变温度为50-150℃，所述退火处理的温度为120-180℃。
  5. 如权利要求1所述的量子点薄膜的制备方法，其特征在于，所述退火处理的温度与所述高分子聚合物的玻璃化转变温度的差值最多为220℃。
  6. 如权利要求1所述的量子点薄膜的制备方法，其特征在于，所述混合溶液中的所述量子点的浓度为10-50mg/ml。
  7. 如权利要求1所述的量子点薄膜的制备方法，其特征在于，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。
  8. 如权利要求1所述的量子点薄膜的制备方法，其特征在于，所述混合溶液中的溶剂选自非极性溶剂。
  9. 如权利要求1所述的量子点薄膜的制备方法，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。
  10. 如权利要求9所述的量子点薄膜的制备方法，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得至少一种。
  11. 一种量子点薄膜，其特征在于，所述量子点发光薄膜的材料包括量子点和高分子聚合物，且所述量子点薄膜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。
  12. 如权利要求11所述的量子点薄膜，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。
  13. 如权利要求11所述的量子点薄膜，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。
  14. 如权利要求11所述的量子点薄膜，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。
  15. 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，其特征在于，所述量子点发光层为权利要求11所述的量子点薄膜。
  16. 如权利要求15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。
  17. 如权利要求15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。
  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。
  19. 如权利要求15所述的量子点发光二极管，其特征在于，所述量子点发光层与所述阳极之间设置有空穴功能层。
  20. 如权利要求15所述的量子点发光二极管，其特征在于，所述量子点发光层与所述阴极之间设置有电子功能层。
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100289001A1 (en) * 2007-10-30 2010-11-18 Kahen Keith B Device containing non-blinking quantum dots
CN107833976A (zh) * 2017-10-24 2018-03-23 深圳市华星光电半导体显示技术有限公司 Qled器件的制作方法及qled器件
CN109888114A (zh) * 2019-01-17 2019-06-14 南京邮电大学 一种钙钛量子点矿膜层的制备方法及其应用
CN109962128A (zh) * 2017-12-26 2019-07-02 Tcl集团股份有限公司 一种薄膜及其制备方法与qled器件
US20190276734A1 (en) * 2018-03-09 2019-09-12 Samsung Electronics Co., Ltd. Quantum dots, production methods thereof, and light emitting device including the same

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2487218A1 (en) * 2011-02-09 2012-08-15 Koninklijke Philips Electronics N.V. Polymeric matrix with organic phosphor and manufactory thereof
CN106098884A (zh) * 2016-07-08 2016-11-09 东华大学 一种量子点发光二极管及其制备方法
KR102618343B1 (ko) * 2018-08-14 2023-12-26 엘지디스플레이 주식회사 양자점 발광소자

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100289001A1 (en) * 2007-10-30 2010-11-18 Kahen Keith B Device containing non-blinking quantum dots
CN107833976A (zh) * 2017-10-24 2018-03-23 深圳市华星光电半导体显示技术有限公司 Qled器件的制作方法及qled器件
CN109962128A (zh) * 2017-12-26 2019-07-02 Tcl集团股份有限公司 一种薄膜及其制备方法与qled器件
US20190276734A1 (en) * 2018-03-09 2019-09-12 Samsung Electronics Co., Ltd. Quantum dots, production methods thereof, and light emitting device including the same
CN109888114A (zh) * 2019-01-17 2019-06-14 南京邮电大学 一种钙钛量子点矿膜层的制备方法及其应用

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