WO2021253786A1 - Matériau composite et son procédé de préparation et diode électroluminescente à points quantiques - Google Patents

Matériau composite et son procédé de préparation et diode électroluminescente à points quantiques Download PDF

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WO2021253786A1
WO2021253786A1 PCT/CN2020/139382 CN2020139382W WO2021253786A1 WO 2021253786 A1 WO2021253786 A1 WO 2021253786A1 CN 2020139382 W CN2020139382 W CN 2020139382W WO 2021253786 A1 WO2021253786 A1 WO 2021253786A1
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oxide nanoparticles
composite material
metal oxide
type metal
quantum dot
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Chinese (zh)
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聂志文
张旋宇
刘文勇
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Tcl科技集团股份有限公司
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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    • 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
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Definitions

  • This application relates to the technical field of light-emitting device materials, in particular to a composite material and a preparation method thereof, and a quantum dot light-emitting diode.
  • Quantum dot electroluminescent devices still have defects such as low efficiency and short lifespan.
  • the construction of high-performance QLED devices is usually prepared by solution method, and inorganic metal oxides such as zinc oxide are usually used as the electron transport layer (Electron Transport Layer, ETL) of QLEDs. .
  • ETL Electro Transport Layer
  • the surface ligands of quantum dots are generally non-polar, which leads to poor contact with inorganic metal oxides and makes electron injection more difficult.
  • existing QLED devices generally have electron mobility much higher than hole mobility, which makes the charge accumulation phenomenon at the QD/ETL interface very serious, which has a very negative impact on the efficiency and life of the QLED device.
  • the film structure of the metal oxide nanoparticles after the spin coating is formed into a film often appears as a disordered loose structure, containing a large number of various defects, such as micropores. At the same time, it is easy to accumulate in some specific directions, and the uniformity is poor.
  • the present application provides a composite material, comprising n-type metal oxide nanoparticles and organic molecules shown in the following formula I attached to the surface of the n-type metal oxide nanoparticles, on the organic molecules The carboxyl group is bound to the surface of the n-type metal oxide nanoparticles;
  • R 1 is -(CH 2 ) n -, and n is an integer greater than or equal to 1.
  • this application provides a method for preparing a composite material, including the following steps:
  • R 1 is -(CH 2 ) n -
  • R 2 is -O(CH 2 ) m CH 3
  • n is an integer greater than or equal to 1
  • m is an integer greater than or equal to 0.
  • 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 an electron transport layer is provided between the cathode and the quantum dot light-emitting layer
  • the electron transport layer is composed of the composite material described in this application.
  • the beneficial effect of the quantum dot light-emitting diode provided by the embodiments of the application is that the electron transport layer in the quantum dot light-emitting diode is composed of a composite material unique to the application, and the composite material has good electrical properties of a crystal structure and can improve electron mobility. , Reduce the surface defects of n-type metal oxide nanoparticles, so the electron transport layer composed of it improves the effective utilization of electrons of the device, reduces defect recombination, enhances electron injection, and reduces the charge at the interface between the quantum dot light-emitting layer and the electron transport layer Accumulation, thereby improving the efficiency and lifespan of QLED devices.
  • Fig. 1 is a flow chart of a method for preparing a composite material according to an embodiment of the application
  • FIG. 2 is a schematic diagram of the structure of a quantum dot light-emitting diode according to an embodiment of the application.
  • Some embodiments of the present application provide a composite material, the composite material includes n-type metal oxide nanoparticles and organic molecules shown in the following formula I connected to the surface of the n-type metal oxide nanoparticles, the organic The carboxyl group on the molecule is bound to the surface of the n-type metal oxide nanoparticle;
  • R 1 is -(CH 2 ) n -, and n is an integer greater than or equal to 1.
  • the composite material provided by the embodiments of the present application includes n-type metal oxide nanoparticles and organic molecules of formula I connected to the n-type metal oxide nanoparticles.
  • the carboxyl groups in the organic molecules can be oxidized with the n-type metal oxide nanoparticles. Because the organic molecule is a small dicarboxylic acid molecule, the organic molecule can be connected to two n-type metal oxide nanoparticles through the carboxyl group, thereby connecting the n-type metal oxide nanoparticles to each other. Connected to form a network-like structure. These network connection structures not only effectively shorten the particle spacing, but also ensure that the nanoparticles will not agglomerate.
  • the organic molecules of the bipolar group are bound to the surface of the n-type metal oxide nanoparticles, which can reduce the surface defects and enhance the nanoparticles.
  • the electron conductivity between particles increases the electron mobility of the composite material, thus enhancing the electron transport ability of the composite material.
  • the mass ratio of the organic molecules to the n-type metal oxide nanoparticles is (0.1-5): 30, specifically, the mass ratio of the organic molecules to the n-type metal oxide nanoparticles may be 0.1:30, 0.5:30, 1:30, 2:30, 4:30, 5:30, etc.; further, the mass ratio of organic molecules to the n-type metal oxide nanoparticles is (1 to 4): 30; Doping the organic molecules shown in formula I within this mass ratio range can better improve the electron transport performance of the composite material.
  • the n-type metal oxide nanoparticles are selected from zinc oxide nanoparticles, titanium oxide nanoparticles, tin oxide nanoparticles, zirconium oxide nanoparticles, and aluminum-doped zinc oxide nanoparticles.
  • oxide nanoparticles specifically, zinc oxides such as ZnO, titanium oxides such as TiO 2 , tin oxides such as SnO 2 , zirconium oxides such as ZrO 2 , aluminum-doped zinc The oxides such as AlZnO.
  • the n-type metal oxide nanoparticles are selected from ZnO nanoparticles.
  • ZnO has good electron transport properties, but the film structure of ZnO nanoparticles after spin-coating is often shown as a disordered loose structure, containing A large number of various defects, such as micropores, etc. In addition, ZnO has poor contact with non-polar ligands on the surface of quantum dots, making electron injection difficult. Therefore, combining the organic molecules represented by formula I on the surface of zinc oxide nanoparticles can reduce surface defects and enhance the electronic conductivity between the nanoparticles, thereby improving the electron transport performance of zinc oxide.
  • the composite material is composed of the n-type metal oxide nanoparticles and the organic molecules.
  • the embodiment of the present application also provides a preparation method of a composite material.
  • the preparation method includes the following steps:
  • S02 Dissolve the n-type metal oxide nanoparticles and the organic dicarboxylic acid monoester in a polar solvent, and perform heating treatment to obtain a mixed solution;
  • R 1 is -(CH 2 ) n -
  • R 2 is -O(CH 2 ) m CH 3
  • n is an integer greater than or equal to 1
  • m is an integer greater than or equal to 0.
  • the preparation method of the composite material provided by the embodiment of the application is by dissolving n-type metal oxide nanoparticles and the dicarboxylic acid monoester organic compound represented by formula II in a polar solvent for heating treatment, the dicarboxylic acid represented by formula II
  • the acid monoester organic matter is hydrolyzed to form an organic molecule represented by formula I.
  • the organic molecule in the composite material obtained by subsequent solid-liquid separation, the organic molecule can be combined with two n-type metal oxide nanoparticles through the carboxyl group, so that the organic molecule will be n-type
  • the metal oxide nanoparticles are connected to each other; the preparation method is not only simple in process, low in cost, and can be prepared on a large scale, and the composite material obtained by such a preparation method not only effectively shortens the particle distance, but also ensures that the nanoparticles will not agglomerate.
  • the organic molecules of the bipolar group are bound to the surface of the n-type metal oxide nanoparticles, which can reduce the surface defects and enhance the electronic conductivity between the nanoparticles, thereby increasing the electron mobility of the composite material, thereby enhancing the composite material The ability of electronic transmission.
  • the composite material provided in the embodiments of the present application is obtained by the above-mentioned preparation method, and the composite material includes n-type metal oxide nanoparticles and the n-type metal oxide nanoparticles connected to the n-type metal oxide nanoparticles as shown in formula I
  • the two carboxyl groups on the organic molecules can respectively bind to the metal ions on the surface of the n-type metal oxide nanoparticles, so that the organic molecules connect the n-type metal oxide nanoparticles to form a network structure, which is specifically prepared The steps are shown above.
  • the unbranched straight chain R 1 within the range of the number of carbon atoms can better connect the n-type metal oxide nanoparticles.
  • the unbranched straight chain R 2 within the range of carbon atoms can be better hydrolyzed to form the organic molecule of the bipolar group represented by formula I.
  • the n-type metal oxide nanoparticles are selected from zinc oxide nanoparticles, titanium oxide nanoparticles, tin oxide nanoparticles, zirconium oxide nanoparticles, and aluminum-doped zinc oxide nanoparticles One or more.
  • the n-type metal oxide nanoparticles and the dicarboxylic acid monoester organic matter are heated and dissolved in a polar solvent to obtain a mixed solution, and the dicarboxylic acid monoester organic matter is hydrolyzed to form the organic bipolar group represented by formula I.
  • the conditions of the heat treatment include: a temperature of 60-120°C and a time of 30min-4h. Under the above conditions, the organic dicarboxylic acid monoester can be better hydrolyzed.
  • the mixed solution is a fatty acid solution of monomethyl suberate and zinc acetate.
  • the monomethyl suberate is converted into suberic acid and then combined with n-type metal oxide nanoparticles.
  • the polar solvent includes one or more of ethanol, methanol, water, N,N-dimethylformamide, and N,N-dimethylacetamide.
  • the mass ratio of the added organic dicarboxylic acid monoester to the n-type metal oxide nanoparticles is (0.1-5): 30; it can be better improved within the range of the mass ratio The electron transport properties of composite materials.
  • the step of solid-liquid separation includes annealing crystallization treatment, for example, the solid-liquid separation includes annealing crystallization at a temperature of 80 to 120°C, for example, the temperature can be 80°C, 100°C, 120°C, etc.; Further, the annealing time is 20min-40min, for example, it can be 20min, 30min, 40min, etc.
  • the mixed solution is deposited on the substrate for annealing and crystallization treatment, thereby obtaining a composite material film layer, which can be used as an electron transport film layer.
  • the composite material film layer obtained after annealing can improve the film-forming crystallinity of the composite material, thereby improving hole transport.
  • Existing n-type metal oxide nanoparticles exist in the form of hydrated particles before film formation. The hydrated particles are nearly twice the size of their own particles. After the film-forming solvent evaporates during the film-forming process, there is no mutual attraction. Under the action of force, the spacing is relatively large; and the n-type metal oxide nanoparticles synthesized in the prior art and the solution method film formation technology usually make the electron transport layer composed of n-type metal oxide nanoparticles disorderly and relatively Many microporous defects and low film crystallinity.
  • the embodiment of the application modifies the n-type metal oxide nanoparticles by doping the organic molecules represented by formula I to improve the film quality and crystallization performance of the ETL layer.
  • the chain dicarboxylic acid monoester organics can be completely hydrolyzed to form organic molecules of the bipolar group shown in formula I, which can connect adjacent metal oxide nanoparticles (such as ZnO nanoparticles) to each other to form an n-type
  • the composite material obtained by the above preparation method improves the conduction and recombination ability of electrons at the interface, improves the transport efficiency of carriers between the interface, balances the hole and electron injection rate of the device, and improves the brightness and life of the device.
  • the embodiments of the present application also provide an application of the above-mentioned composite material or the composite material obtained by the above-mentioned composite material preparation method as an electron transport material. Because the above-mentioned composite material crystals provided by the embodiments of the present application have more excellent planar electrical properties and higher electron mobility, the planar layered crystals are formed by doping organic molecules with bipolar groups in the n-type metal oxide nanoparticles to improve The electrical properties of the electron transport layer, so the composite material can be used as an electron transport material, specifically for the electron transport layer of quantum dot light-emitting diodes.
  • the embodiments of the present application provide a quantum dot light-emitting diode, which includes an anode, a cathode, and a quantum dot light-emitting layer located between the anode and the cathode, and electrons are arranged between the cathode and the quantum dot light-emitting layer.
  • the transport layer, the electron transport layer is composed of the composite material described in the embodiments of the present application.
  • the electron transport layer is composed of a composite material unique to the embodiment of the application.
  • the composite material has good electrical properties of a crystal structure, can improve electron mobility, and reduce n-type metal oxides. Nanoparticle surface defects, so the device improves the effective utilization of electrons, reduces defect recombination, enhances electron injection, reduces charge accumulation at the interface between the quantum dot light-emitting layer and the hole transport layer, and improves the efficiency and life of the QLED device.
  • an electron injection layer is also provided between the electron transport layer and the cathode.
  • a hole function layer such as a hole transport layer, or a stacked hole injection layer and a hole transport layer is provided between the quantum dot light-emitting layer and the anode, wherein the hole injection layer is in phase with the anode. adjacent.
  • the quantum dot light-emitting diode provided by the embodiment of the present application includes an upright structure and an inverted structure.
  • the upright structure quantum dot light-emitting diode includes a laminated structure of an anode and a cathode disposed oppositely, and a quantum dot light-emitting layer disposed between the anode and the cathode is disposed on the cathode and the cathode.
  • the electron transport layer between the quantum dot light-emitting layers, and the anode is disposed on the substrate.
  • an electron injection layer may be provided between the cathode and the electron transport layer, and an electron functional layer such as a hole blocking layer may be provided between the cathode and the quantum dot light-emitting layer;
  • a hole function layer such as a hole transport layer, a hole injection layer, and an electron blocking layer may also be provided between the quantum dot light-emitting layer and the quantum dot light-emitting layer.
  • 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 is disposed on the hole injection layer. The hole transport layer on the surface of the layer, the quantum dot light emitting layer provided on the surface of the hole transport layer, the electron transport layer provided on the surface of the quantum dot light emitting layer, and the cathode provided on the surface of the electron transport layer.
  • the inverted structure quantum dot light-emitting diode includes a stacked structure of an anode and a cathode disposed oppositely, and a quantum dot light-emitting layer disposed between the anode and the cathode is disposed on the cathode and the cathode.
  • the electron transport layer between the quantum dot light-emitting layers, and the cathode is disposed on the substrate.
  • an electron injection layer may be provided between the cathode and the electron transport layer, and an electron functional layer such as a hole blocking layer may be provided between the cathode and the quantum dot light-emitting layer;
  • a hole function layer such as a hole transport layer, a hole injection layer, and an electron blocking layer may also be provided between the quantum dot light-emitting layer and the quantum dot light-emitting layer.
  • the quantum dot light emitting diode includes a substrate, a cathode disposed on the surface of the substrate, the electron transport layer disposed on the surface of the cathode, and the electron transport layer disposed on the surface of the electron transport layer.
  • a method for manufacturing a quantum dot light-emitting diode includes the following steps:
  • E02 Deposit the composite material described in the embodiment of the application or the composite material obtained by the preparation method on the substrate to obtain an electron transport layer.
  • the method for preparing quantum dot light-emitting diodes provided in the embodiments of the application prepares the unique composite material of the embodiments of the application into the electron transport layer of the device. Because the composite material has good electron transport properties, the composite material can be used as the electron transport layer. Improve the luminous efficiency and lifetime of the device.
  • the preparation of a QLED device includes the following steps:
  • a hole injection layer is formed on the anode
  • a hole transport layer is formed on the hole injection layer.
  • a cathode is formed on the electron transport layer.
  • the substrate may be a rigid substrate or a flexible substrate, including but not limited to glass, silicon wafer, and the like.
  • the anode may be a conductive metal oxide, including but not limited to zinc oxide, indium oxide, tin oxide, indium tin oxide (ITO), and the like.
  • the hole injection layer can be polythiophene, WoO 3, and the like.
  • the hole transport layer can be TFB, TPD, etc.
  • the material of the light-emitting layer may be group II-VI such as CdS, group III-V such as GaN, or group IV-VI such as SnS.
  • the cathode can be a metal or alloy, including but not limited to aluminum, silver, and the like.
  • the thickness of the anode is 20-200nm; the thickness of the hole injection layer is 20-200nm; the thickness of the hole transport layer is 30-180nm; the total thickness of the quantum dot hybrid light-emitting layer is 30-180nm.
  • the thickness of the electron transport layer is 10-180 nm; the thickness of the cathode is 40-190 nm.
  • This embodiment provides a QLED device whose structure is shown in FIG. 2.
  • 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 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 CdZnSe /ZnSe quantum dots
  • the material of the electron transport layer 6 is a composite material of suberic acid doped and modified ZnO
  • the material of the cathode 7 is Al.
  • the preparation method of the device includes the following steps:
  • the deposition condition is 3000r/min spin coating for 30s, and then heat at 150°C for 30min to complete the crystallization to obtain the hole transport layer.
  • n-octanoic acid solution of monomethyl suberate added to the ZnO solution dissolved in ethanol.
  • the mass ratio of the doped dicarboxylic acid monoester to the ZnO material is 1:30, and the dicarboxylic acid monoester is completely hydrolyzed to form suberic acid by heating at 80° C. for 2 hours, and solution 1 is obtained. After the solution 1 was spin-coated at 3000 r/min for 30 s, it was heated at 80° C. for 30 min to obtain an electron transport layer.
  • the Al electrode is evaporated, and the QLED device is obtained by packaging with electronic glue.
  • This embodiment provides a QLED device whose structure is shown in FIG. 2.
  • 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 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 CdZnSe /ZnSe/ZnS quantum dots
  • the material of the electron transport layer 6 is a composite material of pimelic acid doped and modified ZnO
  • the material of the cathode 7 is Al.
  • the preparation method of the device includes the following steps:
  • the deposition condition is 3000r/min spin coating for 30s, and then heat at 150°C for 30min to complete the crystallization to obtain the hole transport layer.
  • the Al electrode is evaporated, and the QLED device is obtained by packaging with electronic glue.
  • This embodiment provides a QLED device whose structure is shown in FIG. 2.
  • 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 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 CdZnSe /ZnSe/CdZnS quantum dots
  • the material of the electron transport layer 6 is a composite material of succinic acid doped and modified ZnO
  • the material of the cathode 7 is Al.
  • the preparation method of the device includes the following steps:
  • the deposition condition is 3000r/min spin coating for 30s, and then heat at 150°C for 30min to complete the crystallization to obtain the hole transport layer.
  • n-octanoic acid solution of monomethyl succinate added to the ZnO solution dissolved in ethanol.
  • the mass ratio of the doped dicarboxylic acid monoester to the ZnO material is 2:30, and the dicarboxylic acid monoester is completely hydrolyzed to form succinic acid by heating at 80° C. for 2 hours, and solution 1 is obtained.
  • the solution 1 was spin-coated at 3000r/min for 30s and then heated at 80°C for 60min to obtain an electron transport layer.
  • the Al electrode is evaporated, and the QLED device is obtained by packaging with electronic glue.
  • This embodiment provides a QLED device whose structure is shown in FIG. 2.
  • 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 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 CdZnSeS /ZnS quantum dots
  • the material of the electron transport layer 6 is azelaic acid doped and modified ZnO composite material
  • the material of the cathode 7 is Al.
  • the preparation method of the device includes the following steps:
  • the deposition condition is 3000r/min spin coating for 30s, and then heat at 150°C for 30min to complete the crystallization to obtain the hole transport layer.
  • n-octanoic acid solution of monomethyl azelate To the room temperature, add a certain amount of n-octanoic acid solution of monomethyl azelate to the ZnO solution dissolved in ethanol.
  • the mass ratio of the doped dicarboxylic acid monoester to the ZnO material is 4:30, and the dicarboxylic acid monoester is completely hydrolyzed to form azelaic acid by heating at 80° C. for 2 hours, and solution 1 is obtained.
  • the solution 1 was spin-coated at 3000r/min for 30s and then heated at 80°C for 30min to obtain an electron transport layer.
  • the Al electrode is evaporated, and the QLED device is obtained by packaging with electronic glue.
  • This embodiment provides a QLED device whose structure is shown in FIG. 2.
  • 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 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 CdZnSe /ZnSe quantum dots
  • the material of the electron transport layer 6 is a composite material of suberic acid doped and modified TiO 2
  • the material of the cathode 7 is Al.
  • the preparation method of the device includes the following steps:
  • the deposition condition is 3000r/min spin coating for 30s, and then heat at 150°C for 30min to complete the crystallization to obtain the hole transport layer.
  • n-octanoic acid solution of monomethyl suberate is added to the TiO 2 solution dissolved in ethanol.
  • the mass ratio of the doped dicarboxylic acid monoester to the TiO 2 material is 1:30, and the dicarboxylic acid monoester is completely hydrolyzed to form suberic acid by heating at 80° C. for 2 hours, and solution 1 is obtained. After the solution 1 was spin-coated at 3000 r/min for 30 s, it was heated at 80° C. for 30 min to obtain an electron transport layer.
  • the Al electrode is evaporated, and the QLED device is obtained by packaging with electronic glue.
  • This embodiment provides a QLED device whose structure is shown in FIG. 2.
  • 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 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 CdZnSe /ZnSe quantum dots
  • the material of the electron transport layer 6 is a composite material of suberic acid doped and modified SnO 2
  • the material of the cathode 7 is Al.
  • the preparation method of the device includes the following steps:
  • the deposition condition is 3000r/min spin coating for 30s, and then heat at 150°C for 30min to complete the crystallization to obtain the hole transport layer.
  • n-octanoic acid solution of monomethyl suberate added to the SnO 2 solution dissolved in ethanol.
  • the mass ratio of the doped dicarboxylic acid monoester to the SnO 2 material is 1:30, heated at 80° C. for 2 hours to achieve complete hydrolysis of the dicarboxylic acid monoester to form suberic acid, and solution 1 is obtained.
  • the solution 1 was spin-coated at 3000 r/min for 30 s, it was heated at 80° C. for 30 min to obtain an electron transport layer.
  • the Al electrode is evaporated, and the QLED device is obtained by packaging with electronic glue.
  • This comparative example is the same as Example 1 except that the material of the electron transport layer is undoped ZnO material.
  • This comparative example is the same as Example 2 except that the material of the electron transport layer is undoped ZnO material.
  • This comparative example is the same as Example 3 except that the material of the electron transport layer is undoped ZnO material.
  • This comparative example is the same as Example 4 except that the material of the electron transport layer is undoped ZnO material.
  • This comparative example is the same as in Example 5 except that the material of the electron transport layer is undoped TiO 2 material.
  • This comparative example is the same as Example 6 except that the material of the electron transport layer is undoped SnO 2 material.
  • the quantum dot light-emitting diodes prepared in Comparative Examples 1 to 6 and Examples 1 to 6 were tested for performance, and the test methods are as follows:
  • the ratio of the number of electron-hole pairs injected into the quantum dot into the number of emitted photons, in %, is an important parameter to measure the pros and cons of electroluminescent devices, which can be obtained by measuring with an EQE optical testing instrument.
  • the specific calculation formula is as follows:
  • ⁇ e is the light output coupling efficiency
  • ⁇ r is the ratio of the number of recombined carriers to the number of injected carriers
  • ⁇ is the ratio of the number of excitons that generate photons to the total number of excitons
  • K R is the rate of radiation process
  • K NR is the non-radiation process rate
  • Test conditions carried out at room temperature, with an air humidity of 30-60%.
  • the device life test is usually carried out by accelerating the aging of the device with reference to the OLED device test at high brightness, and the extended exponential decay brightness decay fitting formula is used to fit the life under high brightness, such as: life under 1000nit Counted as T95 1000nit .
  • the specific calculation formula is as follows:
  • T95 L is the life under low brightness
  • T95 H is the measured life under high brightness
  • L H is the acceleration of the device to the highest brightness
  • L L is 1000nit
  • A is the acceleration factor.
  • the value is usually 1.6 ⁇ 2.
  • the A value of 1.7 is obtained by measuring the lifetime of several groups of green QLED devices at rated brightness.
  • the life test system is used to carry out life test on the corresponding device, and the test conditions are: at room temperature, and the air humidity is 30-60%.
  • Electron mobility the average velocity of the carrier under the action of a unit electric field, which reflects the transport capacity of the carrier under the action of the electric field, and the unit is cm 2 /(V ⁇ s). It can be obtained by preparing the corresponding pure electronic device and then using the space charge limited current method (SCLC) measurement.
  • SCLC space charge limited current method
  • the pure electronic device structure is as follows: anode/electron transport layer/cathode.
  • the specific calculation formula is as follows:
  • Test conditions carried out at room temperature, with an air humidity of 30-60%.
  • the electron mobility of the electron transport layer film is significantly higher than that of the corresponding electron transport layer film in the respective comparative examples.
  • the external quantum efficiency and lifetime of the quantum dot light-emitting diodes provided by the embodiments of the present application are significantly higher than those of the corresponding quantum dot light-emitting diodes in the comparative examples, indicating that the quantum dot light-emitting diodes of the embodiments of the present application have better luminous efficiency.

Abstract

La présente invention concerne un matériau composite et son procédé de préparation, ainsi qu'une diode électroluminescente à points quantiques. Le matériau composite comprend des nanoparticules d'oxyde métallique de type n et des molécules organiques représentées par la formule I fixées à la surface des nanoparticules d'oxyde métallique de type n, et des groupes carboxyle sur les molécules organiques sont liés à la surface des nanoparticules d'oxyde métallique de type n ; dans la formule I, R1 est -(CH2)n-, et n est un nombre entier supérieur ou égal à 1. Le matériau composite non seulement raccourcit efficacement l'espacement des nanoparticules d'oxyde métallique, mais assure également que les nanoparticules ne sont pas agglomérées ; de plus, les molécules organiques ayant des groupes bipolaires sont liées à la surface des nanoparticules d'oxyde métallique de type n, de telle sorte que leurs défauts de surface peuvent être réduits, la capacité de conduction d'électrons entre les nanoparticules est améliorée, ce qui permet d'améliorer la mobilité des électrons du matériau composite, et ainsi la capacité de transport d'électrons du matériau composite est améliorée.
PCT/CN2020/139382 2020-06-15 2020-12-25 Matériau composite et son procédé de préparation et diode électroluminescente à points quantiques WO2021253786A1 (fr)

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