WO2022252608A1 - Quantum dot light-emitting diode and preparation method therefor - Google Patents

Quantum dot light-emitting diode and preparation method therefor Download PDF

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Publication number
WO2022252608A1
WO2022252608A1 PCT/CN2021/143375 CN2021143375W WO2022252608A1 WO 2022252608 A1 WO2022252608 A1 WO 2022252608A1 CN 2021143375 W CN2021143375 W CN 2021143375W WO 2022252608 A1 WO2022252608 A1 WO 2022252608A1
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Prior art keywords
quantum dot
electron transport
layer
dot light
emitting diode
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PCT/CN2021/143375
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French (fr)
Chinese (zh)
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林雄风
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Tcl科技集团股份有限公司
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Publication of WO2022252608A1 publication Critical patent/WO2022252608A1/en

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    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • H10K50/10OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/115OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • H10K50/10OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14Carrier transporting layers
    • H10K50/16Electron transporting layers
    • H10K50/165Electron transporting layers comprising dopants
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10Deposition of organic active material
    • H10K71/12Deposition of organic active material using liquid deposition, e.g. spin coating

Definitions

  • the present application relates to the field of display technology, in particular to a method for preparing a quantum dot light-emitting diode and a quantum dot light-emitting diode prepared by applying the method.
  • QLED Quantum Dots Light-Emitting Diode, quantum dot light-emitting device
  • OLED Organic Light-Emitting Diode, organic light-emitting device
  • Quantum dots are particles with a particle diameter of less than 10nm, mainly composed of zinc, cadmium, sulfur, and selenium atoms. When the quantum dot is stimulated by light, it will emit colored light. The color of the light is determined by the material of the quantum dot and the size and shape of the quantum dot.
  • quantum size effect makes them exhibit excellent physical properties, especially optical properties, such as adjustable spectrum, high luminous intensity, high color purity, long fluorescence lifetime, A single light source can excite multicolor fluorescence and other advantages.
  • the luminous efficiency of QLED has basically met the needs of commercialization.
  • QLED has a long lifespan and simple or no packaging process. It is expected to become the next generation of flat panel displays and has broad development prospects.
  • the working life of the quantum dot light-emitting diodes prepared at this stage is far from the theoretical length, and the phenomenon of fluorescence quenching often occurs during the test process, which greatly restricts the quantum dot light-emitting devices.
  • development progress The main reason for such problems is that the transport rate of hole carriers and electron carriers in the quantum dot light-emitting diode is unbalanced, which makes the quantum dot charging and fluorescence quenching.
  • the present application provides a method for preparing a quantum dot light-emitting diode and a quantum dot light-emitting diode prepared by using the method.
  • the embodiment of the present application provides a method for preparing a quantum dot light-emitting diode, which includes the following steps:
  • the quantum dot material is a quantum dot dry film or a quantum dot wet film;
  • a top electrode is formed on the electron transport layer.
  • a transition layer is formed between the quantum dot light-emitting layer and the electron transport layer, and the transition layer contains quantum dots, interface modification materials and electron transport materials.
  • the interface modifying material in the layer fills in the gaps between the quantum dots in the transition layer, in the gaps between the electron transport materials, and in the gaps between the quantum dots and the electron transport materials.
  • a step of standing still is included, and the standing time is 5-10 seconds.
  • a quantum dot material is provided, the quantum dot material is disposed on the bottom electrode to form a quantum dot film, and then the mixed solution is disposed on the quantum dot film surface, specifically:
  • quantum dot material arrange quantum dot material on the bottom electrode, form quantum dot dry film, after obtaining quantum dot light-emitting layer, add the mixed solution on the quantum dot light-emitting layer.
  • a quantum dot material is provided, the quantum dot material is disposed on the bottom electrode to form a quantum dot film, and then the mixed solution is disposed on the quantum dot film surface, specifically:
  • the quantum dot material is provided, and the quantum dot material is arranged on the bottom electrode to form a quantum dot wet film, and then the mixed solution is arranged on the surface of the quantum dot wet film by a solution method.
  • a quantum dot material is provided, the quantum dot material is disposed on the bottom electrode to form a quantum dot film, and then the mixed solution is disposed on the quantum dot film surface, specifically:
  • the quantum dot material is provided, and the quantum dot material is spin-coated on the bottom electrode to form a quantum dot wet film, and the mixed solution is added within a few seconds after the spin coating starts, and the spin coating is stopped after the addition is completed.
  • the rotational speed of the spin coating is 2000-3000 r/.
  • the number of seconds is 2-10 seconds.
  • the interface modification material is selected from polyethyleneimine, polyethoxyethyleneimine, poly[9,9-bis(3'-(N,N-di One of methylamino)propyl)-2,7-fluorene]-2,7-(9,9-dioctylfluorene))], polyethylene glycol, conjugated polyelectrolyte or polyethylene oxide or Several kinds.
  • the electron transport material is selected from metal oxides, doped metal oxides, 2-6 group semiconductor materials, 3-5 group semiconductor materials and 1-3-6 group
  • the metal oxide is selected from one or more of ZnO, TiO 2 , SnO 2
  • the metal oxide in the doped metal oxide is selected from ZnO, TiO 2 , SnO 2 or more
  • the doping element is selected from one or more of aluminum, magnesium, indium, gallium
  • the 2-6 semiconductor group material is selected from one of ZnS, ZnSe, CdS or several
  • the 3-5 group semiconductor material is selected from at least one of InP and GaP
  • the 1-3-6 group semiconductor material is selected from at least one of CuInS and CuGaS.
  • the organic solvent is selected from one or more of ethylene glycol monomethyl ether, isopropanol or ethanol.
  • the concentration of the interface modification material ranges from 0.1wt% to 10wt%.
  • the concentration range of the electron transport material in the mixed solution is 10-30 mg/mL.
  • the embodiment of the present application also provides a quantum dot light-emitting diode, which includes a stacked bottom electrode, a quantum dot light-emitting layer, an electron transport layer, and a top electrode, the quantum dot light-emitting layer contains quantum dots, and the electrons
  • the transport layer contains an electron transport material, wherein the gap between adjacent quantum dots and the electron transport material is filled with an interface modification material.
  • the quantum dot light-emitting diode further includes a transition layer located between the quantum dot light-emitting layer and the electron transport layer, and the transition layer contains quantum dots, interface modification materials, and electrons.
  • the transport material, the interface modifying material in the transition layer is filled in the gaps between the quantum dots in the transition layer, the gaps between the electron transport materials, and the gaps between the quantum dots and the electron transport materials.
  • the interface modification material is also filled between the quantum dot light-emitting layer and the transition layer, and between the transition layer and the electron transport layer.
  • the interface modification material is selected from polyethyleneimine, polyethoxyethyleneimine, poly[9,9-bis(3'-(N,N-di One of methylamino)propyl)-2,7-fluorene]-2,7-(9,9-dioctylfluorene))], polyethylene glycol, conjugated polyelectrolyte or polyethylene oxide or Several kinds.
  • the electron transport material is selected from metal oxides, doped metal oxides, 2-6 group semiconductor materials, 3-5 group semiconductor materials and 1-3-6 group
  • the metal oxide is selected from one or more of ZnO, TiO 2 , SnO 2
  • the metal oxide in the doped metal oxide is selected from ZnO, TiO 2 , SnO 2 or more
  • the doping element is selected from one or more of aluminum, magnesium, indium, gallium
  • the 2-6 semiconductor group material is selected from one of ZnS, ZnSe, CdS or several
  • the 3-5 group semiconductor material is selected from at least one of InP and GaP
  • the 1-3-6 group semiconductor material is selected from at least one of CuInS and CuGaS.
  • the preparation method of the quantum dot light-emitting diode of the present application first mixes the interface modification material with the electron transport material and the organic solvent to obtain a mixed solution, and then when the mixed solution is arranged on the surface of the quantum dot light-emitting layer, the interface modification material will penetrate with the organic solvent into the gap between the quantum dots. In this way, the interface modification material of the prepared quantum dot light-emitting diode is filled in the gaps between the quantum dots of the quantum dot light-emitting layer, the gap between the electron transport materials of the electron transport layer, and the adjacent quantum dots. In the gap between the dots and the electron transport material.
  • the contact mode between the quantum dots and the electron transport material is changed from the conventional point contact to the surface contact, which can effectively increase the effective contact area between the quantum dot light-emitting layer and the electron transport layer, and promote the quantum dot light-emitting layer and electron transport.
  • Electron transport between layers reduces or even avoids the problem of unbalanced transport rates of hole carriers and electron carriers, thereby avoiding quantum dot charging and fluorescence quenching.
  • the preparation method of the quantum dot light-emitting diode of the present application first mixes the interface modification material with the electron transport material and the organic solvent to obtain a mixed solution, and then arranges the mixed solution on the surface of the quantum dot wet film, so that the interface modification material will As the organic solvent penetrates into the gaps of the quantum dots, and the quantum dots on the surface of the quantum dot wet film and the electron transport material will be mixed due to factors such as gravity, the effective contact area between the quantum dot light-emitting layer and the electron transport layer can be further increased. Promote electron transport between the quantum dot light-emitting layer and the electron transport layer.
  • the interface modification material used in the preparation method of the quantum dot light-emitting diode of the present application has the effect of reducing the work function of the material and passivating the surface defects of the material. When it penetrates into the interface between the quantum dot and the electron transport material, it has a regulating effect on the material interface, which can Reduce the interfacial barrier of the material, thereby facilitating the transport of charges.
  • the materials due to the small particle size of quantum dots and electron transport materials, both of which are nanostructures, the materials have a large specific surface area and a high content of surface defects, which will have a strong capture effect on free charges, resulting in non-fluorescence recombination, resulting in device Poor performance.
  • the surface defects of nanoparticles will be passivated, which can reduce non-fluorescence recombination and improve device performance.
  • Fig. 1 is the flow chart of the preparation method of the quantum dot light-emitting diode provided by the embodiment of the present application;
  • FIG. 2 is a schematic diagram of a quantum dot light-emitting diode provided in an embodiment of the present application
  • Fig. 3 is a schematic diagram of another quantum dot light-emitting diode provided by the embodiment of the present application.
  • Fig. 4 is the graph that the current density of the quantum dot light-emitting diode of the application embodiment 1 and comparative example 1 changes with the voltage;
  • Fig. 5 is the graph that the brightness of the quantum dot light-emitting diode of the application embodiment 1 and comparative example 1 changes with voltage;
  • Fig. 6 is the external quantum efficiency-voltage curve diagram of the quantum dot light-emitting diode of embodiment 1 and comparative example 1 of the present application;
  • Fig. 7 is the current efficiency-voltage curve diagram of the quantum dot light-emitting diode of embodiment 1 and comparative example 1 of the present application;
  • Fig. 8 is the luminance-time graph of the quantum dot light-emitting diodes of Example 1 and Comparative Example 1 of the present application;
  • FIG. 9 is a graph of the lifespan of the quantum dot light-emitting diode in Example 1 extrapolated by the present application through an empirical formula.
  • the embodiment of the present application provides a quantum dot light-emitting diode and a preparation method thereof. Each will be described in detail below. It should be noted that the description sequence of the following embodiments is not intended to limit the preferred sequence of the embodiments. In addition, in the description of the present application, the term “including” means “including but not limited to”. The expressions "one or more” and “at least one” in this application refer to one or more of the listed items, and “multiple” refers to any of two or more of these items.
  • Combinations including any combination of single or plural terms (species), for example, "at least one (species) of a, b, or c" or “at least one (species) of a, b, and c" , can represent: a, b, c, a-b (that is, a and b), a-c, b-c, or a-b-c, where a, b, and c can be single or multiple.
  • an embodiment of the present application provides a method for preparing a quantum dot light-emitting diode 100, which includes the following steps:
  • Step S1 providing a substrate 1, and forming a bottom electrode 2 on the substrate 1;
  • Step S2 Provide the interface modification material 3, the electron transport material 51 and an organic solvent, mix them, dissolve the interface modification material 3 in the organic solvent, and disperse the electron transport material 51 in the organic solvent to obtain a mixed solution;
  • Step S3 providing a quantum dot material, placing the quantum dot material on the bottom electrode 2 to form a quantum dot film, and then placing the mixed solution on the surface of the quantum dot film by a solution method, forming a film, drying, Obtain the quantum dot luminescent layer 4 and the electron transport layer 5 combined with the quantum dot luminescent layer 4;
  • Step S4 forming a top electrode 6 on the electron transport layer 5 .
  • the method for disposing the quantum dot material on the bottom electrode 2 may be a chemical film-forming method or a physical film-forming method known in the art.
  • the chemical film-forming methods include: chemical vapor deposition, continuous ion layer adsorption and reaction, anodic oxidation, electrolytic deposition, and co-precipitation.
  • Physical film forming methods include physical coating methods and solution processing methods.
  • physical coating methods include: thermal evaporation coating method, electron beam evaporation coating method, magnetron sputtering method, multi-arc ion coating method, physical vapor deposition method, atomic Layer deposition method, pulsed laser deposition method, etc.; solution processing methods include spin coating method, printing method, inkjet printing method, scraping method, printing method, dipping and pulling method, soaking method, spraying method, roll coating method, casting method , Slit coating method, strip coating method.
  • the quantum dot film may be a dried quantum dot film or an undried quantum dot wet film. Wherein, the quantum dot dry film is the quantum dot light-emitting layer 4 .
  • step S3 is S03: provide quantum dot material, quantum dot material is arranged on the bottom electrode 2, forms quantum dot dry film, after obtaining quantum dot light-emitting layer 4, the The mixed solution is added to the quantum dot light-emitting layer 4, so that the interface modification material 3 penetrates at least into the gap of the quantum dots 41 on the side of the quantum dot light-emitting layer 4 adjacent to the electron transport layer 5 along with the organic solvent to form a film, and dried to obtain the electron transport layer 5.
  • the interface modification material 3 is filled in the gaps between the quantum dots 41 of the quantum dot luminescent layer 4, in the gaps between the electron transport materials 51 of the electron transport layer 5, and between the adjacent quantum dots 41 and In the gap between electron transport materials 51 .
  • the contact mode between the quantum dots 41 and the electron transport material 51 is changed from the conventional point contact to the surface contact, which can effectively increase the effective contact area between the quantum dot method light-emitting layer 4 and the electron transport layer 5, and promote the quantum dot method.
  • the electron transport between the light-emitting layer 4 and the electron transport layer 5 reduces or even avoids the problem of unbalanced transport rates of hole carriers and electron carriers, thereby avoiding charging of quantum dots 41 and quenching of fluorescence.
  • the interface modification material 3 is filled between the quantum dot light emitting layer 4 and the electron transport layer 5 .
  • described step S3 is S13: provide quantum dot material, described quantum dot material is arranged on the bottom electrode 2, forms quantum dot wet film, then described mixed solution passes through The solution method is arranged on the surface of the quantum dot wet film, the quantum dots on the surface of the quantum dot wet film are mixed with the electron transport material, and dried after film formation to obtain the quantum dot light-emitting layer 4, which is combined with the quantum dot light-emitting layer 4
  • the transition layer 10, and the electron transport layer 5 combined with the transition layer 10.
  • the transition layer 10 includes quantum dots 41 , an interface modification material 3 and an electron transport material 51 .
  • the interface modification material 3 in the transition layer 10 is filled in the gaps between the quantum dots 41 in the transition layer 10, the gaps between the electron transport materials 51, and the gaps between the quantum dots 41 and the electron transport materials 51 In other words, the quantum dots 41 and the electron transport material 51 in the transition layer 10 are randomly embedded in the interface modification material 3 .
  • the interface modification material 3 is also filled between the quantum dot luminescent layer 4 and the transition layer 10, between the transition layer 10 and the electron transport layer 5, and the quantum dots of the quantum dot luminescent layer 4 41 , and in the gap between the electron transport materials 51 of the electron transport layer 5 .
  • the mixed solution is arranged on the surface of the quantum dot wet film by a solution method, so that the quantum dots 41 on the surface of the quantum dot wet film can be mixed with the electron transport material 51, and the quantum dots 41 and the electron transport material 51 can be mutually mixed.
  • a mixed transition layer can further increase the effective contact area between the quantum dot light-emitting layer 4 and the electron transport layer 5, and promote the electron transport between the quantum dot light-emitting layer 4 and the electron transport layer 5.
  • said S13 is: provide the quantum dot material, spin coat the quantum dot material on the bottom electrode 2 to form a quantum dot wet film, and within a few seconds after the spin coating starts (that is, the spin coating starts and before the quantum dot material forms a dry film), add the mixed solution, stop the spin coating after the addition, and dry after film formation to obtain the quantum dot light-emitting layer 4, the transition layer 10 combined with the quantum dot light-emitting layer 4, and Electron transport layer 5 bonded to transition layer 10 .
  • the interface modification material 3 will penetrate into the quantum dot gap of the quantum dot wet film along with the organic solvent, and in the spin coating process, the surface of the quantum dot wet film
  • the quantum dots and electron transport materials can be better intermixed.
  • the interstices of all quantum dots in the quantum dot light-emitting layer 4 are filled with the interface modification material 3 .
  • the gap between the quantum dots 41 in the region of the quantum dot light-emitting layer 4 adjacent to the side of the electron transport layer 5 is filled with the interface modification material 3, away from the electron transport layer 5 The gap between the quantum dots 41 in the region on one side is not filled with the interface modification material 3 .
  • the drying method is a method known in the art for drying quantum dot films, such as baking.
  • the choice of the substrate 1 is not limited, a flexible substrate or a hard substrate can be selected.
  • the method for forming the bottom electrode 2 on the substrate 1 is a conventional method in the field, such as evaporation.
  • the bottom electrode 2 is an anode.
  • the anode is an anode commonly used in this field.
  • the anode 2 is ITO (tin-indium oxide).
  • the interface modification material has a permanent dipole moment.
  • the interface modification material can be selected from but not limited to PEI (polyethyleneimine), PEIE (polyethoxyethyleneimine), PFN (poly[9,9-bis(3'-(N,N-dimethyl (amino)propyl)-2,7-fluorene]-2,7-(9,9-dioctylfluorene))]), PEG (polyethylene glycol), CPE (conjugated polyelectrolyte), PEO ( One or more of polyethylene oxide).
  • the interface modification material 3 has the effect of reducing the work function of the material and passivating the surface defects of the material.
  • the quantum dots 41 and the electron transport material 51 both of which are nanostructures, the materials have a large specific surface area and a high content of surface defects, which will have a strong trapping effect on free charges, resulting in non-fluorescent recombination. result in poor device performance.
  • the surface defects of the nanoparticles will be passivated, which can reduce non-fluorescence recombination and improve device performance.
  • the concentration of the interface modification material 3 ranges from 0.1 wt% to 10 wt%. Under this concentration condition, the viscosity of the mixed solution is moderate, and the interface modification material 3 can effectively penetrate into the gaps of the quantum dots 41 of the quantum dot light-emitting layer 4 . If the concentration is too high, the viscosity of the solution mixed solution will be greatly increased, increasing the difficulty of the interface modification material 3 infiltrating into the gap of the quantum dot 41, increasing the thickness of the interface modification material between the quantum dot light-emitting layer 4 and the electron transport layer 5, thereby Increased resistance to charge transfer.
  • the concentration range of the electron transport material 51 is 10-30 mg/mL.
  • the electron transport material 51 is a material conventionally used in the field of electron transport.
  • the electron transport material 51 is selected from but not limited to one or more of metal oxides, doped metal oxides, group 2-6 semiconductor materials, group 3-5 semiconductor materials and group 1-3-6 semiconductor materials .
  • the metal oxide is selected from but not limited to one or more of zinc oxide (ZnO), titanium oxide (TiO 2 ), tin oxide (SnO 2 ); the metal in the doped metal oxide
  • the oxide is selected from but not limited to at least one of ZnO, TiO 2 , and SnO 2
  • the doping element is selected from but not limited to one or more of aluminum, magnesium, indium, and gallium
  • the 2-6 semiconductor group The material is selected from but not limited to one or more of ZnS, ZnSe, and CdS
  • the 3-5 semiconductor group material is selected from but not limited to at least one of InP and GaP
  • the material is selected from but not limited to at least one of CuInS and CuGaS.
  • the electron transport material 51 is nano-ZnO, nano-TiO 2 or nano-SnO 2 .
  • the particle size of the nano ZnO is less than 20nm.
  • the organic solvent is a conventionally used solvent in this field.
  • the organic solvent is a high-viscosity solvent or a low-viscosity solvent.
  • the high-viscosity solvent may be ethylene glycol monomethyl ether (EGME, viscosity 1.7 mPa•s), isopropanol (viscosity 2.4 mPa•s), and the like.
  • the low-viscosity solvent may be ethanol (viscosity 1.2 mPa ⁇ s) or the like.
  • the organic solvent is a low-viscosity solvent, which facilitates the penetration of the interface modification material 3 into the gaps of the quantum dots 41 .
  • the quantum dot material is a quantum dot material conventionally used in the field, such as CdSeZnS, CdSeCdS/ZnS, ZnCdS/ZnS and the like.
  • the quantum dot concentration in the quantum dot material is 10-20mg/mL.
  • the baking temperature is 80-120° C., and the baking time is 5-30 minutes.
  • the step S03 after adding the mixed solution to the quantum dot luminescent layer 4, it also includes a step of standing still, so that the interface modification material 3 can fully penetrate into the vicinity of the quantum dot luminescent layer 4 In the gap between the quantum dots 41 on the side of the electron transport layer 5 .
  • the resting time is 5-10 seconds.
  • the method for forming the quantum dot film is spin coating film formation, the spin coating film formation speed ranges from 2000-3000r/s, and the time range is 20-30s.
  • the rotation speed of the spin coating is 2000-3000r/s, and the time is 25-35s.
  • the mixed solution is added dropwise within 2-10 seconds after the spin coating starts.
  • the method of forming the top electrode 6 on the electron transport layer 5 is a conventional method in the field, such as evaporation and the like.
  • the top electrode 6 is a cathode, and the cathode is a cathode commonly used in this field, such as Al, Ag, Al/Ag, Cu, Au and alloy electrodes.
  • the vapor deposition method is as follows: by thermal evaporation, the vacuum degree is not higher than 3 ⁇ 10 -4 Pa, and the vapor deposition is performed for 1000-2000 seconds at a speed of 0.5-1 angstroms/second.
  • a step of forming at least one of a hole transport layer and a hole injection layer on the bottom electrode 2 is also included.
  • the method for forming the hole transport layer and the hole injection layer is a conventional method in the field, such as evaporation and the like.
  • the method of forming the hole injection layer is: spin-coat the hole injection layer material on the bottom electrode 2 and then bake it.
  • the rotating speed of the spin coating is 4000-5000r/s, and the time is 30 seconds.
  • the baking temperature is 150° C., and the baking time is 15-30 minutes.
  • the material of the hole injection layer is a material conventionally used in the hole injection layer in the field, such as PEDOT (polymer of (3,4-ethylenedioxythiophene monomer)): PSS (sodium polystyrene sulfonate) mixed materials etc.
  • the method of forming the hole transport layer is: spin-coat the material of the hole transport layer on the bottom electrode 2 or the hole injection layer, and then bake.
  • the rotating speed of the spin coating is 3000r/s, and the time is 30 seconds.
  • the baking temperature is 80° C., and the baking time is 10-30 minutes.
  • the material of the hole transport layer is a material conventionally used in the field of the hole transport layer, such as TFB (nickel etchant).
  • a step of forming an electron injection layer on the electron transport layer 5 may also be included.
  • the embodiment of the present application also provides a quantum dot light-emitting diode 100 , which includes a substrate 1 , a bottom electrode 2 , a quantum dot light-emitting layer 4 , an electron transport layer 5 and a top electrode 6 which are sequentially stacked.
  • the quantum dot light-emitting layer 4 includes quantum dots 41
  • the electron transport layer 5 includes an electron transport material 51 .
  • the quantum dot LED 100 also includes an interface modification material 3 .
  • the interface modification material 3 is filled in the gaps between the quantum dots 41 of the quantum dot luminescent layer 4, in the gaps between the electron transport materials 51 of the electron transport layer 5, and between the adjacent quantum dots 41 and In the gap between electron transport materials 51 .
  • the interface modification material 3 is filled between the quantum dot light emitting layer 4 and the electron transport layer 5 .
  • the gaps of all the quantum dots 41 in the quantum dot light-emitting layer 4 are filled with the interface modification material 3 .
  • the gap between the quantum dots 41 in the region of the quantum dot luminescent layer 4 adjacent to the electron transport layer 5 is filled with an interface modification material 3, and the quantum dot luminescent layer 4 The gap between the quantum dots 41 in the region on the side away from the electron transport layer 5 is not filled with the interface modification material 3 .
  • the quantum dot light emitting diode 100 further includes a hole transport layer and a hole injection layer sequentially stacked on the bottom electrode 2 .
  • the quantum dot LED 100 also includes an electron injection layer located between the electron transport layer 5 and the top electrode 6 .
  • the embodiment of the present application also provides another quantum dot light-emitting diode 100 , which includes a substrate 1 , a bottom electrode 2 , a quantum dot light-emitting layer 4 , a transition layer 10 , an electron transport layer 5 and a top electrode 6 stacked in sequence.
  • the quantum dot light-emitting layer 4 includes quantum dots 41
  • the electron transport layer 5 includes an electron transport material 51 .
  • the quantum dot LED 100 also includes an interface modification material 3 .
  • the transition layer 10 includes quantum dots 41 , electron transport materials 51 and interface modification materials 3 .
  • the gaps between the quantum dots 41 in the transition layer 10, the gaps between the electron transport materials 51, and the gaps between the quantum dots 41 and the electron transport materials 51 are filled with the interface modification material 3, in other words , the quantum dots 41 and the electron transport material 51 in the transition layer 10 are randomly embedded in the interface modification material 3 .
  • the interface modification material 3 is also filled between the quantum dot luminescent layer 4 and the transition layer 10, between the transition layer 10 and the electron transport layer 5, and between the quantum dots 41 of the quantum dot luminescent layer 4 In the gap between, and in the gap between the electron transport material 51 of the electron transport layer 5 .
  • the gaps of all the quantum dots 41 in the quantum dot light-emitting layer 4 are filled with the interface modification material 3 .
  • the gap between the quantum dots 41 in the region of the quantum dot luminescent layer 4 adjacent to the transition layer 10 is filled with the interface modification material 3, and the quantum dot luminescent layer 4 The gap between the quantum dots 41 in the region away from the transition layer 10 is not filled with the interface modification material 3 .
  • the quantum dot light emitting diode 100 further includes a hole transport layer and a hole injection layer sequentially stacked on the bottom electrode 2 .
  • the quantum dot LED 100 also includes an electron injection layer located between the electron transport layer 5 and the top electrode 6 .
  • a substrate 1 with an ITO bottom electrode 2 bonded to its surface is provided;
  • interface modification material PEI electron transport material nano-ZnO and organic solvent ethylene glycol monomethyl ether, add PEI and nano-ZnO to ethylene glycol monomethyl ether, and mix well to obtain a mixed solution of PEI:nano-ZnO, wherein, The concentration of PEI is 0.1wt%;
  • an Ag electrode was vapor-deposited at a rate of 1 ⁇ /sec for 200 seconds, and the thickness of Ag was 20 nm to obtain a quantum dot light-emitting diode 100 .
  • the interface modification material 3 of the quantum dot light-emitting diode 100 in this embodiment is filled between the quantum dot light-emitting layer 4 and the electron transport layer 5, on the side of the quantum dot light-emitting layer 4 adjacent to the electron transport layer 5 In the gaps between the quantum dots 41 in the region, and in the gaps between the electron transport materials 51 of the electron transport layer 5 .
  • a substrate 1 with an ITO bottom electrode 2 bonded to its surface is provided;
  • interface modification material PEI electron transport material nano-ZnO and organic solvent ethylene glycol monomethyl ether, add PEI and nano-ZnO to ethylene glycol monomethyl ether, and mix well to obtain a mixed solution of PEI:nano-ZnO, wherein, The concentration of PEI is 0.1wt%;
  • the Ag electrode Under the condition of a vacuum degree of 3 ⁇ 10 ⁇ 4 Pa, the Ag electrode was vapor-deposited at a rate of 1 angstrom/second for 1000 seconds, and the Ag thickness was 100 nm to obtain a quantum dot light-emitting diode 100 .
  • the interface modification material 3 of the quantum dot light-emitting diode 100 in this embodiment is filled between the quantum dot light-emitting layer 4 and the electron transport layer 5, on the side of the quantum dot light-emitting layer 4 adjacent to the electron transport layer 5 In the gaps between the quantum dots 41 in the region, and in the gaps between the electron transport materials 51 of the electron transport layer 5 .
  • a substrate 1 with an ITO bottom electrode 2 bonded to its surface is provided;
  • interface modification material PEI electron transport material nano-ZnO and organic solvent ethylene glycol monomethyl ether, add PEI and nano-ZnO to ethylene glycol monomethyl ether, and mix well to obtain a mixed solution of PEI:nano-ZnO, wherein, The concentration of PEI is 0.1wt%;
  • the surface of the hole transport layer is spin-coated with a concentration of 20mg/mL quantum dot material for 30 seconds at a speed of 2000r/s, and the mixed solution is added dropwise within 2 seconds after the start of the spin coating. Baking at °C for 5 minutes to obtain the quantum dot light-emitting layer 4, the transition layer 10 combined with the quantum dot light-emitting layer 4, and the electron transport layer 5 combined with the transition layer 10;
  • an Ag electrode was vapor-deposited at a rate of 1 ⁇ /sec for 200 seconds, and the thickness of Ag was 20 nm to obtain a quantum dot light-emitting diode 100 .
  • the quantum dot light-emitting diode 100 of this embodiment in the gaps between the quantum dots 41 in the transition layer 10, in the gaps between the electron transport materials 51, and in the gaps between the quantum dots 41 and the electron transport materials 51 Both are filled with the interface modifying material 3 .
  • the interface modification material 3 is also filled between the quantum dot luminescent layer 4 and the transition layer 10, between the transition layer 10 and the electron transport layer 5, and adjacent to the quantum dot luminescent layer 4.
  • the gap between the quantum dots 41 in the region on one side of the transition layer 10 and in the gap between the electron transport materials of the electron transport layer 5 In the gap between the quantum dots 41 in the region on one side of the transition layer 10 and in the gap between the electron transport materials of the electron transport layer 5 .
  • a substrate 1 with an ITO bottom electrode 2 bonded to its surface is provided;
  • interface modification material PEI electron transport material nano-ZnO and organic solvent ethylene glycol monomethyl ether, add PEI and nano-ZnO to ethylene glycol monomethyl ether, and mix well to obtain a mixed solution of PEI:nano-ZnO, wherein, The concentration of PEI is 0.1wt%;
  • the surface of the hole transport layer is spin-coated with a concentration of 20mg/mL quantum dot material for 30 seconds at a speed of 2000r/s, and the mixed solution is added dropwise within 2 seconds after the start of the spin coating. Baking at °C for 5 minutes to obtain the quantum dot light-emitting layer 4, the transition layer 10 combined with the quantum dot light-emitting layer 4, and the electron transport layer 5 combined with the transition layer 10;
  • the Ag electrode Under the condition of a vacuum degree of 3 ⁇ 10 ⁇ 4 Pa, the Ag electrode was vapor-deposited at a rate of 1 angstrom/second for 1000 seconds, and the Ag thickness was 100 nm to obtain a quantum dot light-emitting diode 100 .
  • the quantum dot light-emitting diode 100 of this embodiment in the gaps between the quantum dots 41 in the transition layer 10, in the gaps between the electron transport materials 51, and in the gaps between the quantum dots 41 and the electron transport materials 51 Both are filled with the interface modifying material 3 .
  • the interface modification material 3 is also filled between the quantum dot luminescent layer 4 and the transition layer 10, between the transition layer 10 and the electron transport layer 5, and adjacent to the quantum dot luminescent layer 4.
  • the gap between the quantum dots 41 in the region on one side of the transition layer 10 and in the gap between the electron transport materials of the electron transport layer 5 In the gap between the quantum dots 41 in the region on one side of the transition layer 10 and in the gap between the electron transport materials of the electron transport layer 5 .
  • a substrate 1 with an ITO bottom electrode 2 bonded to its surface is provided;
  • interface modification material PEI electron transport material nano-ZnO and organic solvent ethanol, add PEI and nano-ZnO to ethanol, after mixing evenly, obtain PEI:nano-ZnO mixed solution, wherein, the concentration of PEI is 0.1wt%;
  • an Ag electrode was vapor-deposited at a rate of 1 ⁇ /sec for 200 seconds, and the thickness of Ag was 20 nm to obtain a quantum dot light-emitting diode 100 .
  • the interface modification material 3 of the quantum dot light-emitting diode 100 in this embodiment is filled between the quantum dot light-emitting layer 4 and the electron transport layer 5, on the side of the quantum dot light-emitting layer 4 adjacent to the electron transport layer 5 In the gaps between the quantum dots 41 in the region, and in the gaps between the electron transport materials 51 of the electron transport layer 5 .
  • a substrate 1 with an ITO bottom electrode 2 bonded to its surface is provided;
  • interface modification material PEI electron transport material nano-ZnO and organic solvent ethanol, add PEI and nano-ZnO to ethanol, after mixing evenly, obtain PEI:nano-ZnO mixed solution, wherein, the concentration of PEI is 0.1wt%;
  • the Ag electrode Under the condition of a vacuum degree of 3 ⁇ 10 ⁇ 4 Pa, the Ag electrode was vapor-deposited at a rate of 1 angstrom/second for 1000 seconds, and the Ag thickness was 100 nm to obtain a quantum dot light-emitting diode 100 .
  • the interface modification material 3 of the quantum dot light-emitting diode 100 in this embodiment is filled between the quantum dot light-emitting layer 4 and the electron transport layer 5, on the side of the quantum dot light-emitting layer 4 adjacent to the electron transport layer 5 In the gaps between the quantum dots 41 in the region, and in the gaps between the electron transport materials 51 of the electron transport layer 5 .
  • a substrate 1 with an ITO bottom electrode 2 bonded to its surface is provided;
  • interface modification material PEI electron transport material nano-ZnO and organic solvent ethanol, add PEI and nano-ZnO to ethanol, after mixing evenly, obtain PEI:nano-ZnO mixed solution, wherein, the concentration of PEI is 0.1wt%;
  • an Ag electrode was vapor-deposited at a rate of 1 ⁇ /sec for 200 seconds, and the thickness of Ag was 20 nm to obtain a quantum dot light-emitting diode 100 .
  • the quantum dot light-emitting diode 100 of this embodiment in the gaps between the quantum dots 41 in the transition layer 10, in the gaps between the electron transport materials 51, and in the gaps between the quantum dots 41 and the electron transport materials 51 Both are filled with the interface modifying material 3 .
  • the interface modification material 3 is also filled between the quantum dot luminescent layer 4 and the transition layer 10, between the transition layer 10 and the electron transport layer 5, and adjacent to the quantum dot luminescent layer 4.
  • the gap between the quantum dots 41 in the region on one side of the transition layer 10 and in the gap between the electron transport materials of the electron transport layer 5 In the gap between the quantum dots 41 in the region on one side of the transition layer 10 and in the gap between the electron transport materials of the electron transport layer 5 .
  • a substrate 1 with an ITO bottom electrode 2 bonded to its surface is provided;
  • interface modification material PEI electron transport material nano-ZnO and organic solvent ethanol, add PEI and nano-ZnO to ethanol, after mixing evenly, obtain a mixed solution of PEI:nano-ZnO, wherein the concentration of PEI/PEIE is 0.1wt%;
  • the surface of the hole transport layer is spin-coated with a concentration of 20mg/mL quantum dot material for 30 seconds at a speed of 2000r/s, and the mixed solution is added dropwise within 2 seconds after the start of the spin coating. Baking at °C for 5 minutes to obtain the quantum dot light-emitting layer 4, the transition layer 10 combined with the quantum dot light-emitting layer 4, and the electron transport layer 5 combined with the transition layer 10;
  • the Ag electrode Under the condition of a vacuum degree of 3 ⁇ 10 ⁇ 4 Pa, the Ag electrode was vapor-deposited at a rate of 1 angstrom/second for 1000 seconds, and the Ag thickness was 100 nm to obtain a quantum dot light-emitting diode 100 .
  • the quantum dot light-emitting diode 100 of this embodiment in the gaps between the quantum dots 41 in the transition layer 10, in the gaps between the electron transport materials 51, and in the gaps between the quantum dots 41 and the electron transport materials 51 Both are filled with the interface modifying material 3 .
  • the interface modification material 3 is also filled between the quantum dot luminescent layer 4 and the transition layer 10, between the transition layer 10 and the electron transport layer 5, and adjacent to the quantum dot luminescent layer 4.
  • the gap between the quantum dots 41 in the region on one side of the transition layer 10 and in the gap between the electron transport materials of the electron transport layer 5 In the gap between the quantum dots 41 in the region on one side of the transition layer 10 and in the gap between the electron transport materials of the electron transport layer 5 .
  • a substrate with an ITO bottom electrode bonded to its surface is provided;
  • an Ag electrode was evaporated at a rate of 1 angstrom/second for 200 seconds, and the thickness of Ag was 20 nm to obtain a conventional quantum dot light-emitting diode.
  • a substrate with an ITO bottom electrode bonded to its surface is provided;
  • an Ag electrode was evaporated at a rate of 1 angstrom/second for 1000 seconds, and the Ag thickness was 20 nm to obtain a conventional quantum dot light-emitting diode.
  • the QLED JVL test method is: use Keithley2400 to apply a voltage to the quantum dot light-emitting diode from -0.6V, where the voltage step is 0.2V, and the voltage application range is -0.6V to 8V; with the application of the voltage, record the device current density and The change of luminance with voltage, the graph of the change of current density with voltage (refer to Figure 4), the graph of the change of luminance with voltage (refer to Fig. 5); the external quantum efficiency and current efficiency of the device can be obtained by calculation, and the external quantum efficiency can be obtained Efficiency-voltage curve (see Figure 6), current efficiency-voltage curve (see Figure 7).
  • the 128-channel QLED life test system controls the digital IO card of NI (National Instruments) through the PCI bus communication of the central processing computer to realize the chip selection of the number of channels and the output of digital signals, and the corresponding digital signals are converted to analog through the D/A chip. signal, complete the current output (I), and realize data acquisition through the data acquisition card.
  • the acquisition of brightness converts the optical signal into an electrical signal through the sensor, and uses the electrical signal to simulate the brightness change (L).
  • Select 3-4 different constant current densities (such as 100mA/cm 2 , 50mA/cm 2 , 20mA/cm 2 , 10mA/cm 2 ), and test the initial brightness under corresponding conditions; maintain a constant current and record the brightness and the change of device voltage with time to obtain the brightness-time curve (refer to Figure 8); record the time T95, T80, T75 and T50; calculate the acceleration factor by curve fitting; extrapolate the time T for the brightness of the device to decay from 1000 nits to 95% by empirical formula, that is, the life of the device.
  • LMAX is the highest brightness
  • A is the acceleration factor

Abstract

The present application discloses a quantum dot light-emitting diode and a preparation method therefor. The preparation method comprises: forming a quantum dot film on a bottom electrode, then applying a mixed solution formed by an interface modification material, an electron transport material and an organic solvent to the surface of the quantum dot film, and drying to obtain a light-emitting layer and an electron transport layer. Thus, a contact mode between quantum dots and the electron transport material can be changed from conventional point contact to surface contact, thereby facilitating electron transport between the light-emitting layer and the electron transport layer.

Description

一种量子点发光二极管及其制备方法A quantum dot light-emitting diode and its preparation method
本申请要求于2021年06月04日在中国专利局提交的、申请号为202110622011.3、申请名称为“一种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。This application claims the priority of the Chinese patent application with the application number 202110622011.3 and the application title "A Quantum Dot Light-Emitting Diode and Its Preparation Method" filed at the China Patent Office on June 4, 2021, the entire contents of which are incorporated by reference incorporated in this application.
技术领域technical field
本申请涉及显示技术领域,尤其涉及一种量子点发光二极管的制备方法及应用所述方法制得的量子点发光二极管。The present application relates to the field of display technology, in particular to a method for preparing a quantum dot light-emitting diode and a quantum dot light-emitting diode prepared by applying the method.
背景技术Background technique
QLED(Quantum Dots Light-Emitting Diode,量子点发光器件)是一种新兴的显示器件,其结构与OLED(Organic Light-Emitting Diode,有机发光器件)相似,是一项介于液晶和OLED之间的新型技术。QLED技术的核心为量子点。量子点是一种粒子直径不足10nm的颗粒,主要由锌、镉、硫、硒原子组成。当量子点受到光电刺激时,会发出有色的光线,光线的颜色是由组成量子点的材料和量子点的大小及形状决定。量子点独特的量子尺寸效应、宏观量子隧道效应、量子尺寸效应和表面效应使其展现出出色的物理性能,尤其是光学性能,例如光谱可调、发光强度大、色纯度高、荧光寿命长、单光源可激发多色荧光等优势。QLED (Quantum Dots Light-Emitting Diode, quantum dot light-emitting device) is a new display device, its structure is similar to that of OLED (Organic Light-Emitting Diode, organic light-emitting device) is a new technology between liquid crystal and OLED. The core of QLED technology is quantum dots. Quantum dots are particles with a particle diameter of less than 10nm, mainly composed of zinc, cadmium, sulfur, and selenium atoms. When the quantum dot is stimulated by light, it will emit colored light. The color of the light is determined by the material of the quantum dot and the size and shape of the quantum dot. The unique quantum size effect, macroscopic quantum tunneling effect, quantum size effect and surface effect of quantum dots make them exhibit excellent physical properties, especially optical properties, such as adjustable spectrum, high luminous intensity, high color purity, long fluorescence lifetime, A single light source can excite multicolor fluorescence and other advantages.
目前,QLED的发光效率已经基本达到商业化的需求。此外,QLED的寿命长,封装工艺简单或无需封装,有望成为下一代平板显示器,具有广阔发展前景。然而,实际上现阶段制备的量子点发光二极管工作寿命远没有达到理论应有的长度,并且测试过程中经常会出现荧光猝灭的现象,此种情况的发生极大的制约了量子点发光器件的研发进展。而出现此类问题的主要原因是量子点发光二极管中的空穴载流子和电子载流子的传输速率不平衡使得量子点充电以及荧光淬灭。At present, the luminous efficiency of QLED has basically met the needs of commercialization. In addition, QLED has a long lifespan and simple or no packaging process. It is expected to become the next generation of flat panel displays and has broad development prospects. However, in fact, the working life of the quantum dot light-emitting diodes prepared at this stage is far from the theoretical length, and the phenomenon of fluorescence quenching often occurs during the test process, which greatly restricts the quantum dot light-emitting devices. development progress. The main reason for such problems is that the transport rate of hole carriers and electron carriers in the quantum dot light-emitting diode is unbalanced, which makes the quantum dot charging and fluorescence quenching.
技术问题technical problem
因此,现有技术中的量子点发光二极管中的空穴载流子和电子载流子的传输速率平衡有待进一步提高。Therefore, the balance of the transmission rate of hole carriers and electron carriers in the quantum dot light-emitting diodes in the prior art needs to be further improved.
技术解决方案technical solution
因此,本申请提供一种量子点发光二极管的制备方法及应用所述方法制得的量子点发光二极管。Therefore, the present application provides a method for preparing a quantum dot light-emitting diode and a quantum dot light-emitting diode prepared by using the method.
本申请实施例提供一种量子点发光二极管的制备方法,其包括如下步骤:The embodiment of the present application provides a method for preparing a quantum dot light-emitting diode, which includes the following steps:
提供衬底,在所述衬底上形成底电极;providing a substrate on which a bottom electrode is formed;
提供界面修饰材料、电子传输材料及有机溶剂,混合,得到混合溶液;Provide interface modification materials, electron transport materials and organic solvents, and mix them to obtain a mixed solution;
提供量子点材料,将所述量子点材料设置在底电极上,形成量子点膜,再将所述混合溶液设置在所述量子点膜的表面,干燥以得到量子点发光层及电子传输层,其中,所述量子点膜为量子点干膜或量子点湿膜;Provide a quantum dot material, arrange the quantum dot material on the bottom electrode to form a quantum dot film, then place the mixed solution on the surface of the quantum dot film, and dry to obtain a quantum dot light-emitting layer and an electron transport layer, Wherein, the quantum dot film is a quantum dot dry film or a quantum dot wet film;
在所述电子传输层上形成顶电极。A top electrode is formed on the electron transport layer.
可选的,在本申请的一些实施例中,所述量子点发光层及电子传输层之间形成有过渡层,所述过渡层内包含量子点、界面修饰材料及电子传输材料,所述过渡层中的界面修饰材料填充在所述过渡层中的量子点之间的间隙中、电子传输材料之间的间隙中、及量子点与电子传输材料之间的间隙中。Optionally, in some embodiments of the present application, a transition layer is formed between the quantum dot light-emitting layer and the electron transport layer, and the transition layer contains quantum dots, interface modification materials and electron transport materials. The interface modifying material in the layer fills in the gaps between the quantum dots in the transition layer, in the gaps between the electron transport materials, and in the gaps between the quantum dots and the electron transport materials.
可选的,在本申请的一些实施例中,将所述混合溶液设置在所述量子点膜的表面之后还包括静置的步骤,所述静置时间为5-10秒。Optionally, in some embodiments of the present application, after disposing the mixed solution on the surface of the quantum dot film, a step of standing still is included, and the standing time is 5-10 seconds.
可选的,在本申请的一些实施例中,提供量子点材料,将所述量子点材料设置在所述底电极上,形成量子点膜,再将所述混合溶液设置在所述量子点膜的表面,具体为:Optionally, in some embodiments of the present application, a quantum dot material is provided, the quantum dot material is disposed on the bottom electrode to form a quantum dot film, and then the mixed solution is disposed on the quantum dot film surface, specifically:
提供量子点材料,将量子点材料设置在底电极上,形成量子点干膜,得到量子点发光层后,将所述混合溶液添加至所述量子点发光层上。Provide quantum dot material, arrange quantum dot material on the bottom electrode, form quantum dot dry film, after obtaining quantum dot light-emitting layer, add the mixed solution on the quantum dot light-emitting layer.
可选的,在本申请的一些实施例中,提供量子点材料,将所述量子点材料设置在所述底电极上,形成量子点膜,再将所述混合溶液设置在所述量子点膜的表面,具体为:Optionally, in some embodiments of the present application, a quantum dot material is provided, the quantum dot material is disposed on the bottom electrode to form a quantum dot film, and then the mixed solution is disposed on the quantum dot film surface, specifically:
提供量子点材料,将所述量子点材料设置在底电极上,形成量子点湿膜,再将所述混合溶液通过溶液法设置在所述量子点湿膜的表面。The quantum dot material is provided, and the quantum dot material is arranged on the bottom electrode to form a quantum dot wet film, and then the mixed solution is arranged on the surface of the quantum dot wet film by a solution method.
可选的,在本申请的一些实施例中,提供量子点材料,将所述量子点材料设置在所述底电极上,形成量子点膜,再将所述混合溶液设置在所述量子点膜的表面,具体为:Optionally, in some embodiments of the present application, a quantum dot material is provided, the quantum dot material is disposed on the bottom electrode to form a quantum dot film, and then the mixed solution is disposed on the quantum dot film surface, specifically:
提供量子点材料,将量子点材料旋涂在所述底电极上,形成量子点湿膜,并在旋涂开始后数秒内添加所述混合溶液,添加结束后停止旋涂。The quantum dot material is provided, and the quantum dot material is spin-coated on the bottom electrode to form a quantum dot wet film, and the mixed solution is added within a few seconds after the spin coating starts, and the spin coating is stopped after the addition is completed.
可选的,在本申请的一些实施例中,所述旋涂的转速为2000-3000r/。Optionally, in some embodiments of the present application, the rotational speed of the spin coating is 2000-3000 r/.
可选的,在本申请的一些实施例中,所述数秒为2-10秒。Optionally, in some embodiments of the present application, the number of seconds is 2-10 seconds.
可选的,在本申请的一些实施例中,所述界面修饰材料选自聚乙烯亚胺、聚乙氧基乙烯亚胺、聚[9,9-二(3’-(N,N-二甲基氨基)丙基)-2,7-芴]-2,7-(9,9-二辛基芴))]、聚乙二醇、共轭聚合电解质或聚氧化乙烯中的一种或几种。Optionally, in some embodiments of the present application, the interface modification material is selected from polyethyleneimine, polyethoxyethyleneimine, poly[9,9-bis(3'-(N,N-di One of methylamino)propyl)-2,7-fluorene]-2,7-(9,9-dioctylfluorene))], polyethylene glycol, conjugated polyelectrolyte or polyethylene oxide or Several kinds.
可选的,在本申请的一些实施例中,所述电子传输材料选自金属氧化物、掺杂金属氧化物、2-6族半导体材料、3-5族半导体材料及1-3-6族半导体材料中的一种或几种,所述金属氧化物选自ZnO、TiO 2、SnO 2中的一种或几种;所述掺杂金属氧化物中的金属氧化物选自ZnO、TiO 2、SnO 2中的一种或几种,掺杂元素选自铝、镁、铟、镓中的一种或几种;所述2-6半导体族材料选自ZnS、ZnSe、CdS中的一种或几种;所述3-5半导体族材料选自InP、GaP中的至少一种;所述1-3-6族半导体材料选自CuInS、CuGaS中的至少一种。 Optionally, in some embodiments of the present application, the electron transport material is selected from metal oxides, doped metal oxides, 2-6 group semiconductor materials, 3-5 group semiconductor materials and 1-3-6 group One or more of semiconductor materials, the metal oxide is selected from one or more of ZnO, TiO 2 , SnO 2 ; the metal oxide in the doped metal oxide is selected from ZnO, TiO 2 , SnO 2 or more, the doping element is selected from one or more of aluminum, magnesium, indium, gallium; the 2-6 semiconductor group material is selected from one of ZnS, ZnSe, CdS or several; the 3-5 group semiconductor material is selected from at least one of InP and GaP; the 1-3-6 group semiconductor material is selected from at least one of CuInS and CuGaS.
可选的,在本申请的一些实施例中,所述有机溶剂选自乙二醇单甲醚、异丙醇或乙醇中的一种或几种。Optionally, in some embodiments of the present application, the organic solvent is selected from one or more of ethylene glycol monomethyl ether, isopropanol or ethanol.
可选的,在本申请的一些实施例中,所述混合溶液中,所述界面修饰材料的浓度范围为0.1wt%-10wt%。Optionally, in some embodiments of the present application, in the mixed solution, the concentration of the interface modification material ranges from 0.1wt% to 10wt%.
可选的,在本申请的一些实施例中,所述混合溶液中,所述电子传输材料的浓度范围为10-30mg/mL。Optionally, in some embodiments of the present application, the concentration range of the electron transport material in the mixed solution is 10-30 mg/mL.
相应的,本申请实施例还提供一种量子点发光二极管,其包括层叠设置的底电极、量子点发光层、电子传输层及顶电极,所述量子点发光层中包含量子点,所述电子传输层包含电子传输材料,其中,相邻的量子点和电子传输材料之间的间隙中填充有界面修饰材料。Correspondingly, the embodiment of the present application also provides a quantum dot light-emitting diode, which includes a stacked bottom electrode, a quantum dot light-emitting layer, an electron transport layer, and a top electrode, the quantum dot light-emitting layer contains quantum dots, and the electrons The transport layer contains an electron transport material, wherein the gap between adjacent quantum dots and the electron transport material is filled with an interface modification material.
可选的,在本申请的一些实施例中,所述量子点发光层的邻近电子传输层一侧的量子点之间的间隙中、及所述电子传输层的电子传输材料之间的间隙中也填充有所述界面修饰材料。Optionally, in some embodiments of the present application, in the gap between the quantum dots on the side adjacent to the electron transport layer of the quantum dot light-emitting layer, and in the gap between the electron transport materials of the electron transport layer Also filled with the interface modifying material.
可选的,在本申请的一些实施例中,所述量子点发光二极管还包括位于量子点发光层与电子传输层之间的过渡层,所述过渡层内包含量子点、界面修饰材料及电子传输材料,所述过渡层中的界面修饰材料填充在所述过渡层中的量子点之间的间隙中、电子传输材料之间的间隙中、及量子点与电子传输材料之间的间隙中。Optionally, in some embodiments of the present application, the quantum dot light-emitting diode further includes a transition layer located between the quantum dot light-emitting layer and the electron transport layer, and the transition layer contains quantum dots, interface modification materials, and electrons. The transport material, the interface modifying material in the transition layer is filled in the gaps between the quantum dots in the transition layer, the gaps between the electron transport materials, and the gaps between the quantum dots and the electron transport materials.
可选的,在本申请的一些实施例中,所述界面修饰材料还填充在所述量子点发光层与过渡层之间、所述过渡层与所述电子传输层之间。Optionally, in some embodiments of the present application, the interface modification material is also filled between the quantum dot light-emitting layer and the transition layer, and between the transition layer and the electron transport layer.
可选的,在本申请的一些实施例中,所述界面修饰材料选自聚乙烯亚胺、聚乙氧基乙烯亚胺、聚[9,9-二(3’-(N,N-二甲基氨基)丙基)-2,7-芴]-2,7-(9,9-二辛基芴))]、聚乙二醇、共轭聚合电解质或聚氧化乙烯中的一种或几种。Optionally, in some embodiments of the present application, the interface modification material is selected from polyethyleneimine, polyethoxyethyleneimine, poly[9,9-bis(3'-(N,N-di One of methylamino)propyl)-2,7-fluorene]-2,7-(9,9-dioctylfluorene))], polyethylene glycol, conjugated polyelectrolyte or polyethylene oxide or Several kinds.
可选的,在本申请的一些实施例中,所述电子传输材料选自金属氧化物、掺杂金属氧化物、2-6族半导体材料、3-5族半导体材料及1-3-6族半导体材料中的一种或几种,所述金属氧化物选自ZnO、TiO 2、SnO 2中的一种或几种;所述掺杂金属氧化物中的金属氧化物选自ZnO、TiO 2、SnO 2中的一种或几种,掺杂元素选自铝、镁、铟、镓中的一种或几种;所述2-6半导体族材料选自ZnS、ZnSe、CdS中的一种或几种;所述3-5半导体族材料选自InP、GaP中的至少一种;所述1-3-6族半导体材料选自CuInS、CuGaS中的至少一种。 Optionally, in some embodiments of the present application, the electron transport material is selected from metal oxides, doped metal oxides, 2-6 group semiconductor materials, 3-5 group semiconductor materials and 1-3-6 group One or more of semiconductor materials, the metal oxide is selected from one or more of ZnO, TiO 2 , SnO 2 ; the metal oxide in the doped metal oxide is selected from ZnO, TiO 2 , SnO 2 or more, the doping element is selected from one or more of aluminum, magnesium, indium, gallium; the 2-6 semiconductor group material is selected from one of ZnS, ZnSe, CdS or several; the 3-5 group semiconductor material is selected from at least one of InP and GaP; the 1-3-6 group semiconductor material is selected from at least one of CuInS and CuGaS.
有益效果Beneficial effect
本申请的量子点发光二极管的制备方法先将界面修饰材料与电子传输材料及有机溶剂混合得到混合溶液,再将混合溶液设置在量子点发光层的表面时,界面修饰材料将随着有机溶剂渗透至量子点的间隙中。如此,制备得到的量子点发光二极管的界面修饰材料填充在所述量子点发光层的量子点之间的间隙中、所述电子传输层的电子传输材料之间的间隙中、及相邻的量子点和电子传输材料之间的间隙中。如此,量子点与电子传输材料之间的接触模式由常规的点接触改为面接触,可以有效的增加量子点发光层与电子传输层之间的有效接触面积,促进量子点发光层与电子传输层之间的电子传输,减少甚至避免空穴载流子和电子载流子的传输速率不平衡的问题,进而避免量子点充电以及荧光淬灭的现象。The preparation method of the quantum dot light-emitting diode of the present application first mixes the interface modification material with the electron transport material and the organic solvent to obtain a mixed solution, and then when the mixed solution is arranged on the surface of the quantum dot light-emitting layer, the interface modification material will penetrate with the organic solvent into the gap between the quantum dots. In this way, the interface modification material of the prepared quantum dot light-emitting diode is filled in the gaps between the quantum dots of the quantum dot light-emitting layer, the gap between the electron transport materials of the electron transport layer, and the adjacent quantum dots. In the gap between the dots and the electron transport material. In this way, the contact mode between the quantum dots and the electron transport material is changed from the conventional point contact to the surface contact, which can effectively increase the effective contact area between the quantum dot light-emitting layer and the electron transport layer, and promote the quantum dot light-emitting layer and electron transport. Electron transport between layers reduces or even avoids the problem of unbalanced transport rates of hole carriers and electron carriers, thereby avoiding quantum dot charging and fluorescence quenching.
本申请的量子点发光二极管的制备方法先将界面修饰材料与电子传输材料及有机溶剂混合得到混合溶液,再将所述混合溶液设置在所述量子点湿膜的表面,如此,界面修饰材料将随着有机溶剂渗透至量子点的间隙中,且量子点湿膜表面的量子点与电子传输材料会因重力等因素产生互混,可以进一步提高量子点发光层与电子传输层的有效接触面积,促进量子点发光层与电子传输层之间的电子传输。The preparation method of the quantum dot light-emitting diode of the present application first mixes the interface modification material with the electron transport material and the organic solvent to obtain a mixed solution, and then arranges the mixed solution on the surface of the quantum dot wet film, so that the interface modification material will As the organic solvent penetrates into the gaps of the quantum dots, and the quantum dots on the surface of the quantum dot wet film and the electron transport material will be mixed due to factors such as gravity, the effective contact area between the quantum dot light-emitting layer and the electron transport layer can be further increased. Promote electron transport between the quantum dot light-emitting layer and the electron transport layer.
本申请的量子点发光二极管的制备方法使用的界面修饰材料具有降低材料功函以及钝化材料表面缺陷的效果,当其渗入到量子点与电子传输材料界面时,对材料界面有调节作用,可以降低材料的界面势垒,从而促进电荷的传输。此外,由于量子点与电子传输材料的颗粒尺寸小,均为纳米结构,材料的比表面积大,表面缺陷含量高,这将对自由电荷产生很强的捕获作用,从而发生非荧光复合,造成器件性能不佳。但是在界面修饰材料的包覆作用下,纳米颗粒表面缺陷将被钝化,可以减少非荧光复合,提升器件性能。The interface modification material used in the preparation method of the quantum dot light-emitting diode of the present application has the effect of reducing the work function of the material and passivating the surface defects of the material. When it penetrates into the interface between the quantum dot and the electron transport material, it has a regulating effect on the material interface, which can Reduce the interfacial barrier of the material, thereby facilitating the transport of charges. In addition, due to the small particle size of quantum dots and electron transport materials, both of which are nanostructures, the materials have a large specific surface area and a high content of surface defects, which will have a strong capture effect on free charges, resulting in non-fluorescence recombination, resulting in device Poor performance. However, under the coating effect of interface modification materials, the surface defects of nanoparticles will be passivated, which can reduce non-fluorescence recombination and improve device performance.
附图说明Description of drawings
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他的附图。In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings that need to be used in the description of the embodiments will be briefly introduced below. Obviously, the drawings in the following description are only some embodiments of the present application. For those skilled in the art, other drawings can also be obtained based on these drawings without any creative effort.
图1是本申请实施例提供的量子点发光二极管的制备方法流程图;Fig. 1 is the flow chart of the preparation method of the quantum dot light-emitting diode provided by the embodiment of the present application;
图2是本申请实施例提供的量子点发光二极管的示意图;2 is a schematic diagram of a quantum dot light-emitting diode provided in an embodiment of the present application;
图3是本申请实施例提供的另一种量子点发光二极管的示意图;Fig. 3 is a schematic diagram of another quantum dot light-emitting diode provided by the embodiment of the present application;
图4是本申请实施例1及对比例1的量子点发光二极管的电流密度随电压的变化的曲线图;Fig. 4 is the graph that the current density of the quantum dot light-emitting diode of the application embodiment 1 and comparative example 1 changes with the voltage;
图5是本申请实施例1及对比例1的量子点发光二极管的亮度随电压的变化的曲线图;Fig. 5 is the graph that the brightness of the quantum dot light-emitting diode of the application embodiment 1 and comparative example 1 changes with voltage;
图6是本申请实施例1及对比例1的量子点发光二极管的外量子效率-电压曲线图;Fig. 6 is the external quantum efficiency-voltage curve diagram of the quantum dot light-emitting diode of embodiment 1 and comparative example 1 of the present application;
图7是本申请实施例1及对比例1的量子点发光二极管的电流效率-电压曲线图;Fig. 7 is the current efficiency-voltage curve diagram of the quantum dot light-emitting diode of embodiment 1 and comparative example 1 of the present application;
图8是本申请实施例1及对比例1的量子点发光二极管的亮度-时间曲线图;Fig. 8 is the luminance-time graph of the quantum dot light-emitting diodes of Example 1 and Comparative Example 1 of the present application;
图9是本申请通过经验公式外推的实施例1的量子点发光二极管的寿命曲线图。FIG. 9 is a graph of the lifespan of the quantum dot light-emitting diode in Example 1 extrapolated by the present application through an empirical formula.
本申请的实施方式Embodiment of this application
下面将结合本申请实施例中的附图,对本申请实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本申请一部分实施例,而不是全部的实施例。基于本申请中的实施例,本领域技术人员在没有做出创造性劳动前提下所获得的所有其它实施例,都属于本申请保护的范围。The following will clearly and completely describe the technical solutions in the embodiments of the application with reference to the drawings in the embodiments of the application. Apparently, the described embodiments are only some of the embodiments of the application, not all of them. Based on the embodiments in this application, all other embodiments obtained by those skilled in the art without making creative efforts belong to the scope of protection of this application.
本申请实施例提供一种量子点发光二极管及其制备方法。以下分别进行详细说明。需说明的是,以下实施例的描述顺序不作为对实施例优选顺序的限定。另外,在本申请的描述中,术语“包括”是指“包括但不限于”。 本申请中“一种或多种”和“至少一种”等表述,是指所列举多项中的一种或者多种,“多种”是指这些项中两种或两种以上的任意组合,包括单项(种)或复数项(种)的任意组合,例如,“a、b或c中的至少一项(种)”或“a、b和c中的至少一项(种)”,均可以表示:a,b,c,a-b(即a和b),a-c,b-c,或a-b-c,其中a,b,c分别可以是单个,也可以是多个。本申请的各种实施例可以以一个范围的型式存在;应当理解,以一范围型式的描述仅仅是因为方便及简洁,不应理解为对本申请范围的硬性限制;因此,应当认为所述的范围描述已经具体公开所有可能的子范围以及该范围内的单一数值。例如,应当认为从1到6的范围描述已经具体公开子范围,例如从1到3,从1到4,从1到5,从2到4,从2到6,从3到6等,以及所述范围内的单一数字,例如1、2、3、4、5及6,此不管范围为何皆适用。另外,每当在本文中指出数值范围,是指包括所指范围内的任何引用的数字(分数或整数)。The embodiment of the present application provides a quantum dot light-emitting diode and a preparation method thereof. Each will be described in detail below. It should be noted that the description sequence of the following embodiments is not intended to limit the preferred sequence of the embodiments. In addition, in the description of the present application, the term "including" means "including but not limited to". The expressions "one or more" and "at least one" in this application refer to one or more of the listed items, and "multiple" refers to any of two or more of these items. Combinations, including any combination of single or plural terms (species), for example, "at least one (species) of a, b, or c" or "at least one (species) of a, b, and c" , can represent: a, b, c, a-b (that is, a and b), a-c, b-c, or a-b-c, where a, b, and c can be single or multiple. Various embodiments of the present application may exist in the form of a range; it should be understood that the description in the form of a range is only for convenience and brevity, and should not be construed as a rigid limitation on the scope of the application; therefore, the described range should be regarded as The description has specifically disclosed all possible subranges as well as individual values within that range. For example, a description of a range from 1 to 6 should be considered to have specifically disclosed subranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., and Single numbers within the stated ranges, eg 1, 2, 3, 4, 5 and 6, apply regardless of the range. Additionally, whenever a numerical range is indicated herein, it is meant to include any cited numeral (fractional or integral) within the indicated range.
请参阅图1-3,本申请一实施例提供一种量子点发光二极管100的制备方法,其包括如下步骤:Please refer to FIGS. 1-3 , an embodiment of the present application provides a method for preparing a quantum dot light-emitting diode 100, which includes the following steps:
步骤S1:提供衬底1,在所述衬底1上形成底电极2;Step S1: providing a substrate 1, and forming a bottom electrode 2 on the substrate 1;
步骤S2:提供界面修饰材料3、电子传输材料51及有机溶剂,混合,使界面修饰材料3溶解在有机溶剂中,并使电子传输材料51分散在有机溶剂中,得到混合溶液;Step S2: Provide the interface modification material 3, the electron transport material 51 and an organic solvent, mix them, dissolve the interface modification material 3 in the organic solvent, and disperse the electron transport material 51 in the organic solvent to obtain a mixed solution;
步骤S3:提供量子点材料,将所述量子点材料设置在底电极2上,形成量子点膜,再将所述混合溶液通过溶液法设置在所述量子点膜的表面,成膜,干燥,得到量子点发光层4及结合于量子点发光层4的电子传输层5;Step S3: providing a quantum dot material, placing the quantum dot material on the bottom electrode 2 to form a quantum dot film, and then placing the mixed solution on the surface of the quantum dot film by a solution method, forming a film, drying, Obtain the quantum dot luminescent layer 4 and the electron transport layer 5 combined with the quantum dot luminescent layer 4;
步骤S4:在所述电子传输层5上形成顶电极6。Step S4: forming a top electrode 6 on the electron transport layer 5 .
所述步骤S3中,将所述量子点材料设置在底电极2上的方法可以为本领域已知的化学成膜法或物理成膜法。其中化学成膜法包括:化学气相沉积法、连续离子层吸附与反应法、阳极氧化法、电解沉积法、共沉淀法。物理成膜法包括物理镀膜法和溶液加工法,具体的,物理镀膜法包括:热蒸发镀膜法、电子束蒸发镀膜法、磁控溅射法、多弧离子镀膜法、物理气相沉积法、原子层沉积法、脉冲激光沉积法等;溶液加工法包括旋涂法、印刷法、喷墨打印法、刮涂法、打印法、浸渍提拉法、浸泡法、喷涂法、滚涂法、浇铸法、狭缝式涂布法、条状涂布法。In the step S3, the method for disposing the quantum dot material on the bottom electrode 2 may be a chemical film-forming method or a physical film-forming method known in the art. The chemical film-forming methods include: chemical vapor deposition, continuous ion layer adsorption and reaction, anodic oxidation, electrolytic deposition, and co-precipitation. Physical film forming methods include physical coating methods and solution processing methods. Specifically, physical coating methods include: thermal evaporation coating method, electron beam evaporation coating method, magnetron sputtering method, multi-arc ion coating method, physical vapor deposition method, atomic Layer deposition method, pulsed laser deposition method, etc.; solution processing methods include spin coating method, printing method, inkjet printing method, scraping method, printing method, dipping and pulling method, soaking method, spraying method, roll coating method, casting method , Slit coating method, strip coating method.
所述量子点膜可以为已经干燥的量子点干膜或未干燥的量子点湿膜。其中,所述量子点干膜即为量子点发光层4。The quantum dot film may be a dried quantum dot film or an undried quantum dot wet film. Wherein, the quantum dot dry film is the quantum dot light-emitting layer 4 .
请参阅图2,在一实施例中,所述步骤S3为S03:提供量子点材料,将量子点材料设置在底电极2上,形成量子点干膜,得到量子点发光层4后,将所述混合溶液添加至所述量子点发光层4上,使界面修饰材料3随着有机溶剂至少渗透至所述量子点发光层4邻近电子传输层5一侧的量子点41的间隙中后,成膜,干燥,得到电子传输层5。所述界面修饰材料3填充在所述量子点发光层4的量子点41之间的间隙中、所述电子传输层5的电子传输材料51之间的间隙中、及相邻的量子点41和电子传输材料51之间的间隙中。如此,量子点41与电子传输材料51之间的接触模式由常规的点接触改为面接触,可以有效的增加量子点法发光层4与电子传输层5之间的有效接触面积,促进量子点发光层4与电子传输层5之间的电子传输,减少甚至避免空穴载流子和电子载流子的传输速率不平衡的问题,进而避免量子点41充电以及荧光淬灭的现象。Please refer to Fig. 2, in one embodiment, described step S3 is S03: provide quantum dot material, quantum dot material is arranged on the bottom electrode 2, forms quantum dot dry film, after obtaining quantum dot light-emitting layer 4, the The mixed solution is added to the quantum dot light-emitting layer 4, so that the interface modification material 3 penetrates at least into the gap of the quantum dots 41 on the side of the quantum dot light-emitting layer 4 adjacent to the electron transport layer 5 along with the organic solvent to form a film, and dried to obtain the electron transport layer 5. The interface modification material 3 is filled in the gaps between the quantum dots 41 of the quantum dot luminescent layer 4, in the gaps between the electron transport materials 51 of the electron transport layer 5, and between the adjacent quantum dots 41 and In the gap between electron transport materials 51 . In this way, the contact mode between the quantum dots 41 and the electron transport material 51 is changed from the conventional point contact to the surface contact, which can effectively increase the effective contact area between the quantum dot method light-emitting layer 4 and the electron transport layer 5, and promote the quantum dot method. The electron transport between the light-emitting layer 4 and the electron transport layer 5 reduces or even avoids the problem of unbalanced transport rates of hole carriers and electron carriers, thereby avoiding charging of quantum dots 41 and quenching of fluorescence.
在至少一实施例中,所述量子点发光层4与电子传输层5之间填充有界面修饰材料3。In at least one embodiment, the interface modification material 3 is filled between the quantum dot light emitting layer 4 and the electron transport layer 5 .
请参阅图3,在又一实施例中,所述步骤S3为S13:提供量子点材料,将所述量子点材料设置在底电极2上,形成量子点湿膜,再将所述混合溶液通过溶液法设置在所述量子点湿膜的表面,使量子点湿膜表面的量子点与电子传输材料互混,成膜后干燥,得到量子点发光层4、结合于所述量子点发光层4的过渡层10、及结合于过渡层10的电子传输层5。所述过渡层10内包含量子点41、界面修饰材料3及电子传输材料51。所述过渡层10中的界面修饰材料3填充在过渡层10中的量子点41之间的间隙中、电子传输材料51之间的间隙中、及量子点41与电子传输材料51之间的间隙中,换言之,所述过渡层10中的量子点41和电子传输材料51无规则的镶嵌在界面修饰材料3中。所述界面修饰材料3还填充在所述量子点发光层4与所述过渡层10之间、所述过渡层10与所述电子传输层5之间、所述量子点发光层4的量子点41之间的间隙中、及所述电子传输层5的电子传输材料51之间的间隙中。所述将所述混合溶液通过溶液法设置在所述量子点湿膜的表面,可以使量子点湿膜表面的量子点41与电子传输材料51互混,得到量子点41与电子传输材料51互混的过渡层,如此可以进一步提高量子点发光层4与电子传输层5的有效接触面积,促进量子点发光层4与电子传输层5之间的电子传输。Please refer to Fig. 3, in another embodiment, described step S3 is S13: provide quantum dot material, described quantum dot material is arranged on the bottom electrode 2, forms quantum dot wet film, then described mixed solution passes through The solution method is arranged on the surface of the quantum dot wet film, the quantum dots on the surface of the quantum dot wet film are mixed with the electron transport material, and dried after film formation to obtain the quantum dot light-emitting layer 4, which is combined with the quantum dot light-emitting layer 4 The transition layer 10, and the electron transport layer 5 combined with the transition layer 10. The transition layer 10 includes quantum dots 41 , an interface modification material 3 and an electron transport material 51 . The interface modification material 3 in the transition layer 10 is filled in the gaps between the quantum dots 41 in the transition layer 10, the gaps between the electron transport materials 51, and the gaps between the quantum dots 41 and the electron transport materials 51 In other words, the quantum dots 41 and the electron transport material 51 in the transition layer 10 are randomly embedded in the interface modification material 3 . The interface modification material 3 is also filled between the quantum dot luminescent layer 4 and the transition layer 10, between the transition layer 10 and the electron transport layer 5, and the quantum dots of the quantum dot luminescent layer 4 41 , and in the gap between the electron transport materials 51 of the electron transport layer 5 . The mixed solution is arranged on the surface of the quantum dot wet film by a solution method, so that the quantum dots 41 on the surface of the quantum dot wet film can be mixed with the electron transport material 51, and the quantum dots 41 and the electron transport material 51 can be mutually mixed. A mixed transition layer can further increase the effective contact area between the quantum dot light-emitting layer 4 and the electron transport layer 5, and promote the electron transport between the quantum dot light-emitting layer 4 and the electron transport layer 5.
在一较佳的实施例中,所述S13为:提供量子点材料,将量子点材料旋涂在底电极2上,形成量子点湿膜,并在旋涂开始后数秒内(即旋涂开始后且量子点材料形成干膜前)添加所述混合溶液,添加结束后停止旋涂,成膜后干燥,得到量子点发光层4、结合于所述量子点发光层4的过渡层10、及结合于过渡层10的电子传输层5。在旋涂量子点材料开始后数秒内滴加所述混合溶液,界面修饰材料3将随着有机溶剂渗透至量子点湿膜的量子点的间隙中,且旋涂过程中,量子点湿膜表面的量子点与电子传输材料可以更好的互混。In a preferred embodiment, said S13 is: provide the quantum dot material, spin coat the quantum dot material on the bottom electrode 2 to form a quantum dot wet film, and within a few seconds after the spin coating starts (that is, the spin coating starts and before the quantum dot material forms a dry film), add the mixed solution, stop the spin coating after the addition, and dry after film formation to obtain the quantum dot light-emitting layer 4, the transition layer 10 combined with the quantum dot light-emitting layer 4, and Electron transport layer 5 bonded to transition layer 10 . Add the mixed solution dropwise within a few seconds after the start of the spin-coating quantum dot material, the interface modification material 3 will penetrate into the quantum dot gap of the quantum dot wet film along with the organic solvent, and in the spin coating process, the surface of the quantum dot wet film The quantum dots and electron transport materials can be better intermixed.
可以理解的,在一实施例中,所述量子点发光层4的所有量子点的间隙中均填充有所述界面修饰材料3。在又一实施例中,所述量子点发光层4的邻近所述电子传输层5的一侧的区域中的量子点41之间的间隙填充有界面修饰材料3,远离所述电子传输层5的一侧的区域中的量子点41之间的间隙中没有填充界面修饰材料3。It can be understood that, in one embodiment, the interstices of all quantum dots in the quantum dot light-emitting layer 4 are filled with the interface modification material 3 . In yet another embodiment, the gap between the quantum dots 41 in the region of the quantum dot light-emitting layer 4 adjacent to the side of the electron transport layer 5 is filled with the interface modification material 3, away from the electron transport layer 5 The gap between the quantum dots 41 in the region on one side is not filled with the interface modification material 3 .
所述干燥的方法为本领域已知用于干燥量子点膜的方法,如烘烤等。The drying method is a method known in the art for drying quantum dot films, such as baking.
所述步骤S1中,所述衬底1的选择不受限制,可以选择柔性衬底,也可以选择硬质衬底。在所述衬底1上形成底电极2的方法为本领域常规的方法,如蒸镀。所述底电极2为阳极。所述阳极为本领域常规应用的阳极。在至少一实施例中,所述阳极2为ITO(锡-铟氧化物)。In the step S1, the choice of the substrate 1 is not limited, a flexible substrate or a hard substrate can be selected. The method for forming the bottom electrode 2 on the substrate 1 is a conventional method in the field, such as evaporation. The bottom electrode 2 is an anode. The anode is an anode commonly used in this field. In at least one embodiment, the anode 2 is ITO (tin-indium oxide).
所述步骤S2中,所述界面修饰材料具有永久偶极矩。所述界面修饰材料可以选自但不限于PEI(聚乙烯亚胺)、PEIE(聚乙氧基乙烯亚胺)、PFN(聚[9,9-二(3’-(N,N-二甲基氨基)丙基)-2,7-芴]-2,7-(9,9-二辛基芴))])、PEG(聚乙二醇)、CPE(共轭聚合电解质)、PEO(聚氧化乙烯)中的一种或几种。所述界面修饰材料3具有降低材料功函以及钝化材料表面缺陷的效果,当其渗入到量子点41与电子传输材料51界面时,对材料界面有调节作用,可以降低材料的界面势垒,从而促进电荷的传输。此外,由于量子点41与电子传输材料51材料颗粒尺寸小,均为纳米结构,材料的比表面积大,表面缺陷含量高,这将对自由电荷产生很强的捕获作用,从而发生非荧光复合,造成器件性能不佳。但是在界面修饰材料3的包覆作用下,纳米颗粒表面缺陷将被钝化,可以减少非荧光复合,提升器件性能。In the step S2, the interface modification material has a permanent dipole moment. The interface modification material can be selected from but not limited to PEI (polyethyleneimine), PEIE (polyethoxyethyleneimine), PFN (poly[9,9-bis(3'-(N,N-dimethyl (amino)propyl)-2,7-fluorene]-2,7-(9,9-dioctylfluorene))]), PEG (polyethylene glycol), CPE (conjugated polyelectrolyte), PEO ( One or more of polyethylene oxide). The interface modification material 3 has the effect of reducing the work function of the material and passivating the surface defects of the material. When it penetrates into the interface between the quantum dot 41 and the electron transport material 51, it can regulate the interface of the material, and can reduce the interface barrier of the material. thereby facilitating the transport of charges. In addition, due to the small particle size of the quantum dots 41 and the electron transport material 51, both of which are nanostructures, the materials have a large specific surface area and a high content of surface defects, which will have a strong trapping effect on free charges, resulting in non-fluorescent recombination. result in poor device performance. However, under the coating effect of the interface modification material 3, the surface defects of the nanoparticles will be passivated, which can reduce non-fluorescence recombination and improve device performance.
在一些实施例中,所述混合溶液中,所述界面修饰材料3的浓度范围为0.1wt%-10wt%。在该浓度条件下混合溶液的黏度适中,界面修饰材料3可以有效的渗入量子点发光层4的量子点41的间隙中。浓度过高将造成溶液混合溶液的粘度大幅提高,增大界面修饰材料3渗入量子点41的间隙中的难度,增加量子点发光层4与电子传输层5之间的界面修饰材料的厚度,从而增加电荷传输的电阻。In some embodiments, in the mixed solution, the concentration of the interface modification material 3 ranges from 0.1 wt% to 10 wt%. Under this concentration condition, the viscosity of the mixed solution is moderate, and the interface modification material 3 can effectively penetrate into the gaps of the quantum dots 41 of the quantum dot light-emitting layer 4 . If the concentration is too high, the viscosity of the solution mixed solution will be greatly increased, increasing the difficulty of the interface modification material 3 infiltrating into the gap of the quantum dot 41, increasing the thickness of the interface modification material between the quantum dot light-emitting layer 4 and the electron transport layer 5, thereby Increased resistance to charge transfer.
所述混合溶液中,所述电子传输材料51的浓度范围为10-30mg/mL。所述电子传输材料51为本领域常规应用于电子传层输的材料。所述电子传输材料51选自但不限于金属氧化物、掺杂金属氧化物、2-6族半导体材料、3-5族半导体材料及1-3-6族半导体材料中的一种或几种。具体的,所述金属氧化物选自但不限于氧化锌(ZnO)、氧化钛(TiO 2)、氧化锡(SnO 2)中的一种或几种;所述掺杂金属氧化物中的金属氧化物选自但不限于ZnO、TiO 2、SnO 2中的至少一种,掺杂元素选自但不限于铝、镁、铟、镓中的一种或几种;所述2-6半导体族材料选自但不限于ZnS、ZnSe、CdS中的一种或几种;所述3-5半导体族材料选自但不限于InP、GaP中的至少一种;所述1-3-6族半导体材料选自但不限于CuInS、CuGaS中的至少一种。在一些实施例中,所述电子传输材料51为纳米ZnO、纳米TiO 2或纳米SnO 2。在至少一具体的实施例中,所述纳米ZnO的粒径小于20nm。 In the mixed solution, the concentration range of the electron transport material 51 is 10-30 mg/mL. The electron transport material 51 is a material conventionally used in the field of electron transport. The electron transport material 51 is selected from but not limited to one or more of metal oxides, doped metal oxides, group 2-6 semiconductor materials, group 3-5 semiconductor materials and group 1-3-6 semiconductor materials . Specifically, the metal oxide is selected from but not limited to one or more of zinc oxide (ZnO), titanium oxide (TiO 2 ), tin oxide (SnO 2 ); the metal in the doped metal oxide The oxide is selected from but not limited to at least one of ZnO, TiO 2 , and SnO 2 , and the doping element is selected from but not limited to one or more of aluminum, magnesium, indium, and gallium; the 2-6 semiconductor group The material is selected from but not limited to one or more of ZnS, ZnSe, and CdS; the 3-5 semiconductor group material is selected from but not limited to at least one of InP and GaP; the 1-3-6 group semiconductor The material is selected from but not limited to at least one of CuInS and CuGaS. In some embodiments, the electron transport material 51 is nano-ZnO, nano-TiO 2 or nano-SnO 2 . In at least one specific embodiment, the particle size of the nano ZnO is less than 20nm.
所述有机溶剂为本领域常规应用的溶剂。所述有机溶剂为高粘度溶剂或低粘度溶剂。所述高粘度溶剂可以为乙二醇单甲醚(EGME,粘度1.7mPa•s)、异丙醇(粘度2.4mPa•s)等。所述低粘度溶剂可以为乙醇(粘度1.2mPa•s)等。在一些实施例中,所述有机溶剂为低粘度溶剂,如此有利于所述界面修饰材料3渗透至量子点41的间隙中。The organic solvent is a conventionally used solvent in this field. The organic solvent is a high-viscosity solvent or a low-viscosity solvent. The high-viscosity solvent may be ethylene glycol monomethyl ether (EGME, viscosity 1.7 mPa•s), isopropanol (viscosity 2.4 mPa•s), and the like. The low-viscosity solvent may be ethanol (viscosity 1.2 mPa·s) or the like. In some embodiments, the organic solvent is a low-viscosity solvent, which facilitates the penetration of the interface modification material 3 into the gaps of the quantum dots 41 .
所述步骤S3中,所述量子点材料为本领域常规使用的量子点材料,如CdSeZnS、CdSeCdS/ZnS、ZnCdS/ZnS等。所述量子点材料中量子点的浓度为10-20mg/mL。所述烘烤的温度为80-120℃,时间为5-30min。In the step S3, the quantum dot material is a quantum dot material conventionally used in the field, such as CdSeZnS, CdSeCdS/ZnS, ZnCdS/ZnS and the like. The quantum dot concentration in the quantum dot material is 10-20mg/mL. The baking temperature is 80-120° C., and the baking time is 5-30 minutes.
所述步骤S03中,在将所述混合溶液添加至所述量子点发光层4上,之后还包括静置的步骤,以使所述界面修饰材料3充分渗透至所述量子点发光层4邻近电子传输层5一侧的量子点41的间隙中。在一些实施例中,所述静置时间为5-10秒。在一些实施例中,所述形成量子点膜的方法为旋涂法成膜,旋涂成膜的转速范围为2000-3000r/s,时间范围为20-30s。In the step S03, after adding the mixed solution to the quantum dot luminescent layer 4, it also includes a step of standing still, so that the interface modification material 3 can fully penetrate into the vicinity of the quantum dot luminescent layer 4 In the gap between the quantum dots 41 on the side of the electron transport layer 5 . In some embodiments, the resting time is 5-10 seconds. In some embodiments, the method for forming the quantum dot film is spin coating film formation, the spin coating film formation speed ranges from 2000-3000r/s, and the time range is 20-30s.
所述步骤S13中,将量子点材料旋涂在底电极2上时,旋涂的转速为2000-3000r/s,时间为25-35s。在旋涂开始后2-10秒内滴加所述混合溶液。In the step S13, when the quantum dot material is spin-coated on the bottom electrode 2, the rotation speed of the spin coating is 2000-3000r/s, and the time is 25-35s. The mixed solution is added dropwise within 2-10 seconds after the spin coating starts.
所述步骤S4中,在所述电子传输层5上形成顶电极6的方法为本领域常规的方法,如蒸镀等。所述顶电极6为阴极,所述阴极为本领域常规应用的阴极,如为Al、Ag、Al/Ag、Cu、Au及合金电极等。在至少一实施例中,所述蒸镀的方法为:通过热蒸发,真空度不高于3×10 -4Pa,以0.5-1埃/秒的速度,蒸镀1000-2000秒。 In the step S4, the method of forming the top electrode 6 on the electron transport layer 5 is a conventional method in the field, such as evaporation and the like. The top electrode 6 is a cathode, and the cathode is a cathode commonly used in this field, such as Al, Ag, Al/Ag, Cu, Au and alloy electrodes. In at least one embodiment, the vapor deposition method is as follows: by thermal evaporation, the vacuum degree is not higher than 3×10 -4 Pa, and the vapor deposition is performed for 1000-2000 seconds at a speed of 0.5-1 angstroms/second.
可以理解的,在所述底电极2上形成量子点发光层4之前,还包括在底电极2上形成空穴传输层及空穴注入层中的至少一层的步骤。形成所述空穴传输层及空穴注入层的方法为本领域常规的方法,如蒸镀等。It can be understood that before forming the quantum dot light-emitting layer 4 on the bottom electrode 2, a step of forming at least one of a hole transport layer and a hole injection layer on the bottom electrode 2 is also included. The method for forming the hole transport layer and the hole injection layer is a conventional method in the field, such as evaporation and the like.
在至少一实施例中,形成所述空穴注入层的方法为:在所述底电极2上旋涂空穴注入层材料,然后烘烤。所述旋涂的转速为4000-5000r/s,时间为30秒。所述烘烤的温度为150℃,时间为15-30min。所述空穴注入层材料为本领域常规应用于空穴注入层的材料,如PEDOT((3,4-乙烯二氧噻吩单体)的聚合物):PSS(聚苯乙烯磺酸钠)的混合材料等。In at least one embodiment, the method of forming the hole injection layer is: spin-coat the hole injection layer material on the bottom electrode 2 and then bake it. The rotating speed of the spin coating is 4000-5000r/s, and the time is 30 seconds. The baking temperature is 150° C., and the baking time is 15-30 minutes. The material of the hole injection layer is a material conventionally used in the hole injection layer in the field, such as PEDOT (polymer of (3,4-ethylenedioxythiophene monomer)): PSS (sodium polystyrene sulfonate) mixed materials etc.
在至少一实施例中,形成所述空穴传输层的方法为:在所述底电极2或所述空穴注入层上旋涂空穴传输层材料,然后烘烤。所述旋涂的转速为3000r/s,时间为30秒。所述烘烤的温度为80℃,时间为10-30min。所述空穴传输层材料为本领域常规应用于空穴传输层的材料,如TFB(镍蚀刻剂)等。In at least one embodiment, the method of forming the hole transport layer is: spin-coat the material of the hole transport layer on the bottom electrode 2 or the hole injection layer, and then bake. The rotating speed of the spin coating is 3000r/s, and the time is 30 seconds. The baking temperature is 80° C., and the baking time is 10-30 minutes. The material of the hole transport layer is a material conventionally used in the field of the hole transport layer, such as TFB (nickel etchant).
可以理解的,在所述电子传输层5上形成顶电极6之前,还可以包括在所述电子传输层5上形成电子注入层的步骤。It can be understood that before forming the top electrode 6 on the electron transport layer 5 , a step of forming an electron injection layer on the electron transport layer 5 may also be included.
本申请实施例还提供一种量子点发光二极管100,其包括依次层叠设置的衬底1、底电极2、量子点发光层4、电子传输层5及顶电极6。所述量子点发光层4中包含量子点41,所述电子传输层5包含电子传输材料51。所述量子点发光二极管100还包括界面修饰材料3。所述界面修饰材料3填充在所述量子点发光层4的量子点41之间的间隙中、所述电子传输层5的电子传输材料51之间的间隙中、及相邻的量子点41和电子传输材料51之间的间隙中。The embodiment of the present application also provides a quantum dot light-emitting diode 100 , which includes a substrate 1 , a bottom electrode 2 , a quantum dot light-emitting layer 4 , an electron transport layer 5 and a top electrode 6 which are sequentially stacked. The quantum dot light-emitting layer 4 includes quantum dots 41 , and the electron transport layer 5 includes an electron transport material 51 . The quantum dot LED 100 also includes an interface modification material 3 . The interface modification material 3 is filled in the gaps between the quantum dots 41 of the quantum dot luminescent layer 4, in the gaps between the electron transport materials 51 of the electron transport layer 5, and between the adjacent quantum dots 41 and In the gap between electron transport materials 51 .
在至少一实施例中,所述量子点发光层4与电子传输层5之间填充有界面修饰材料3。In at least one embodiment, the interface modification material 3 is filled between the quantum dot light emitting layer 4 and the electron transport layer 5 .
在一实施例中,所述量子点发光层4的所有量子点41的间隙中均填充有所述界面修饰材料3。在又一实施例中,所述量子点发光层4的邻近所述电子传输层5的一侧的区域中的量子点41之间的间隙填充有界面修饰材料3,所述量子点发光层4的远离所述电子传输层5的一侧的区域中的量子点41之间的间隙中没有填充界面修饰材料3。In one embodiment, the gaps of all the quantum dots 41 in the quantum dot light-emitting layer 4 are filled with the interface modification material 3 . In yet another embodiment, the gap between the quantum dots 41 in the region of the quantum dot luminescent layer 4 adjacent to the electron transport layer 5 is filled with an interface modification material 3, and the quantum dot luminescent layer 4 The gap between the quantum dots 41 in the region on the side away from the electron transport layer 5 is not filled with the interface modification material 3 .
在一实施例中,所述量子点发光二极管100还包括依次层叠在底电极2上的空穴传输层及空穴注入层。In one embodiment, the quantum dot light emitting diode 100 further includes a hole transport layer and a hole injection layer sequentially stacked on the bottom electrode 2 .
可以理解的,所述量子点发光二极管100还包括位于电子传输层5与顶电极6之间的电子注入层。It can be understood that the quantum dot LED 100 also includes an electron injection layer located between the electron transport layer 5 and the top electrode 6 .
本申请实施例还提供另外一种量子点发光二极管100,其包括依次层叠设置的衬底1、底电极2、量子点发光层4、过渡层10、电子传输层5及顶电极6。所述量子点发光层4中包含量子点41,所述电子传输层5包含电子传输材料51。所述量子点发光二极管100还包括界面修饰材料3。所述过渡层10内包含量子点41、电子传输材料51及界面修饰材料3。所述过渡层10中的量子点41之间的间隙中、电子传输材料51之间的间隙中、及量子点41与电子传输材料51之间的间隙中填充有所述界面修饰材料3,换言之,所述过渡层10中的量子点41和电子传输材料51无规则的镶嵌在界面修饰材料3中。所述界面修饰材料3还填充在所述量子点发光层4与过渡层10之间、所述过渡层10与所述电子传输层5之间、所述量子点发光层4的量子点41之间的间隙中、及所述电子传输层5的电子传输材料51之间的间隙中。The embodiment of the present application also provides another quantum dot light-emitting diode 100 , which includes a substrate 1 , a bottom electrode 2 , a quantum dot light-emitting layer 4 , a transition layer 10 , an electron transport layer 5 and a top electrode 6 stacked in sequence. The quantum dot light-emitting layer 4 includes quantum dots 41 , and the electron transport layer 5 includes an electron transport material 51 . The quantum dot LED 100 also includes an interface modification material 3 . The transition layer 10 includes quantum dots 41 , electron transport materials 51 and interface modification materials 3 . The gaps between the quantum dots 41 in the transition layer 10, the gaps between the electron transport materials 51, and the gaps between the quantum dots 41 and the electron transport materials 51 are filled with the interface modification material 3, in other words , the quantum dots 41 and the electron transport material 51 in the transition layer 10 are randomly embedded in the interface modification material 3 . The interface modification material 3 is also filled between the quantum dot luminescent layer 4 and the transition layer 10, between the transition layer 10 and the electron transport layer 5, and between the quantum dots 41 of the quantum dot luminescent layer 4 In the gap between, and in the gap between the electron transport material 51 of the electron transport layer 5 .
在一实施例中,所述量子点发光层4的所有量子点41的间隙中均填充有所述界面修饰材料3。在又一实施例中,所述量子点发光层4的邻近所述过渡层10的一侧的区域中的量子点41之间的间隙填充有界面修饰材料3,所述量子点发光层4的远离所述过渡层10的一侧的区域中的量子点41之间的间隙中没有填充界面修饰材料3。In one embodiment, the gaps of all the quantum dots 41 in the quantum dot light-emitting layer 4 are filled with the interface modification material 3 . In yet another embodiment, the gap between the quantum dots 41 in the region of the quantum dot luminescent layer 4 adjacent to the transition layer 10 is filled with the interface modification material 3, and the quantum dot luminescent layer 4 The gap between the quantum dots 41 in the region away from the transition layer 10 is not filled with the interface modification material 3 .
在一实施例中,所述量子点发光二极管100还包括依次层叠在底电极2上的空穴传输层及空穴注入层。In one embodiment, the quantum dot light emitting diode 100 further includes a hole transport layer and a hole injection layer sequentially stacked on the bottom electrode 2 .
可以理解的,所述量子点发光二极管100还包括位于电子传输层5与顶电极6之间的电子注入层。It can be understood that the quantum dot LED 100 also includes an electron injection layer located between the electron transport layer 5 and the top electrode 6 .
下面通过具体实施例来对本申请进行具体说明,以下实施例仅是本申请的部分实施方式,不是对本申请的限定。The following examples will be used to describe the present application in detail. The following examples are only partial implementations of the present application, and are not intended to limit the present application.
实施例1Example 1
制备量子点发光二极管100Preparation of Quantum Dot Light-Emitting Diode 100
提供一表面结合有ITO底电极2的衬底1;A substrate 1 with an ITO bottom electrode 2 bonded to its surface is provided;
在ITO底电极2上打印PEDOT:PSS混合材料,然后150℃下烘烤15min,得到空穴注入层;Print the PEDOT:PSS hybrid material on the ITO bottom electrode 2, and then bake at 150°C for 15 minutes to obtain the hole injection layer;
在所述空穴注入层上打印浓度为8mg/mL的TFB,然后80℃下烘烤10min,得到空穴传输层;Printing TFB with a concentration of 8 mg/mL on the hole injection layer, and then baking at 80° C. for 10 minutes to obtain a hole transport layer;
提供界面修饰材料PEI、电子传输材料纳米ZnO及有机溶剂乙二醇单甲醚,将PEI及纳米ZnO加入乙二醇单甲醚中,混合均匀后,得到PEI:纳米ZnO的混合溶液,其中,PEI的浓度为0.1wt%;Provide interface modification material PEI, electron transport material nano-ZnO and organic solvent ethylene glycol monomethyl ether, add PEI and nano-ZnO to ethylene glycol monomethyl ether, and mix well to obtain a mixed solution of PEI:nano-ZnO, wherein, The concentration of PEI is 0.1wt%;
在所述空穴传输层的表面打印浓度为20mg/mL的量子点材料,得到量子点发光层4;Printing a quantum dot material with a concentration of 20 mg/mL on the surface of the hole transport layer to obtain a quantum dot light-emitting layer 4;
在所述量子点发光层4上打印所述混合溶液,静置5秒后,在80℃下烘烤5min,得到电子传输层5;Print the mixed solution on the quantum dot light-emitting layer 4, and after standing for 5 seconds, bake at 80° C. for 5 minutes to obtain an electron transport layer 5;
在真空度为3×10 -4Pa的条件下,以1埃/秒的速度蒸镀Al电极100秒,Al的厚度为10nm; Under the condition of vacuum degree of 3×10 -4 Pa, evaporate the Al electrode at a speed of 1 Angstrom/second for 100 seconds, and the thickness of Al is 10nm;
在真空度为3×10 -4Pa的条件下,以1埃/秒的速度蒸镀Ag电极200秒,Ag的厚度为20nm,得到量子点发光二极管100。 Under the condition of a vacuum degree of 3×10 −4 Pa, an Ag electrode was vapor-deposited at a rate of 1 Å/sec for 200 seconds, and the thickness of Ag was 20 nm to obtain a quantum dot light-emitting diode 100 .
本实施例的量子点发光二极管100的界面修饰材料3填充在所述量子点发光层4与电子传输层5之间、所述量子点发光层4的邻近所述电子传输层5的一侧的区域中的量子点41之间的间隙中、及所述电子传输层5的电子传输材料51之间的间隙中。The interface modification material 3 of the quantum dot light-emitting diode 100 in this embodiment is filled between the quantum dot light-emitting layer 4 and the electron transport layer 5, on the side of the quantum dot light-emitting layer 4 adjacent to the electron transport layer 5 In the gaps between the quantum dots 41 in the region, and in the gaps between the electron transport materials 51 of the electron transport layer 5 .
实施例2Example 2
制备量子点发光二极管100Preparation of Quantum Dot Light-Emitting Diode 100
提供一表面结合有ITO底电极2的衬底1;A substrate 1 with an ITO bottom electrode 2 bonded to its surface is provided;
在ITO底电极2上打印PEDOT:PSS混合材料,然后150℃下烘烤15min,得到空穴注入层;Print the PEDOT:PSS hybrid material on the ITO bottom electrode 2, and then bake at 150°C for 15 minutes to obtain the hole injection layer;
在所述空穴注入层上打印浓度为8mg/mL的TFB,然后80℃下烘烤10min,得到空穴传输层;Printing TFB with a concentration of 8 mg/mL on the hole injection layer, and then baking at 80° C. for 10 minutes to obtain a hole transport layer;
提供界面修饰材料PEI、电子传输材料纳米ZnO及有机溶剂乙二醇单甲醚,将PEI及纳米ZnO加入乙二醇单甲醚中,混合均匀后,得到PEI:纳米ZnO的混合溶液,其中,PEI的浓度为0.1wt%;Provide interface modification material PEI, electron transport material nano-ZnO and organic solvent ethylene glycol monomethyl ether, add PEI and nano-ZnO to ethylene glycol monomethyl ether, and mix well to obtain a mixed solution of PEI:nano-ZnO, wherein, The concentration of PEI is 0.1wt%;
在所述空穴传输层的表面以2000r/s的转速旋涂浓度为20mg/mL的量子点材料30秒,得到量子点发光层4;Spin coating a quantum dot material with a concentration of 20mg/mL on the surface of the hole transport layer at a speed of 2000r/s for 30 seconds to obtain a quantum dot light-emitting layer 4;
将所述混合溶液滴加在所述量子点发光层4上,静置5秒,待界面修饰材料3渗透至所述量子点发光层4的量子点41的间隙中后,以3000r/s的转速旋涂30秒,然后在80℃下烘烤5min,得到电子传输层5;Add the mixed solution dropwise on the quantum dot luminescent layer 4, and let it stand for 5 seconds. After the interface modification material 3 penetrates into the gaps of the quantum dots 41 of the quantum dot luminescent layer 4, start the process at a speed of 3000r/s. Spin coating at a rotational speed for 30 seconds, and then bake at 80° C. for 5 minutes to obtain an electron transport layer 5;
在真空度为3×10 -4Pa的条件下,以1埃/秒的速度蒸镀Ag电极1000秒,Ag的厚度为100nm,得到量子点发光二极管100。 Under the condition of a vacuum degree of 3×10 −4 Pa, the Ag electrode was vapor-deposited at a rate of 1 angstrom/second for 1000 seconds, and the Ag thickness was 100 nm to obtain a quantum dot light-emitting diode 100 .
本实施例的量子点发光二极管100的界面修饰材料3填充在所述量子点发光层4与电子传输层5之间、所述量子点发光层4的邻近所述电子传输层5的一侧的区域中的量子点41之间的间隙中、及所述电子传输层5的电子传输材料51之间的间隙中。The interface modification material 3 of the quantum dot light-emitting diode 100 in this embodiment is filled between the quantum dot light-emitting layer 4 and the electron transport layer 5, on the side of the quantum dot light-emitting layer 4 adjacent to the electron transport layer 5 In the gaps between the quantum dots 41 in the region, and in the gaps between the electron transport materials 51 of the electron transport layer 5 .
实施例3Example 3
制备量子点发光二极管100Preparation of Quantum Dot Light-Emitting Diode 100
提供一表面结合有ITO底电极2的衬底1;A substrate 1 with an ITO bottom electrode 2 bonded to its surface is provided;
在ITO底电极2上打印PEDOT:PSS混合材料,然后150℃下烘烤15min,得到空穴注入层;Print the PEDOT:PSS hybrid material on the ITO bottom electrode 2, and then bake at 150°C for 15 minutes to obtain the hole injection layer;
在所述空穴注入层上打印浓度为8mg/mL的TFB,然后80℃下烘烤10min,得到空穴传输层;Printing TFB with a concentration of 8 mg/mL on the hole injection layer, and then baking at 80° C. for 10 minutes to obtain a hole transport layer;
提供界面修饰材料PEI、电子传输材料纳米ZnO及有机溶剂乙二醇单甲醚,将PEI及纳米ZnO加入乙二醇单甲醚中,混合均匀后,得到PEI:纳米ZnO的混合溶液,其中,PEI的浓度为0.1wt%;Provide interface modification material PEI, electron transport material nano-ZnO and organic solvent ethylene glycol monomethyl ether, add PEI and nano-ZnO to ethylene glycol monomethyl ether, and mix well to obtain a mixed solution of PEI:nano-ZnO, wherein, The concentration of PEI is 0.1wt%;
在所述空穴传输层的表面以2000r/s的转速旋涂浓度为20mg/mL的量子点材料30秒,并在旋涂开始后2秒内滴加所述混合溶液,成膜后在80℃下烘烤5min,得到量子点发光层4、结合于所述量子点发光层4的过渡层10、及结合于过渡层10的电子传输层5;The surface of the hole transport layer is spin-coated with a concentration of 20mg/mL quantum dot material for 30 seconds at a speed of 2000r/s, and the mixed solution is added dropwise within 2 seconds after the start of the spin coating. Baking at ℃ for 5 minutes to obtain the quantum dot light-emitting layer 4, the transition layer 10 combined with the quantum dot light-emitting layer 4, and the electron transport layer 5 combined with the transition layer 10;
在真空度为3×10 -4Pa的条件下,以1埃/秒的速度蒸镀Al电极100秒,Al的厚度为10nm; Under the condition of vacuum degree of 3×10 -4 Pa, evaporate the Al electrode at a speed of 1 Angstrom/second for 100 seconds, and the thickness of Al is 10nm;
在真空度为3×10 -4Pa的条件下,以1埃/秒的速度蒸镀Ag电极200秒,Ag的厚度为20nm,得到量子点发光二极管100。 Under the condition of a vacuum degree of 3×10 −4 Pa, an Ag electrode was vapor-deposited at a rate of 1 Å/sec for 200 seconds, and the thickness of Ag was 20 nm to obtain a quantum dot light-emitting diode 100 .
本实施例的量子点发光二极管100中,所述过渡层10中的量子点41之间的间隙中、电子传输材料51之间的间隙、及量子点41与电子传输材料51之间的间隙中均填充有所述界面修饰材料3。所述界面修饰材料3还填充在所述量子点发光层4与所述过渡层10之间、所述过渡层10与所述电子传输层5之间、所述量子点发光层4的邻近所述过渡层10的一侧的区域中的量子点41之间的间隙中、及所述电子传输层5的电子传输材料之间的间隙中。In the quantum dot light-emitting diode 100 of this embodiment, in the gaps between the quantum dots 41 in the transition layer 10, in the gaps between the electron transport materials 51, and in the gaps between the quantum dots 41 and the electron transport materials 51 Both are filled with the interface modifying material 3 . The interface modification material 3 is also filled between the quantum dot luminescent layer 4 and the transition layer 10, between the transition layer 10 and the electron transport layer 5, and adjacent to the quantum dot luminescent layer 4. In the gap between the quantum dots 41 in the region on one side of the transition layer 10 and in the gap between the electron transport materials of the electron transport layer 5 .
实施例4Example 4
制备量子点发光二极管100Preparation of Quantum Dot Light-Emitting Diode 100
提供一表面结合有ITO底电极2的衬底1;A substrate 1 with an ITO bottom electrode 2 bonded to its surface is provided;
在ITO底电极2上打印PEDOT:PSS混合材料,然后150℃下烘烤15min,得到空穴注入层;Print the PEDOT:PSS hybrid material on the ITO bottom electrode 2, and then bake at 150°C for 15 minutes to obtain the hole injection layer;
在所述空穴注入层上打印浓度为8mg/mL的TFB,然后80℃下烘烤10min,得到空穴传输层;Printing TFB with a concentration of 8 mg/mL on the hole injection layer, and then baking at 80° C. for 10 minutes to obtain a hole transport layer;
提供界面修饰材料PEI、电子传输材料纳米ZnO及有机溶剂乙二醇单甲醚,将PEI及纳米ZnO加入乙二醇单甲醚中,混合均匀后,得到PEI:纳米ZnO的混合溶液,其中,PEI的浓度为0.1wt%;Provide interface modification material PEI, electron transport material nano-ZnO and organic solvent ethylene glycol monomethyl ether, add PEI and nano-ZnO to ethylene glycol monomethyl ether, and mix well to obtain a mixed solution of PEI:nano-ZnO, wherein, The concentration of PEI is 0.1wt%;
在所述空穴传输层的表面以2000r/s的转速旋涂浓度为20mg/mL的量子点材料30秒,并在旋涂开始后2秒内滴加所述混合溶液,成膜后在80℃下烘烤5min,得到量子点发光层4、结合于所述量子点发光层4的过渡层10、及结合于过渡层10的电子传输层5;The surface of the hole transport layer is spin-coated with a concentration of 20mg/mL quantum dot material for 30 seconds at a speed of 2000r/s, and the mixed solution is added dropwise within 2 seconds after the start of the spin coating. Baking at ℃ for 5 minutes to obtain the quantum dot light-emitting layer 4, the transition layer 10 combined with the quantum dot light-emitting layer 4, and the electron transport layer 5 combined with the transition layer 10;
在真空度为3×10 -4Pa的条件下,以1埃/秒的速度蒸镀Ag电极1000秒,Ag的厚度为100nm,得到量子点发光二极管100。 Under the condition of a vacuum degree of 3×10 −4 Pa, the Ag electrode was vapor-deposited at a rate of 1 angstrom/second for 1000 seconds, and the Ag thickness was 100 nm to obtain a quantum dot light-emitting diode 100 .
本实施例的量子点发光二极管100中,所述过渡层10中的量子点41之间的间隙中、电子传输材料51之间的间隙、及量子点41与电子传输材料51之间的间隙中均填充有所述界面修饰材料3。所述界面修饰材料3还填充在所述量子点发光层4与所述过渡层10之间、所述过渡层10与所述电子传输层5之间、所述量子点发光层4的邻近所述过渡层10的一侧的区域中的量子点41之间的间隙中、及所述电子传输层5的电子传输材料之间的间隙中。In the quantum dot light-emitting diode 100 of this embodiment, in the gaps between the quantum dots 41 in the transition layer 10, in the gaps between the electron transport materials 51, and in the gaps between the quantum dots 41 and the electron transport materials 51 Both are filled with the interface modifying material 3 . The interface modification material 3 is also filled between the quantum dot luminescent layer 4 and the transition layer 10, between the transition layer 10 and the electron transport layer 5, and adjacent to the quantum dot luminescent layer 4. In the gap between the quantum dots 41 in the region on one side of the transition layer 10 and in the gap between the electron transport materials of the electron transport layer 5 .
实施例5Example 5
制备量子点发光二极管100Preparation of Quantum Dot Light-Emitting Diode 100
提供一表面结合有ITO底电极2的衬底1;A substrate 1 with an ITO bottom electrode 2 bonded to its surface is provided;
在ITO底电极2上打印PEDOT:PSS混合材料,然后150℃下烘烤15min,得到空穴注入层;Print the PEDOT:PSS hybrid material on the ITO bottom electrode 2, and then bake at 150°C for 15 minutes to obtain the hole injection layer;
在所述空穴注入层上打印浓度为8mg/mL的TFB,然后80℃下烘烤10min,得到空穴传输层;Printing TFB with a concentration of 8 mg/mL on the hole injection layer, and then baking at 80° C. for 10 minutes to obtain a hole transport layer;
提供界面修饰材料PEI、电子传输材料纳米ZnO及有机溶剂乙醇,将PEI及纳米ZnO加入乙醇中,混合均匀后,得到PEI:纳米ZnO的混合溶液,其中,PEI的浓度为0.1wt%;Provide interface modification material PEI, electron transport material nano-ZnO and organic solvent ethanol, add PEI and nano-ZnO to ethanol, after mixing evenly, obtain PEI:nano-ZnO mixed solution, wherein, the concentration of PEI is 0.1wt%;
在所述空穴传输层的表面打印浓度为20mg/mL的量子点材料,得到量子点发光层4;Printing a quantum dot material with a concentration of 20 mg/mL on the surface of the hole transport layer to obtain a quantum dot light-emitting layer 4;
将所述混合溶液滴加在所述量子点发光层4上,静置5秒,待界面修饰材料3渗透至所述量子点发光层4的量子点41的间隙中后,成膜,然后在80℃下烘烤5min,得到电子传输层5;Add the mixed solution dropwise on the quantum dot luminescent layer 4, and let it stand for 5 seconds. After the interface modification material 3 penetrates into the gaps of the quantum dots 41 of the quantum dot luminescent layer 4, a film is formed, and then Bake at 80°C for 5 minutes to obtain electron transport layer 5;
在真空度为3×10 -4Pa的条件下,以1埃/秒的速度蒸镀Al电极100秒,Al的厚度为10nm; Under the condition of vacuum degree of 3×10 -4 Pa, evaporate the Al electrode at a speed of 1 Angstrom/second for 100 seconds, and the thickness of Al is 10nm;
在真空度为3×10 -4Pa的条件下,以1埃/秒的速度蒸镀Ag电极200秒,Ag的厚度为20nm,得到量子点发光二极管100。 Under the condition of a vacuum degree of 3×10 −4 Pa, an Ag electrode was vapor-deposited at a rate of 1 Å/sec for 200 seconds, and the thickness of Ag was 20 nm to obtain a quantum dot light-emitting diode 100 .
本实施例的量子点发光二极管100的界面修饰材料3填充在所述量子点发光层4与电子传输层5之间、所述量子点发光层4的邻近所述电子传输层5的一侧的区域中的量子点41之间的间隙中、及所述电子传输层5的电子传输材料51之间的间隙中。The interface modification material 3 of the quantum dot light-emitting diode 100 in this embodiment is filled between the quantum dot light-emitting layer 4 and the electron transport layer 5, on the side of the quantum dot light-emitting layer 4 adjacent to the electron transport layer 5 In the gaps between the quantum dots 41 in the region, and in the gaps between the electron transport materials 51 of the electron transport layer 5 .
实施例6Example 6
制备量子点发光二极管100Preparation of Quantum Dot Light-Emitting Diode 100
提供一表面结合有ITO底电极2的衬底1;A substrate 1 with an ITO bottom electrode 2 bonded to its surface is provided;
在ITO底电极2上打印PEDOT:PSS混合材料,然后150℃下烘烤15min,得到空穴注入层;Print the PEDOT:PSS hybrid material on the ITO bottom electrode 2, and then bake at 150°C for 15 minutes to obtain the hole injection layer;
在所述空穴注入层上打印浓度为8mg/mL的TFB,然后80℃下烘烤10min,得到空穴传输层;Printing TFB with a concentration of 8 mg/mL on the hole injection layer, and then baking at 80° C. for 10 minutes to obtain a hole transport layer;
提供界面修饰材料PEI、电子传输材料纳米ZnO及有机溶剂乙醇,将PEI及纳米ZnO加入乙醇中,混合均匀后,得到PEI:纳米ZnO的混合溶液,其中,PEI的浓度为0.1wt%;Provide interface modification material PEI, electron transport material nano-ZnO and organic solvent ethanol, add PEI and nano-ZnO to ethanol, after mixing evenly, obtain PEI:nano-ZnO mixed solution, wherein, the concentration of PEI is 0.1wt%;
在所述空穴传输层的表面打印量子点材料,得到量子点发光层4;Printing quantum dot materials on the surface of the hole transport layer to obtain a quantum dot light-emitting layer 4;
将所述混合溶液滴加在所述量子点发光层4上,静置5秒,待界面修饰材料3渗透至所述量子点发光层4的量子点41的间隙中后,涂布成膜,然后在80℃下烘烤5min,得到电子传输层5;Add the mixed solution dropwise on the quantum dot luminescent layer 4, and let it stand for 5 seconds. After the interface modification material 3 penetrates into the gaps of the quantum dots 41 of the quantum dot luminescent layer 4, it is coated to form a film. Then bake at 80° C. for 5 minutes to obtain the electron transport layer 5;
在真空度为3×10 -4Pa的条件下,以1埃/秒的速度蒸镀Ag电极1000秒,Ag的厚度为100nm,得到量子点发光二极管100。 Under the condition of a vacuum degree of 3×10 −4 Pa, the Ag electrode was vapor-deposited at a rate of 1 angstrom/second for 1000 seconds, and the Ag thickness was 100 nm to obtain a quantum dot light-emitting diode 100 .
本实施例的量子点发光二极管100的界面修饰材料3填充在所述量子点发光层4与电子传输层5之间、所述量子点发光层4的邻近所述电子传输层5的一侧的区域中的量子点41之间的间隙中、及所述电子传输层5的电子传输材料51之间的间隙中。The interface modification material 3 of the quantum dot light-emitting diode 100 in this embodiment is filled between the quantum dot light-emitting layer 4 and the electron transport layer 5, on the side of the quantum dot light-emitting layer 4 adjacent to the electron transport layer 5 In the gaps between the quantum dots 41 in the region, and in the gaps between the electron transport materials 51 of the electron transport layer 5 .
实施例7Example 7
制备量子点发光二极管100Preparation of Quantum Dot Light-Emitting Diode 100
提供一表面结合有ITO底电极2的衬底1;A substrate 1 with an ITO bottom electrode 2 bonded to its surface is provided;
在ITO底电极2上以打印PEDOT:PSS混合材料,然后150℃下烘烤15min,得到空穴注入层;Print the PEDOT:PSS mixed material on the ITO bottom electrode 2, and then bake at 150°C for 15 minutes to obtain the hole injection layer;
在所述空穴注入层上打印浓度为8mg/mL的TFB,然后80℃下烘烤10min,得到空穴传输层;Printing TFB with a concentration of 8 mg/mL on the hole injection layer, and then baking at 80° C. for 10 minutes to obtain a hole transport layer;
提供界面修饰材料PEI、电子传输材料纳米ZnO及有机溶剂乙醇,将PEI及纳米ZnO加入乙醇中,混合均匀后,得到PEI:纳米ZnO的混合溶液,其中,PEI的浓度为0.1wt%;Provide interface modification material PEI, electron transport material nano-ZnO and organic solvent ethanol, add PEI and nano-ZnO to ethanol, after mixing evenly, obtain PEI:nano-ZnO mixed solution, wherein, the concentration of PEI is 0.1wt%;
在所述空穴传输层的表面打印量子点材料,得到量子点湿膜,然后在所述量子点湿膜的表面滴加所述混合溶液,成膜后在80℃下烘烤5min,得到量子点发光层4、结合于所述量子点发光层4的过渡层10、及结合于过渡层10的电子传输层5;Print quantum dot materials on the surface of the hole transport layer to obtain a quantum dot wet film, then drop the mixed solution on the surface of the quantum dot wet film, and bake at 80°C for 5 minutes after film formation to obtain a quantum dot wet film. The dot light-emitting layer 4, the transition layer 10 combined with the quantum dot light-emitting layer 4, and the electron transport layer 5 combined with the transition layer 10;
在真空度为3×10 -4Pa的条件下,以1埃/秒的速度蒸镀Al电极100秒,Al的厚度为10nm; Under the condition of vacuum degree of 3×10 -4 Pa, evaporate the Al electrode at a speed of 1 Angstrom/second for 100 seconds, and the thickness of Al is 10nm;
在真空度为3×10 -4Pa的条件下,以1埃/秒的速度蒸镀Ag电极200秒,Ag的厚度为20nm,得到量子点发光二极管100。 Under the condition of a vacuum degree of 3×10 −4 Pa, an Ag electrode was vapor-deposited at a rate of 1 Å/sec for 200 seconds, and the thickness of Ag was 20 nm to obtain a quantum dot light-emitting diode 100 .
本实施例的量子点发光二极管100中,所述过渡层10中的量子点41之间的间隙中、电子传输材料51之间的间隙、及量子点41与电子传输材料51之间的间隙中均填充有所述界面修饰材料3。所述界面修饰材料3还填充在所述量子点发光层4与所述过渡层10之间、所述过渡层10与所述电子传输层5之间、所述量子点发光层4的邻近所述过渡层10的一侧的区域中的量子点41之间的间隙中、及所述电子传输层5的电子传输材料之间的间隙中。In the quantum dot light-emitting diode 100 of this embodiment, in the gaps between the quantum dots 41 in the transition layer 10, in the gaps between the electron transport materials 51, and in the gaps between the quantum dots 41 and the electron transport materials 51 Both are filled with the interface modifying material 3 . The interface modification material 3 is also filled between the quantum dot luminescent layer 4 and the transition layer 10, between the transition layer 10 and the electron transport layer 5, and adjacent to the quantum dot luminescent layer 4. In the gap between the quantum dots 41 in the region on one side of the transition layer 10 and in the gap between the electron transport materials of the electron transport layer 5 .
实施例8Example 8
制备量子点发光二极管100Preparation of Quantum Dot Light-Emitting Diode 100
提供一表面结合有ITO底电极2的衬底1;A substrate 1 with an ITO bottom electrode 2 bonded to its surface is provided;
在ITO底电极2上以5000r/s的转速旋涂PEDOT:PSS混合材料30秒,然后150℃下烘烤15min,得到空穴注入层;Spin-coat the PEDOT:PSS hybrid material on the ITO bottom electrode 2 at a speed of 5000r/s for 30 seconds, and then bake at 150°C for 15 minutes to obtain a hole injection layer;
在所述空穴注入层上以3000r/s的转速旋涂浓度为8mg/mL的TFB30秒,然后80℃下烘烤10min,得到空穴传输层;Spin-coat TFB with a concentration of 8 mg/mL on the hole injection layer at a speed of 3000 r/s for 30 seconds, and then bake at 80° C. for 10 minutes to obtain a hole transport layer;
提供界面修饰材料PEI、电子传输材料纳米ZnO及有机溶剂乙醇,将PEI及纳米ZnO加入乙醇中,混合均匀后,得到PEI:纳米ZnO的混合溶液,其中,PEI/PEIE的浓度为0.1wt%;Provide interface modification material PEI, electron transport material nano-ZnO and organic solvent ethanol, add PEI and nano-ZnO to ethanol, after mixing evenly, obtain a mixed solution of PEI:nano-ZnO, wherein the concentration of PEI/PEIE is 0.1wt%;
在所述空穴传输层的表面以2000r/s的转速旋涂浓度为20mg/mL的量子点材料30秒,并在旋涂开始后2秒内滴加所述混合溶液,成膜后在80℃下烘烤5min,得到量子点发光层4、结合于所述量子点发光层4的过渡层10、及结合于过渡层10的电子传输层5;The surface of the hole transport layer is spin-coated with a concentration of 20mg/mL quantum dot material for 30 seconds at a speed of 2000r/s, and the mixed solution is added dropwise within 2 seconds after the start of the spin coating. Baking at ℃ for 5 minutes to obtain the quantum dot light-emitting layer 4, the transition layer 10 combined with the quantum dot light-emitting layer 4, and the electron transport layer 5 combined with the transition layer 10;
在真空度为3×10 -4Pa的条件下,以1埃/秒的速度蒸镀Ag电极1000秒,Ag的厚度为100nm,得到量子点发光二极管100。 Under the condition of a vacuum degree of 3×10 −4 Pa, the Ag electrode was vapor-deposited at a rate of 1 angstrom/second for 1000 seconds, and the Ag thickness was 100 nm to obtain a quantum dot light-emitting diode 100 .
本实施例的量子点发光二极管100中,所述过渡层10中的量子点41之间的间隙中、电子传输材料51之间的间隙、及量子点41与电子传输材料51之间的间隙中均填充有所述界面修饰材料3。所述界面修饰材料3还填充在所述量子点发光层4与所述过渡层10之间、所述过渡层10与所述电子传输层5之间、所述量子点发光层4的邻近所述过渡层10的一侧的区域中的量子点41之间的间隙中、及所述电子传输层5的电子传输材料之间的间隙中。In the quantum dot light-emitting diode 100 of this embodiment, in the gaps between the quantum dots 41 in the transition layer 10, in the gaps between the electron transport materials 51, and in the gaps between the quantum dots 41 and the electron transport materials 51 Both are filled with the interface modifying material 3 . The interface modification material 3 is also filled between the quantum dot luminescent layer 4 and the transition layer 10, between the transition layer 10 and the electron transport layer 5, and adjacent to the quantum dot luminescent layer 4. In the gap between the quantum dots 41 in the region on one side of the transition layer 10 and in the gap between the electron transport materials of the electron transport layer 5 .
对比例1Comparative example 1
常规的量子点发光二极管的制备Fabrication of Conventional Quantum Dot Light-Emitting Diodes
提供一表面结合有ITO底电极的衬底;A substrate with an ITO bottom electrode bonded to its surface is provided;
在ITO底电极上打印PEDOT:PSS混合材料,然后150℃下烘烤15min,得到空穴注入层;Print the PEDOT:PSS hybrid material on the ITO bottom electrode, and then bake at 150°C for 15min to obtain the hole injection layer;
在所述空穴注入层上打印浓度为8mg/mL的TFB,然后80℃下烘烤10min,得到空穴传输层;Printing TFB with a concentration of 8 mg/mL on the hole injection layer, and then baking at 80° C. for 10 minutes to obtain a hole transport layer;
在所述空穴传输层的表面打印浓度为20mg/mL的量子点材料,得到量子点发光层;Printing a quantum dot material with a concentration of 20 mg/mL on the surface of the hole transport layer to obtain a quantum dot light-emitting layer;
在所述量子点发光层上打印浓度为30mg/mL的纳米ZnO,然后80℃下烘烤30min,得到电子传输层;Print nano-ZnO with a concentration of 30mg/mL on the quantum dot light-emitting layer, and then bake at 80°C for 30min to obtain an electron transport layer;
在真空度为3×10 -4Pa的条件下,以1埃/秒的速度蒸镀Al电极100秒,Al的厚度为10nm; Under the condition of vacuum degree of 3×10 -4 Pa, evaporate the Al electrode at a speed of 1 Angstrom/second for 100 seconds, and the thickness of Al is 10nm;
在真空度为3×10 -4Pa的条件下,以1埃/秒的速度蒸镀Ag电极200秒,Ag的厚度为20nm,得到常规的量子点发光二极管。 Under the condition of a vacuum degree of 3×10 -4 Pa, an Ag electrode was evaporated at a rate of 1 angstrom/second for 200 seconds, and the thickness of Ag was 20 nm to obtain a conventional quantum dot light-emitting diode.
对比例2Comparative example 2
常规的量子点发光二极管的制备Fabrication of Conventional Quantum Dot Light-Emitting Diodes
提供一表面结合有ITO底电极的衬底;A substrate with an ITO bottom electrode bonded to its surface is provided;
在ITO底电极上打印PEDOT:PSS混合材料,然后150℃下烘烤15min,得到空穴注入层;Print the PEDOT:PSS hybrid material on the ITO bottom electrode, and then bake at 150°C for 15min to obtain the hole injection layer;
在所述空穴注入层上打印浓度为8mg/mL的TFB,然后80℃下烘烤10min,得到空穴传输层;Printing TFB with a concentration of 8 mg/mL on the hole injection layer, and then baking at 80° C. for 10 minutes to obtain a hole transport layer;
在所述空穴传输层的表面打印浓度为20mg/mL的量子点材料,得到量子点发光层;Printing a quantum dot material with a concentration of 20 mg/mL on the surface of the hole transport layer to obtain a quantum dot light-emitting layer;
在所述量子点发光层上打印浓度为30mg/mL的纳米ZnO,然后80℃下烘烤30min,得到电子传输层;Print nano-ZnO with a concentration of 30mg/mL on the quantum dot light-emitting layer, and then bake at 80°C for 30min to obtain an electron transport layer;
在真空度为3×10 -4Pa的条件下,以1埃/秒的速度蒸镀Ag电极1000秒,Ag的厚度为20nm,得到常规的量子点发光二极管。 Under the condition of a vacuum degree of 3×10 -4 Pa, an Ag electrode was evaporated at a rate of 1 angstrom/second for 1000 seconds, and the Ag thickness was 20 nm to obtain a conventional quantum dot light-emitting diode.
测试所述实施例1及对比例1制备的量子点发光二极管的JVL数据。The JVL data of the quantum dot light-emitting diodes prepared in Example 1 and Comparative Example 1 were tested.
QLED JVL测试方法为:使用Keithley2400对量子点发光二极管从-0.6V开始施加电压,其中,电压台阶为0.2V,电压施加范围为-0.6V至8V;随着电压的施加,记录器件电流密度和亮度随电压的变化,得到电流密度随电压的变化的曲线图(参图4),亮度随电压的变化的曲线图(参图5);通过计算得到器件外量子效率以及电流效率,得到外量子效率-电压曲线图(参图6),电流效率-电压曲线图(参图7)。The QLED JVL test method is: use Keithley2400 to apply a voltage to the quantum dot light-emitting diode from -0.6V, where the voltage step is 0.2V, and the voltage application range is -0.6V to 8V; with the application of the voltage, record the device current density and The change of luminance with voltage, the graph of the change of current density with voltage (refer to Figure 4), the graph of the change of luminance with voltage (refer to Fig. 5); the external quantum efficiency and current efficiency of the device can be obtained by calculation, and the external quantum efficiency can be obtained Efficiency-voltage curve (see Figure 6), current efficiency-voltage curve (see Figure 7).
由图5-7可知:当使用实施例1的方案制备量子点发光二极管时,器件的启亮电压将由于PEI的修饰而下降,同时器件亮度、外量子效率、电流效率都将大幅提升。It can be seen from Figures 5-7 that when the quantum dot light-emitting diode is prepared using the scheme of Example 1, the turn-on voltage of the device will be reduced due to the modification of PEI, and the brightness, external quantum efficiency, and current efficiency of the device will be greatly improved.
测试所述实施例1及对比例1制备的量子点发光二极管的工作寿命。The working life of the quantum dot light-emitting diodes prepared in Example 1 and Comparative Example 1 was tested.
QLED寿命测试的工作原理:How QLED life test works:
128路QLED寿命测试系统通过中央处理计算机的PCI总线通信,控制NI(美国国家仪器)的数字IO卡实现路数的片选以及数字信号的输出,相应的数字信号通过D/A芯片转换为模拟信号,完成电流输出(I),并通过数据采集卡实现数据采集。亮度的采集通过传感器将光信号转换为电信号,利用电信号模拟亮度变化(L)。The 128-channel QLED life test system controls the digital IO card of NI (National Instruments) through the PCI bus communication of the central processing computer to realize the chip selection of the number of channels and the output of digital signals, and the corresponding digital signals are converted to analog through the D/A chip. signal, complete the current output (I), and realize data acquisition through the data acquisition card. The acquisition of brightness converts the optical signal into an electrical signal through the sensor, and uses the electrical signal to simulate the brightness change (L).
QLED寿命测试方法:QLED life test method:
选择3-4个不同的恒定电流密度,(比如100mA/cm 2、50mA/cm 2、20mA/cm 2、10mA/cm 2),测试在相应条件下的起始亮度;维持恒定电流,记录亮度和器件电压随时间的变化,得到亮度-时间曲线图(参图8);记录在不同恒定电流下器件亮度衰减到95%、80%、75%及50%的所经历的时间T95、T80、T75及T50;通过曲线拟合计算加速因子;通过经验公式外推器件的亮度从1000nits衰减到95%所经历的时间T,即器件的寿命。 Select 3-4 different constant current densities (such as 100mA/cm 2 , 50mA/cm 2 , 20mA/cm 2 , 10mA/cm 2 ), and test the initial brightness under corresponding conditions; maintain a constant current and record the brightness and the change of device voltage with time to obtain the brightness-time curve (refer to Figure 8); record the time T95, T80, T75 and T50; calculate the acceleration factor by curve fitting; extrapolate the time T for the brightness of the device to decay from 1000 nits to 95% by empirical formula, that is, the life of the device.
所述经验公式为:T=(LMA×/1000)A*T95。The empirical formula is: T=(LMA×/1000)A*T95.
其中,LMAX为最高亮度,A为加速因子。Among them, LMAX is the highest brightness, and A is the acceleration factor.
通过上述经验公式外推的实施例1的量子点发光二极管的寿命曲线图参见图9。The lifetime curve of the quantum dot light-emitting diode in Example 1 extrapolated by the above empirical formula is shown in FIG. 9 .
由图9可知:当使用实施例1的方案制备量子点发光二极管时,器件的寿命(T95)将有大幅提升。It can be seen from FIG. 9 that when the quantum dot light-emitting diode is prepared using the scheme of Example 1, the lifetime (T95) of the device will be greatly improved.
以上对本申请实施例所提供的量子点发光二极管的制备方法进行了详细介绍,本文中应用了具体个例对本申请的原理及实施方式进行了阐述,以上实施例的说明只是用于帮助理解本申请的方法及其核心思想;同时,对于本领域的技术人员,依据本申请的思想,在具体实施方式及应用范围上均会有改变之处,综上所述,本说明书内容不应理解为对本申请的限制。The preparation method of the quantum dot light-emitting diode provided by the embodiment of the present application has been introduced in detail above. In this paper, specific examples are used to illustrate the principle and implementation of the present application. The description of the above embodiment is only used to help understand the present application. method and its core idea; at the same time, for those skilled in the art, according to the idea of this application, there will be changes in the specific implementation and application scope. Application Restrictions.

Claims (20)

  1. 一种量子点发光二极管的制备方法,其包括如下步骤:A method for preparing a quantum dot light-emitting diode, comprising the steps of:
    提供衬底,在所述衬底上形成底电极;providing a substrate on which a bottom electrode is formed;
    提供界面修饰材料、电子传输材料及有机溶剂,混合,得到混合溶液;Provide interface modification materials, electron transport materials and organic solvents, and mix them to obtain a mixed solution;
    提供量子点材料,将所述量子点材料设置在所述底电极上,形成量子点膜,再将所述混合溶液设置在所述量子点膜的表面,干燥以得到量子点发光层及电子传输层,其中,所述量子点膜为量子点干膜或量子点湿膜;Provide a quantum dot material, arrange the quantum dot material on the bottom electrode to form a quantum dot film, then place the mixed solution on the surface of the quantum dot film, and dry to obtain a quantum dot light-emitting layer and electron transport layer, wherein the quantum dot film is a quantum dot dry film or a quantum dot wet film;
    在所述电子传输层上形成顶电极。A top electrode is formed on the electron transport layer.
  2. 如权利要求1所述的量子点发光二极管的制备方法,其中,所述量子点发光层及电子传输层之间形成有过渡层,所述过渡层内包含量子点、界面修饰材料及电子传输材料,所述过渡层中的界面修饰材料填充在所述过渡层中的量子点之间的间隙中、电子传输材料之间的间隙中、及量子点与电子传输材料之间的间隙中。The method for preparing a quantum dot light-emitting diode according to claim 1, wherein a transition layer is formed between the quantum dot luminescent layer and the electron transport layer, and the transition layer includes quantum dots, an interface modification material and an electron transport material , the interface modifying material in the transition layer is filled in the gaps between the quantum dots in the transition layer, the gaps between the electron transport materials, and the gaps between the quantum dots and the electron transport materials.
  3. 如权利要求1所述的量子点发光二极管的制备方法,其中,将所述混合溶液设置在所述量子点膜的表面之后还包括静置的步骤,所述静置时间为5-10秒。The method for preparing quantum dot light-emitting diodes according to claim 1, wherein after disposing the mixed solution on the surface of the quantum dot film, it further includes a step of standing, and the standing time is 5-10 seconds.
  4. 如权利要求1所述的量子点发光二极管的制备方法,其中,提供量子点材料,将所述量子点材料设置在所述底电极上,形成量子点膜,再将所述混合溶液设置在所述量子点膜的表面,包括:The preparation method of quantum dot light-emitting diode as claimed in claim 1, wherein, provide quantum dot material, described quantum dot material is arranged on the described bottom electrode, forms quantum dot film, then described mixed solution is arranged on the said bottom electrode The surface of the quantum dot film, including:
    提供量子点材料,将量子点材料设置在底电极上,形成量子点干膜,得到量子点发光层后,将所述混合溶液添加至所述量子点发光层上。Provide quantum dot material, arrange quantum dot material on the bottom electrode, form quantum dot dry film, after obtaining quantum dot light-emitting layer, add the mixed solution on the quantum dot light-emitting layer.
  5. 如权利要求1所述的量子点发光二极管的制备方法,其中,提供量子点材料,将所述量子点材料设置在所述底电极上,形成量子点膜,再将所述混合溶液设置在所述量子点膜的表面,包括:The preparation method of quantum dot light-emitting diode as claimed in claim 1, wherein, provide quantum dot material, described quantum dot material is arranged on the described bottom electrode, forms quantum dot film, then described mixed solution is arranged on the said bottom electrode The surface of the quantum dot film, including:
    提供量子点材料,将所述量子点材料设置在底电极上,形成量子点湿膜,再将所述混合溶液通过溶液法设置在所述量子点湿膜的表面。The quantum dot material is provided, and the quantum dot material is arranged on the bottom electrode to form a quantum dot wet film, and then the mixed solution is arranged on the surface of the quantum dot wet film by a solution method.
  6. 如权利要求1所述的量子点发光二极管的制备方法,其中,提供量子点材料,将所述量子点材料设置在所述底电极上,形成量子点膜,再将所述混合溶液设置在所述量子点膜的表面,包括:The preparation method of quantum dot light-emitting diode as claimed in claim 1, wherein, provide quantum dot material, described quantum dot material is arranged on the described bottom electrode, forms quantum dot film, then described mixed solution is arranged on the said bottom electrode The surface of the quantum dot film, including:
    提供量子点材料,将量子点材料旋涂在所述底电极上,形成量子点湿膜,并在旋涂开始后且量子点材料形成干膜前添加所述混合溶液,添加结束后停止旋涂。Quantum dot material is provided, the quantum dot material is spin-coated on the bottom electrode to form a quantum dot wet film, and the mixed solution is added after the spin coating starts and before the quantum dot material forms a dry film, and the spin coating is stopped after the addition .
  7. 如权利要求6所述的量子点发光二极管的制备方法,其中,所述旋涂的转速为2000-3000r/s,时间范围为20-30s。The method for preparing quantum dot light-emitting diodes according to claim 6, wherein the rotation speed of the spin coating is 2000-3000r/s, and the time range is 20-30s.
  8. 如权利要求6所述的量子点发光二极管的制备方法,其中,所述在旋涂开始后且量子点材料形成干膜前的时间为2-10秒。The method for preparing a quantum dot light-emitting diode as claimed in claim 6, wherein the time after the start of the spin coating and before the quantum dot material forms a dry film is 2-10 seconds.
  9. 如权利要求1所述的量子点发光二极管的制备方法,其中,所述量子点材料中量子点的浓度为10-20mg/mL,所述量子点材料选自CdSeZnS、CdSeCdS/ZnS或ZnCdS/ZnS。The preparation method of quantum dot light-emitting diode as claimed in claim 1, wherein, the concentration of quantum dot in the said quantum dot material is 10-20mg/mL, and said quantum dot material is selected from CdSeZnS, CdSeCdS/ZnS or ZnCdS/ZnS .
  10. 如权利要求1所述的量子点发光二极管的制备方法,其中,所述界面修饰材料选自聚乙烯亚胺、聚乙氧基乙烯亚胺、聚[9,9-二(3’-(N,N-二甲基氨基)丙基)-2,7-芴]-2,7-(9,9-二辛基芴))]、聚乙二醇、共轭聚合电解质或聚氧化乙烯中的一种或几种。The preparation method of quantum dot light-emitting diode as claimed in claim 1, wherein, said interface modification material is selected from polyethyleneimine, polyethoxyethyleneimine, poly[9,9-bis(3'-(N , N-dimethylamino)propyl)-2,7-fluorene]-2,7-(9,9-dioctylfluorene))], polyethylene glycol, conjugated polyelectrolyte or polyethylene oxide one or more of.
  11. 如权利要求1所述的量子点发光二极管的制备方法,其中,所述电子传输材料选自金属氧化物、掺杂金属氧化物、2-6族半导体材料、3-5族半导体材料及1-3-6族半导体材料中的一种或几种,所述金属氧化物选自ZnO、TiO 2、SnO 2中的一种或几种;所述掺杂金属氧化物中的金属氧化物选自ZnO、TiO 2、SnO 2中的一种或几种,掺杂元素选自铝、镁、铟、镓中的一种或几种;所述2-6半导体族材料选自ZnS、ZnSe、CdS中的一种或几种;所述3-5半导体族材料选自InP、GaP中的至少一种;所述1-3-6族半导体材料选自CuInS、CuGaS中的至少一种。 The preparation method of quantum dot light-emitting diodes as claimed in claim 1, wherein, the electron transport material is selected from metal oxides, doped metal oxides, 2-6 group semiconductor materials, 3-5 group semiconductor materials and 1- One or more of Group 3-6 semiconductor materials, the metal oxide is selected from one or more of ZnO, TiO 2 , SnO 2 ; the metal oxide in the doped metal oxide is selected from One or more of ZnO, TiO 2 , SnO 2 , the doping element is selected from one or more of aluminum, magnesium, indium, gallium; the 2-6 semiconductor group materials are selected from ZnS, ZnSe, CdS One or more of them; the 3-5 group semiconductor materials are selected from at least one of InP and GaP; the 1-3-6 group semiconductor materials are selected from at least one of CuInS and CuGaS.
  12. 如权利要求1所述的量子点发光二极管的制备方法,其中,所述有机溶剂选自乙二醇单甲醚、异丙醇或乙醇中的一种或几种。The method for preparing quantum dot light-emitting diodes according to claim 1, wherein the organic solvent is selected from one or more of ethylene glycol monomethyl ether, isopropanol or ethanol.
  13. 如权利要求1所述的量子点发光二极管的制备方法,其中,所述混合溶液中,所述界面修饰材料的浓度范围为0.1wt%-10wt%。The method for preparing quantum dot light-emitting diodes according to claim 1, wherein, in the mixed solution, the concentration range of the interface modification material is 0.1wt%-10wt%.
  14. 如权利要求1所述的量子点发光二极管的制备方法,其中,所述混合溶液中,所述电子传输材料的浓度范围为10-30mg/mL。The method for preparing quantum dot light-emitting diodes according to claim 1, wherein, in the mixed solution, the concentration range of the electron transport material is 10-30 mg/mL.
  15. 一种量子点发光二极管,其包括层叠设置的底电极、量子点发光层、电子传输层及顶电极,所述量子点发光层中包含量子点,所述电子传输层包含电子传输材料,其中,相邻的量子点和电子传输材料之间的间隙中填充有界面修饰材料。A quantum dot light-emitting diode, which includes a stacked bottom electrode, a quantum dot light-emitting layer, an electron transport layer, and a top electrode, wherein the quantum dot light-emitting layer includes quantum dots, and the electron transport layer includes an electron transport material, wherein, The gaps between adjacent quantum dots and electron transport materials are filled with interface modification materials.
  16. 如权利要求15所述的量子点发光二极管,其中,所述量子点发光层的邻近电子传输层一侧的量子点之间的间隙中、及所述电子传输层的电子传输材料之间的间隙中也填充有所述界面修饰材料。The quantum dot light-emitting diode according to claim 15, wherein, in the gap between the quantum dots on the side of the quantum dot light-emitting layer adjacent to the electron transport layer, and the gap between the electron transport materials of the electron transport layer is also filled with the interface modifying material.
  17. 如权利要求15所述的量子点发光二极管,其中,所述量子点发光二极管还包括位于量子点发光层与电子传输层之间的过渡层,所述过渡层内包含量子点、界面修饰材料及电子传输材料,所述过渡层中的界面修饰材料填充在所述过渡层中的量子点之间的间隙中、电子传输材料之间的间隙中、及量子点与电子传输材料之间的间隙中。The quantum dot light-emitting diode according to claim 15, wherein the quantum dot light-emitting diode further comprises a transition layer between the quantum dot light-emitting layer and the electron transport layer, and the transition layer includes quantum dots, interface modification materials and Electron transport material, the interface modifying material in the transition layer is filled in the gaps between the quantum dots in the transition layer, in the gaps between the electron transport materials, and in the gaps between the quantum dots and the electron transport materials .
  18. 如权利要求17所述的量子点发光二极管,其中,所述界面修饰材料还填充在所述量子点发光层与过渡层之间、所述过渡层与所述电子传输层之间。The quantum dot light-emitting diode according to claim 17, wherein the interface modification material is also filled between the quantum dot light-emitting layer and the transition layer, and between the transition layer and the electron transport layer.
  19. 如权利要求15所述的量子点发光二极管,其中,所述界面修饰材料选自聚乙烯亚胺、聚乙氧基乙烯亚胺、聚[9,9-二(3’-(N,N-二甲基氨基)丙基)-2,7-芴]-2,7-(9,9-二辛基芴))]、聚乙二醇、共轭聚合电解质或聚氧化乙烯中的一种或几种。The quantum dot light-emitting diode according to claim 15, wherein the interface modification material is selected from polyethyleneimine, polyethoxyethyleneimine, poly[9,9-bis(3'-(N,N- One of dimethylamino)propyl)-2,7-fluorene]-2,7-(9,9-dioctylfluorene))], polyethylene glycol, conjugated polyelectrolyte or polyethylene oxide or several.
  20. 如权利要求15所述的量子点发光二极管,其中,所述电子传输材料选自金属氧化物、掺杂金属氧化物、2-6族半导体材料、3-5族半导体材料及1-3-6族半导体材料中的一种或几种,所述金属氧化物选自ZnO、TiO 2、SnO 2中的一种或几种;所述掺杂金属氧化物中的金属氧化物选自ZnO、TiO 2、SnO 2中的一种或几种,掺杂元素选自铝、镁、铟、镓中的一种或几种;所述2-6半导体族材料选自ZnS、ZnSe、CdS中的一种或几种;所述3-5半导体族材料选自InP、GaP中的至少一种;所述1-3-6族半导体材料选自CuInS、CuGaS中的至少一种。 The quantum dot light-emitting diode according to claim 15, wherein the electron transport material is selected from metal oxides, doped metal oxides, 2-6 group semiconductor materials, 3-5 group semiconductor materials and 1-3-6 One or more of the group semiconductor materials, the metal oxide is selected from one or more of ZnO, TiO 2 , SnO 2 ; the metal oxide in the doped metal oxide is selected from ZnO, TiO 2. One or more of SnO 2 , the doping element is selected from one or more of aluminum, magnesium, indium, and gallium; the 2-6 semiconductor group material is selected from one or more of ZnS, ZnSe, and CdS one or several kinds; the 3-5 semiconductor group materials are selected from at least one of InP and GaP; the 1-3-6 group semiconductor materials are selected from at least one of CuInS and CuGaS.
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