WO2022135405A1 - 发光二极管及其制备方法 - Google Patents

发光二极管及其制备方法 Download PDF

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Publication number
WO2022135405A1
WO2022135405A1 PCT/CN2021/140130 CN2021140130W WO2022135405A1 WO 2022135405 A1 WO2022135405 A1 WO 2022135405A1 CN 2021140130 W CN2021140130 W CN 2021140130W WO 2022135405 A1 WO2022135405 A1 WO 2022135405A1
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light
emitting diode
film
electron transport
layer
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PCT/CN2021/140130
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English (en)
French (fr)
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张天朔
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Tcl科技集团股份有限公司
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Publication of WO2022135405A1 publication Critical patent/WO2022135405A1/zh
Priority to US17/935,701 priority Critical patent/US20230038312A1/en

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/17—Carrier injection layers
    • H10K50/171—Electron injection layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots

Definitions

  • the present application relates to the technical field of optoelectronic devices, and in particular, to a light-emitting diode and a preparation method thereof.
  • Quantum dots a class of nanomaterials composed of a small number of atoms, whose radii are usually smaller or close to the exciton Bohr radius, exhibit remarkable quantum confinement effects and have unique optical properties such as luminescence.
  • the spectrum is continuously adjustable by the size and composition of the material itself, narrow half-peak width, high fluorescence efficiency, long life, excellent monodispersity and strong photothermal stability. These unique properties make them widely used in displays, lighting, biomarkers, and solar cells.
  • Quantum dot electroluminescence is a new type of solid-state lighting technology. It has the advantages of low cost, light weight, fast response speed and high color saturation. It has broad development prospects and has become a new generation of light emitting diode (LED) lighting. one of the important research directions.
  • the existing quantum dot light-emitting diode (Quantum Dot Light Emitting Diode, QLED) mainly includes a cathode, an anode and a quantum dot light-emitting layer.
  • QLED will also introduce functional layers such as a hole transport layer, an electron transport layer, and an electron injection layer.
  • the water-oxygen environmental stability of the electrical properties especially the relative humidity (RH)>75%) is always an unsolvable problem.
  • One of the purposes of the embodiments of the present application is to provide a light emitting diode and a method for manufacturing the same.
  • a light-emitting diode comprising an anode and a cathode disposed opposite to each other, a light-emitting layer disposed between the anode and the cathode, an electron transport layer disposed between the cathode and the light-emitting layer, and a composite film disposed between the cathode and the electron transport layer, wherein the composite film comprises an aluminum oxide film disposed adjacent to the electron transport layer, and a nano metal disposed away from the electron transport layer oxide film or silicon nitride film.
  • the material of the nano metal oxide thin film is selected from at least one of TiO 2 , ZrO 2 , and SiO 2 .
  • the thickness of the composite film is less than or equal to 25 nm.
  • the thickness of the composite film is 15-25 nm.
  • the thickness ratio of the aluminum oxide thin film and the nano metal oxide thin film is 3:1 to 1:3.
  • the thickness ratio of the aluminum oxide film and the nano metal oxide film is 1:3, 1:2, 1:1, 2:1, 3:1 .
  • the thickness ratio of the aluminum oxide film and the silicon nitride film is 3:1 ⁇ 1:3.
  • the thickness ratio of the aluminum oxide film and the silicon nitride film is 1:3, 1:2, 1:1, 2:1, 3:1.
  • the light emitting diode further includes a hole functional layer disposed between the anode and the light emitting layer.
  • the hole functional layer includes at least one of a hole injection layer, a hole transport layer, and a hole blocking layer.
  • the light emitting diode is a vertical structure light emitting diode, and the anode is disposed on the substrate.
  • the light-emitting layer is a quantum dot light-emitting layer or an organic light-emitting layer.
  • a method for preparing a light-emitting diode comprising the following steps:
  • a prefabricated device includes an anode substrate, and a light-emitting layer disposed on the anode surface of the anode substrate;
  • a thin aluminum oxide film is prepared on the surface of the electron transport layer on the side away from the light-emitting layer, and a nanometer metal oxide thin film is prepared on the surface of the aluminum oxide thin film on the side away from the electron transport layer to obtain a composite thin film or silicon nitride film;
  • a cathode is prepared on the surface of the composite film away from the electron transport layer to obtain the light emitting diode.
  • the temperature of the annealing treatment ranges from 30°C to 120°C.
  • the temperature of the annealing treatment ranges from 30°C to 50°C.
  • the beneficial effect of the light-emitting diode provided by the embodiments of the present application is that a composite film is introduced between the cathode of the light-emitting diode and the electron transport layer as a transition layer, and the transition layer selects an aluminum oxide film and a nano-metal oxide film to form a composite film or
  • the aluminum oxide film and the silicon nitride film are selected to form a composite film to improve the stability of the water and oxygen environment. details as follows:
  • aluminum oxide, nano-metal oxide materials and silicon nitride itself have good gas barrier properties after film formation, and have good thermal stability. In an environment with unfriendly relative humidity and temperature, they can still be It plays a good anti-aging effect between the electron transport layer and the electrode, and improves the overall stability of the device. At the same time, the optical transmittance of these materials is high, which will not affect the light output of the device itself too much and cause the optical performance to be attenuated. It should be noted that the pure Al2O3 film has poor chemical stability due to irregular film-forming crystals, so the gas barrier performance is not good in the environment of high humidity (RH>75%).
  • the present application adopts a composite film and introduces a nanometer metal oxide film to avoid the problem of irregular film formation and poor chemical stability of the aluminum oxide film.
  • the stability of the light-emitting diode is effectively improved, especially the stability in a high humidity (RH>75%) environment.
  • the aluminum oxide film with the conduction band of 3.2eV is arranged near the electron transport layer, and the nano metal oxide film or silicon nitride film is arranged near the cathode, so that the electron transport layer-
  • the energy level between the aluminum oxide film-nano metal oxide film or the silicon nitride film-cathode is more matched, so as to avoid the obvious influence of the introduction of the composite film on the injection of carriers, so that the application is approved by The introduction of the composite film can maintain the good electrical properties of the device, with good stability, especially in the water and oxygen environment.
  • Al2O3, nano-metal oxide materials and silicon nitride have good deposition adhesion on various electron transport materials and cathode materials, and have good film-forming properties, which are suitable for various electron transport layer substrates or cathode substrates. It will not cause the problem of poor film formation and affect the electrical performance.
  • the beneficial effect of the method for preparing a light-emitting diode provided by the embodiment of the present application is that: the method only needs to prepare an aluminum oxide film and a nano-metal oxide between the electron transport layer and the cathode on the basis of the conventional preparation method of the light-emitting diode.
  • a composite film formed by a composite film or a composite film formed by an aluminum oxide film and a silicon nitride film may be used, and the aluminum oxide film may be disposed adjacent to the electron transport layer.
  • the method is simple in operation, mature in technology, and has good application prospects.
  • FIG. 1 is a schematic structural diagram of a light emitting diode provided by an embodiment of the present application
  • FIG. 2 is a flow chart of a manufacturing process of a light-emitting diode provided by an embodiment of the present application
  • FIG. 3 is a schematic structural diagram of a light-emitting diode with an upright structure provided by an embodiment of the present application
  • FIG. 4 is a schematic structural diagram of a light emitting diode with an upright structure provided by an embodiment of the present application.
  • the term "and/or" describes the association relationship of associated objects, indicating that there can be three kinds of relationships.
  • a and/or B can represent three cases where A exists alone, A and B exist simultaneously, and B exists alone. where A and B can be singular or plural.
  • the character "/" generally indicates that the associated objects are an "or" relationship.
  • At least one means one or more
  • plural items means two or more.
  • At least one item(s) below” or similar expressions thereof refer to any combination of these items, including any combination of single item(s) or plural items(s).
  • at least one (one) of a, b, or c or, “at least one (one) of a, b, and c” can mean: 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 respectively.
  • first and second are used for descriptive purposes only, to distinguish objects such as substances, interfaces, messages, requests and terminals from each other, and should not be understood as indicating or implying relative importance or implying that the number of technical characteristics.
  • first XX may also be referred to as the second XX
  • second XX may also be referred to as the first XX.
  • a feature defined as “first” or “second” may expressly or implicitly include one or more of that feature.
  • the environmental stability of electrical performance (especially high humidity RH>75%) is always an unsolvable problem. Specifically, after the water molecules in the environment enter the QLED device, it will have a certain positive aging effect on the interface layer between the electron transport layer and the electrode layer. Although the electrical performance and life of the QLED device are improved in a short time, it will also As a result, the QLED device quickly enters the decay period, and the aging of the device leads to an increase in leakage current and a significant decrease in life span.
  • the reason for this aging phenomenon may be that the water and oxygen infiltrated into the QLED device have a certain oxidation effect on the interface layer between the cathode and the electron transport layer, or the water and the defects on the surface of the electron transport layer are attached or coordinated. .
  • This phenomenon is more pronounced when the ambient relative humidity (RH) is greater than 75%.
  • the embodiments of the present application provide a new light-emitting diode and a method for manufacturing the same.
  • an embodiment of the present application provides a light-emitting diode, comprising an anode 1 and a cathode 7 arranged opposite to each other, a light-emitting layer 4 arranged between the anode 1 and the cathode 7 , and a light-emitting layer 4 arranged between the cathode 7 and the light-emitting layer 4
  • a nanometer metal oxide film 621 or a silicon nitride film 622 is provided.
  • a composite film 6 is introduced between the cathode of the light-emitting diode and the electron transport layer as a transition layer, and the transition layer selects the aluminum oxide film 61 and the nano-metal oxide film 621 to form the composite film 6 or
  • the aluminum oxide film 61 and the silicon nitride film 622 are selected to form the composite film 6 to improve the stability of the water and oxygen environment. details as follows:
  • aluminum oxide, nano-metal oxide materials and silicon nitride itself have good gas barrier properties after film formation, and have good thermal stability. In an environment with unfriendly relative humidity and temperature, they can still be It plays a good anti-aging effect between the electron transport layer and the electrode, and improves the overall stability of the device. At the same time, the optical transmittance of these materials is high, which will not affect the light output of the device itself too much and cause the optical performance to be attenuated. It should be noted that the pure Al2O3 film has poor chemical stability due to irregular film-forming crystals, so the gas barrier performance is not good in the environment of high humidity (RH>75%).
  • the embodiment of the present application adopts the composite film 6 and introduces the nano metal oxide film 62 to avoid the problem of irregular film formation and poor chemical stability of the aluminum oxide film 61 .
  • the stability of the light-emitting diode is effectively improved, especially the stability in a high humidity (RH>75%) environment.
  • the aluminum oxide film 61 with the conduction band of 3.2 eV is arranged near the electron transport layer 5
  • the nano metal oxide film 621 or the silicon nitride film 622 is arranged near the cathode 7 at the same time.
  • the implantation of ions has a significant impact, so that the present application can have better stability, especially better water-oxygen environment stability, on the premise of maintaining good electrical properties of the device by introducing the composite film 6 .
  • Al2O3 and nano-metal oxide materials have good deposition adhesion on various electron transport materials and cathode materials, and have good film-forming properties. They are suitable for various electron transport layer substrates or cathode substrates, and will not cause formation. The problem that the film is poor and affects the electrical performance.
  • the composite film 6 is disposed at the interface between the cathode 7 and the electron transport layer 5, so as to improve the negative influence of the external water and oxygen on the packaged light-emitting diode.
  • the composite film 6 formed by the aluminum oxide film 61 and the nano metal oxide film 621 or the composite film 6 formed by the aluminum oxide film 61 and the nano metal oxide film 622 is used to improve the encapsulation.
  • the environmental stability of the light emitting diode, especially the stability of the packaged light emitting diode in a high humidity (RH>75%) environment is improved.
  • Al2O3 itself has no electron transport function, but has better air barrier properties, especially water and oxygen barrier properties and good film-forming adhesion.
  • the conduction band of Al2O3 matches the electron transport layer and the electrode. Therefore, the introduction through the thin film can improve the environmental stability of the light-emitting diode without significantly affecting the carrier transport. Disposing the Al2O3 film 61 between the cathode 7 and the electron transport layer 5 alone will accelerate the forward aging efficiency of the light-emitting diode.
  • the luminous efficiency of the device can be improved, due to the forward aging process If the speed is too fast, the luminous efficiency of the device is unstable, and the device quickly enters the decay stage, which is ultimately unfavorable to obtain a light-emitting diode with better stability.
  • the nano metal oxide in the nano metal oxide film 621 and the silicon nitride (SiN 4 ) in the silicon nitride film 622 have certain water and oxygen barrier properties.
  • the material of the nano metal oxide thin film 621 is selected from at least one of TiO 2 , ZrO 2 , and SiO 2 .
  • the formed nano metal oxide film 621 itself not only has good gas barrier properties and thermal stability, but also can improve the film-forming crystallinity of the aluminum oxide film 61, further improving the aluminum oxide film 61.
  • the air isolation performance of the film 61 especially the water and oxygen isolation performance, enables the light-emitting diode to still play a good anti-aging effect between the electron transport layer 5 and the cathode 7 in an environment where relative humidity and temperature are unfriendly, and improve the overall performance of the device. stability.
  • the thickness of the composite film 6 is less than or equal to 25 nm. If the thickness of the composite film 6 is too high, the carrier transmission efficiency will be affected, and the electrical performance will be lowered. In some embodiments, the thickness of the composite film 6 is 15-25 nm. In this case, the composite film 6 has a suitable thickness, which can not only effectively play the role of air isolation, but also not significantly affect the transport efficiency of carriers. Exemplarily, the thickness of the composite film 6 is 15 nm, 16 nm, 17 nm, 18 nm, 19 nm, 20 nm, 21 nm, 22 nm, 23 nm, 24 nm, 25 nm.
  • the thickness ratio of the aluminum oxide film 61 and the nano metal oxide film 621 is 3:1 ⁇ 1:3. In some embodiments, in the composite film 6, the thickness ratio of the aluminum oxide film 61 and the silicon nitride film 622 is 3:1 ⁇ 1:3. In this case, the thickness of the aluminum oxide film 61 accounts for 25% to 75% of the total thickness of the composite film 6, which plays an air barrier function, especially a water and oxygen barrier function, and passes through the remaining thickness of the nano metal oxide film 621 or The silicon nitride film 622 is used to improve the film-forming crystallinity of the aluminum oxide film 61, thereby ensuring the air isolation effect of the aluminum oxide film 61, especially the water and oxygen isolation effect.
  • the nano-metal oxide film 621 or the silicon nitride film 622 with a certain thickness introduced into the light-emitting diode also has an air-isolating effect, which can further improve the air-isolating effect of the light-emitting diode, especially the water-oxygen blocking effect. If the thickness of the aluminum oxide film 61 is too thick, the film formation of the aluminum oxide film 61 will be irregular, and the chemical stability will be worse, which will affect the air barrier effect of the aluminum oxide film 61; If the thickness of the thin film 621 or the silicon nitride thin film 622 is too thick, the electrical transmission performance of the composite thin film 6 will be affected, and the final overall brightness of the light emitting diode device may be reduced.
  • the thickness ratio of the aluminum oxide film 61 and the nano metal oxide film 62 is 1:3, 1:2, 1:1, 2:1, 3:1, but not limited to this. In some embodiments, in the composite film 6, the thickness ratio of the aluminum oxide film 61 and the silicon nitride film 622 is 1:3, 1:2, 1:1, 2:1, 3:1, but not limited to this.
  • the thickness of the composite thin film 6 is less than or equal to 25 nm, and the thickness ratio of the aluminum oxide thin film 61 and the nano metal oxide thin film 621 is 3:1 ⁇ 1:3. In some embodiments, the thickness of the composite film 6 is less than or equal to 25 nm, and the thickness ratio of the aluminum oxide film 61 to the silicon nitride film 622 is 3:1 ⁇ 1:3. Exemplarily, the thickness ratio of the aluminum oxide film 61 and the nano metal oxide film 621 is 1:3, 1:2, 1:1, 2:1, and 3:1. Exemplarily, the thickness ratio of the aluminum oxide film 61 and the silicon nitride film 621 is 1:3, 1:2, 1:1, 2:1, and 3:1.
  • the thickness of the composite film 6 is 20 nm, and the thickness of the aluminum oxide film 61 and the nano metal oxide film 621 are both 10 nm. In some embodiments, the thickness of the composite film 6 is 20 nm, and the thicknesses of the aluminum oxide film 61 and the silicon nitride film 622 are both 10 nm.
  • the light emitting diode further includes a hole functional layer disposed between the anode 1 and the light emitting layer 3 .
  • the hole functional layer includes at least one of a hole injection layer, a hole transport layer, and a hole blocking layer.
  • the light emitting diode may further include a substrate, and the anode 1 or the cathode 7 is disposed on the substrate.
  • the light emitting diodes provided by the embodiments of the present application are classified into a vertical structure light emitting diode and an inverted structure light emitting diode.
  • the upside-down structure light-emitting diode includes an anode 1 and a cathode 7 disposed opposite to each other, a light-emitting layer 4 disposed between the anode 1 and the cathode 7, and an electron transport layer disposed between the cathode 7 and the light-emitting layer 4 5, and the composite thin film 6 arranged between the cathode 7 and the electron transport layer 5, wherein the composite thin film 6 comprises an aluminum oxide thin film 61 set adjacent to the electron transport layer and a nanometer metal oxide thin film set away from the electron transport layer 5 62, and the anode 1 is arranged on the substrate.
  • hole functional layers such as a hole transport layer, a hole injection layer, and an electron blocking layer can be provided between the anode 1 and the light-emitting layer 4 .
  • the stability of the water-oxygen environment of the light-emitting diode can be improved by introducing the composite film 6; Preparation) annealing treatment temperature, so that the aging of the electron transport material is carried out in a low water and oxygen environment, so as to improve the stability of the light emitting diode.
  • the annealing temperature of the electron transport layer 5 to be 30° C. to 50° C.
  • the light-emitting diode includes a substrate 10 , an anode 1 disposed on the surface of the substrate 10 , and a hole injection layer 2 disposed on the surface of the anode 1 .
  • the hole transport layer 3 arranged on the surface of the hole injection layer 2
  • the light emitting layer 4 arranged on the surface of the hole transport layer 3
  • the electron transport layer 5 arranged on the surface of the light emitting layer 4
  • the composite compound arranged on the surface of the electron transport layer 5
  • the film 6 and the cathode 7 arranged on the surface of the composite film 6, wherein the composite film 6 includes an aluminum oxide film 61 arranged adjacent to the electron transport layer and a nanometer metal oxide film 621 or a silicon nitride film arranged away from the electron transport layer 5 622.
  • the inverted structure light-emitting diode includes an anode 1 and a cathode 7 disposed opposite to each other, a light-emitting layer 4 disposed between the anode 1 and the cathode 7, and an electron transport layer 5 disposed between the cathode 7 and the light-emitting layer 4 , and the composite film 6 arranged between the cathode 7 and the electron transport layer 5, wherein the composite film 6 comprises an aluminum oxide film 61 arranged adjacent to the electron transport layer and a nanometer metal oxide film 62 arranged away from the electron transport layer 5 or silicon nitride film 622, and the cathode 7 is disposed on the substrate.
  • hole functional layers such as a hole transport layer, a hole injection layer, and an electron blocking layer can be provided between the anode 1 and the light-emitting layer 4 .
  • the light-emitting diode includes a substrate 10, a cathode 7 disposed on the surface of the substrate 10, a composite film 6 disposed on the surface of the cathode 7, The electron transport layer 5 on the surface of the composite film 6, the light emitting layer 4 on the surface of the electron transport layer 5, the hole transport layer 3 on the surface of the light emitting layer 4, the hole injection layer 3 on the surface of the hole transport layer 3 , the anode 1 disposed on the surface of the hole injection layer 2 .
  • the light-emitting layer is a quantum dot light-emitting layer or an organic light-emitting layer.
  • the light-emitting diodes provided in the embodiments of the present application can be classified into organic light-emitting diodes and quantum dot light-emitting diodes according to the types of light-emitting materials.
  • the substrate 10 may include rigid substrates such as glass, silicon wafers, metal foils, etc., or flexible substrates such as polyimide (PI), polycarbonate (PC), polystyrene (PS), polyethylene (PE), polyvinyl chloride (PV), polyvinylpyrrolidone (PVP), polymethyl methacrylate, polyethylene terephthalate (PET), polyethylene naphthalate A combination of one or more of alcohol esters, polyamides, and polyethersulfones.
  • PI polyimide
  • PC polycarbonate
  • PS polystyrene
  • PE polyethylene
  • PV polyvinyl chloride
  • PV polyvinylpyrrolidone
  • PET polyethylene terephthalate
  • PET polyethylene naphthalate
  • the anode 1 may adopt common anode materials and thicknesses, which are not limited in the embodiments of the present application.
  • the anode material is selected from indium-doped tin oxide (ITO).
  • the material of the hole injection layer 2 can be selected from materials with good hole injection properties.
  • the material of the hole injection layer 2 is selected from poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonic acid) (PEDOT:PSS) and its s - MoO doped One of the derivatives (PEDOT:PSS:s-MoO 3 ).
  • the material of the hole transport layer 3 can be a conventional hole transport material.
  • the material of hole transport layer 3 is selected from poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(4,4'-(N-(p-butylene) phenyl)) diphenylamine)] (TFB), poly(9-vinylcarbazole) (PVK), poly(N,N'bis(4-butylphenyl)-N,N'-bis(benzene) base)benzidine)(Poly-TPD), N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine (NPB) one of the.
  • the material of the light emitting layer 4 is an organic light emitting material.
  • the material of the light emitting layer 4 is quantum dots.
  • the introduction of the composite film 6 to improve the water and oxygen barrier properties of the light emitting diode, thereby improving the stability of the device is more significant.
  • the quantum dots of the quantum dot light-emitting layer are direct bandgap compound semiconductors with light-emitting capability, and conventional quantum dot materials can be selected according to conventional quantum dot types.
  • the quantum dots of the quantum dot light-emitting layer can be one or more of II-VI compounds, III-V compounds, and II-IV-VI compounds, and the quantum dots can be single-component quantum dots or
  • the core-shell structure quantum dots can also be at least one of alloy structure quantum dots, organic-inorganic hybrid perovskite quantum dots, and all-inorganic quantum dot materials.
  • the quantum dots formed by II-VI compounds include, but are not limited to: CdSe, CdS, ZnSe, CdS, PbS, PbSe; the quantum dots formed by III-V compounds include but are not limited to: InP, InAs; II- Quantum dots formed from IV-VI compounds include, but are not limited to, CuInS 2 and AgInS 2 .
  • the material of the electron transport layer 5 conventional electron transport materials can be used.
  • the material of the electron transport layer 5 is selected from one of ZnO, aluminum-doped zinc oxide (AZO), lithium-doped zinc oxide (LZO), and magnesium-doped zinc oxide (MZO).
  • composition and material selection of the composite film 6 are as described above, and in order to save space, they will not be repeated here.
  • the cathode 7 may use common cathode materials and thicknesses, which are not limited in the embodiment of the present application.
  • the material of the cathode 7 is selected from the metal materials aluminum or silver. Using aluminum or silver as the cathode material and the arrangement of the composite film, the obtained light-emitting diode has better stability, especially the stability of water and oxygen.
  • the light emitting diodes with the upright structure provided in the embodiments of the present application can be prepared by the following methods.
  • an embodiment of the present application provides a method for preparing a light-emitting diode, comprising the following steps:
  • the prefabricated device includes an anode substrate, and a light-emitting layer disposed on an anode surface of the anode substrate.
  • the prefabricated device is a local device that already has an anode substrate and after the light-emitting layer is prepared.
  • the prefabricated device further includes a hole functional layer between the anode and the light emitting layer.
  • the hole functional layer includes at least one of a hole injection layer, a hole transport layer and an electron blocking layer.
  • a method for preparing a prefabricated device includes: preparing a hole injection layer on an anode substrate, preparing a hole transport layer on the hole injection layer, and preparing a light emitting layer on the hole transport layer to obtain a prefabricated device.
  • An electron transport material is formed on the surface of the light-emitting layer on the side away from the anode substrate, and an annealing treatment is performed to prepare an electron transport layer.
  • the electron transport material is formed on the surface of the light-emitting layer on the side away from the anode substrate by a solution processing method, and then annealed to form a film to prepare the electron transport layer.
  • the density of the electron transport layer can be improved.
  • the temperature of the annealing treatment is 30°C-120°C. In this case, during the annealing process, as the temperature increases, the thin film formed by the electron transport material will have a certain passivation effect, so that the water and oxygen adhesion ability of the electron transport material will gradually weaken, so that the resulting light-emitting diode will be aged. The required settling time is lengthened or shifted backwards.
  • the temperature of the annealing treatment is 30°C-50°C.
  • the temperature of the annealing treatment is controlled at a lower temperature level, the aging degree of the electron transport material is controlled at an appropriate level, the oxidation level at the interface between the electron transport layer and the cathode is reduced, and the forward aging makes the light-emitting diode achieve better performance.
  • the performance of the light-emitting diode is improved, and the life of the light-emitting diode is improved, and on this basis, the light-emitting diode is given a higher external quantum efficiency through low temperature annealing.
  • the composite film and encapsulating the light-emitting diode the light-emitting diode has good external quantum efficiency and strong stability at the same time.
  • the Al2O3 thin film, the nanometer metal oxide thin film, and the SiN thin film are prepared by plasma enhanced atomic layer deposition (PEALD).
  • PEALD plasma enhanced atomic layer deposition
  • the composite film can be prepared by stable, low-temperature PEALD without destroying the device structure.
  • the electron transport layer is prepared by low temperature annealing treatment, the influence of high temperature on the electron transport layer can be avoided, and the aging degree of the electron transport material during low temperature annealing can be preserved.
  • a cathode is prepared on the surface of the composite film away from the electron transport layer to obtain a light-emitting diode.
  • the cathode is prepared on the surface of the composite film on the side away from the electron transport layer by an evaporation process.
  • the obtained light-emitting diode can also be packaged.
  • the preparation method of the light-emitting diode provided by the embodiment of the present application only needs to prepare a composite film formed by an aluminum oxide film and a nano-metal oxide film between the electron transport layer and the cathode on the basis of the conventional light-emitting diode preparation method. Or a composite film formed by an aluminum oxide film and a silicon nitride film, and the aluminum oxide film can be arranged adjacent to the electron transport layer.
  • the method is simple in operation, mature in technology, and has good application prospects.
  • a quantum dot light-emitting diode with an upright structure is prepared by the following method:
  • PEDOT:PSS:s-MoO 3 was spin-coated on an ITO substrate and annealed in air to prepare a hole injection layer with a thickness of 30 nm;
  • PVK was spin-coated on the hole injection layer and annealed at 140 °C to prepare a hole transport layer with a thickness of 20 nm;
  • CdSe@ZnS quantum dots were spin-coated on the hole transport layer to prepare a quantum dot light-emitting layer with a thickness of 40 nm;
  • MZO was spin-coated on the quantum dot light-emitting layer and annealed at 90 °C for 30 minutes to prepare an electron transport layer with a thickness of 50 nm;
  • a 10 nm Al 2 O 3 film and a 10 nm TiO 2 film were deposited successively on the electron transport layer by plasma-enhanced atomic layer deposition (PEALD) to obtain a composite film;
  • PEALD plasma-enhanced atomic layer deposition
  • the upright structure quantum dot light emitting diode device is obtained.
  • Example 1 The difference from Example 1 is that the 10 nm TiO 2 film is replaced by a 10 nm ZrO 2 film.
  • Example 1 The difference from Example 1 is that the 10 nm TiO 2 film is replaced by a 10 nm SiO 2 film.
  • Example 1 The difference from Example 1 is that the 10 nm TiO 2 film is replaced by 10 nm SiN 4 .
  • Example 1 The difference from Example 1 is that in the step of "spin coating MZO on the quantum dot light-emitting layer and annealing at 90°C for 30 minutes", the annealing temperature was adjusted from 90°C to 40°C.
  • Example 2 The difference from Example 1 is that the step of “depositing a 10 nm Al 2 O 3 film and a 10 nm TiO 2 film successively on the electron transport layer by plasma-enhanced atomic layer deposition (PEALD) to obtain a composite film” is omitted.
  • PEALD plasma-enhanced atomic layer deposition
  • an Al electrode with a thickness of 85 nm was evaporated directly after annealing the electron transport layer.
  • Example 1 The difference from Example 1 is that in Example 1, a 10 nm Al 2 O 3 film and a 10 nm TiO 2 film were successively deposited on the electron transport layer by means of plasma enhanced atomic layer deposition (PEALD) to obtain a composite. "Film” was adjusted to "20 nm Al 2 O 3 thin film deposited by plasma enhanced atomic layer deposition (PEALD) on the electron transport layer".
  • PEALD plasma enhanced atomic layer deposition
  • the quantum dot light-emitting diode devices prepared in Examples 1-5 and Comparative Examples 1-2 were placed in a constant humidity and constant temperature environment with a relative humidity of 80% and a temperature of 40 °C, and the brightness-voltage-current was carried out every seven days. Test and life test, observe the external quantum efficiency and device life value each time. The results are shown in Table 1 below.
  • Comparative Example 1 did not set the composite film, so that the light-emitting diode device first entered forward aging in a constant humidity and constant temperature environment with a relative humidity of 80% and a temperature of 40 °C (the EQE increased rapidly and the lifespan increased), and then Rapidly enters the state of negative aging (rapid quenching, reduced lifespan); while the quantum dot light-emitting diodes provided in Examples 1-5 of the present application introduce Al2O3 thin film and nano-metal oxide between the electron transport layer and the cathode
  • the composite film formed by the metal oxide film improves the stability of the water-oxygen environment of the light-emitting diode in a constant humidity and constant temperature environment with a relative humidity of 80% and a temperature of 40 °C, but the nanometer metal oxide materials of Examples 2-4 are conductive.
  • the band is higher (titanium oxide is also a conduction band of 3.2eV), which affects the electrical properties of the quantum dot light-emitting
  • the quantum dot light-emitting diode provided in Example 1 of the present application has higher external quantum efficiency and device life after being stored in a constant humidity and constant temperature environment with a relative humidity of 80% and a temperature of 40°C for 22 days. stability. This may be attributed to that the quantum dot light-emitting diode provided in Example 1 of the present application contains nano metal oxide films in the composite film introduced between the electron transport layer and the cathode, and the nano metal oxide films improve the aluminum oxide The crystallinity of the thin film significantly improves the stability of the water-oxygen environment of the light-emitting diode. In Comparative Example 2, aluminum oxide is used alone as the transition layer film.
  • Example 5 Comparing Example 1 and Example 5 of the present application, in Example 5, the annealing temperature of the electron transport layer was lowered, and the positive aging rate was slowed down, so that the "passivation" effect of the zinc oxide layer was weakened. case, the electrical performance of the device is improved.

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Abstract

本申请公开了一种发光二极管及其制备方法。所述发光二极管包括相对设置的阳极和阴极，设置在所述阳极和所述阴极之间的发光层，设置在所述阴极和所述发光层之间的电子传输层，以及设置在所述阴极和所述电子传输层之间的复合薄膜，其中，所述复合薄膜包括邻近所述电子传输层设置的三氧化二铝薄膜，以及远离所述电子传输层设置的纳米金属氧化物薄膜或氮化硅薄膜。本申请提供的发光二极管，能够有效阻挡水氧的渗入，提高器件的水氧环境稳定性不足。

Description

发光二极管及其制备方法
本申请要求于2020年12月24日在中国专利局提交的、申请号为202011548093.3、发明名称为“发光二极管及其制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本申请涉及光电器件技术领域，尤其涉及一种发光二极管及其制备方法。
背景技术
量子点(quantum dot，QD)，是一类由少量原子构成的纳米材料，其半径通常小于或接近于激子波尔半径，表现出显著的量子限域效应，具有独特的光学性能，如发光光谱受材料自身尺寸和组份连续可调、半峰宽窄、荧光效率高、长寿命、优良的单分散性和光热稳定性强等。这些独特的性能使其广泛应用在显示、照明、生物标记和太阳能电池等领域。
量子点电致发光一种新型的固态照明技术，具备成本低、重量轻、响应速度快、色彩饱和度高等优点，拥有广阔的发展前景，已成为新一代发光二极管(light emitting diode，LED)照明的重要研究方向之一。现有量子点发光二极管(Quantum Dot Light Emitting Diode，QLED)主要包括阴极、阳极和量子点发光层。为了改善器件性能，在此基础上，QLED还会引入空穴传输层、电子传输层、电子注入层等功能层。QLED器件使用过程中，电学性能的水氧环境稳定性(尤其环境相对湿度(Relative humidity，RH)>75％)始终是无法解决的难题。
技术问题
本申请实施例的目的之一在于：提供一种发光二极管及其制备方法。
技术解决方案
本申请实施例采用的技术方案是：
第一方面，提供一种发光二极管，包括相对设置的阳极和阴极，设置在所述阳极和所述阴极之间的发光层，设置在所述阴极和所述发光层之间的电子传输层，以及设置在所述阴极和所述电子传输层之间的复合薄膜，其中，所述复合薄膜包括邻近所述电子传输层设置的三氧化二铝薄膜，以及远离所述电子传输层设置的纳米金属氧化物薄膜或氮化硅薄膜。
在一些实施例中，所述纳米金属氧化物薄膜的材料选自TiO 2、ZrO 2、SiO 2中的至少一种。
在一些实施例中，所述复合薄膜的厚度小于或等于25nm。
在一些实施例中，所述复合薄膜的厚度为15～25nm。
在一些实施例中，当所述复合薄膜包括所述纳米金属氧化物薄膜时，所述三氧化二铝薄膜和所述纳米金属氧化物薄膜的厚度比为3:1～1:3。
在一些实施例中，所述复合薄膜中，所述三氧化二铝薄膜和所述纳米金属氧化物薄膜的厚度比为1:3、1:2、1:1、2:1、3:1。
在一些实施例中，当所述复合薄膜包括所述三氧化二铝薄膜时，所述三氧化二铝薄膜和所述氮化硅薄膜的厚度比为3:1～1:3。
在一些实施例中，所述三氧化二铝薄膜和所述氮化硅薄膜的厚度比为1:3、1:2、1:1、2:1、3:1。
在一些实施例中，所述发光二极管还包括设置在所述阳极和所述发光层之间的空穴功能层。
在一些实施例中，所述空穴功能层包括空穴注入层、空穴传输层、空穴阻挡层中的至少一种。
在一些实施例中，所述发光二极管为正置结构发光二极管，所述阳极设置在衬底上。
在一些实施例中，所述发光层为量子点发光层或有机发光层。
第二方面，提供一种发光二极管的制备方法，包括以下步骤：
提供预制器件，所述预制器件包括阳极基板，设置在阳极基板的阳极表面的发光层；
在所述发光层背离所述阳极基板的一侧表面形成电子传输材料，退火处理，制备电子传输层；
在所述电子传输层背离所述发光层的一侧表面制备三氧化二铝薄膜，在所述三氧化二铝薄膜背离所述电子传输层的一侧表面制备纳米金属氧化物薄膜，得到复合薄膜或氮化硅薄膜；
在所述复合薄膜背离所述电子传输层的一侧表面制备阴极，得到所述发光二极管。
在一些实施例中，所述退火处理的温度为30℃～120℃。
在一些实施例中，所述退火处理的温度为30℃～50℃。
有益效果
本申请实施例提供的发光二极管的有益效果在于：在发光二极管的阴极与电子传输层之间引入复合薄膜作为过渡层，该过渡层选择三氧化二铝薄膜与纳米金属氧化物薄膜形成复合薄膜或选择三氧化二铝薄膜与氮化硅薄膜形成复合薄膜，以提高水氧环境稳定性。具体如下：
首先，三氧化二铝、纳米金属氧化物材料和氮化硅本身，在成膜后具有较好的气体阻隔性能，且热稳定性较好，在相对湿度及温度不友好的环境中，依然可以为电子传输层及电极之间起到良好的防老化作用，提高器件整体的稳定性。同时，这些材料的光学透射率较高，不会过多影响器件本身的出光而使得光学性能衰减。应当注意的是，单纯的三氧化二铝薄膜，由于成膜结晶不规则，导致化学稳定性差，因此在高湿度(RH>75％)的环境下，气体阻隔性能并不好。正是基于此，本申请采用复合薄膜，通过引入纳米金属氧化物薄膜，来避免三氧化二铝薄膜成膜结晶不规则，导致化学稳定性差的问题。通过三氧化二铝薄膜与纳米金属氧化物薄膜的协同作用，有效提高发光二极管的稳定性，特别是高湿度(RH>75％)的环境下的稳定性。
其次，本申请将导带为3.2eV的三氧化二铝薄膜设置在靠近电子传输层的位置，同时将纳米金属氧化物薄膜或氮化硅薄膜设置在靠近阴极的位置，可以使得电子传输层-三氧化 二铝薄膜-纳米金属氧化物薄膜或氮化硅薄膜-阴极之间的能级更为匹配，从而避免复合薄膜的引入对载流子的注入带来明显的影响，从而使得本申请通过引入复合薄膜可以在保持器件良好的电学性能的前提下，具有较好的稳定性，特别是具有较好的水氧环境稳定性。
再次，三氧化二铝、纳米金属氧化物材料和氮化硅在各类电子传输材料和阴极材料上具有较好的沉积附着性，成膜性能好，适合各类电子传输层基板或阴极基板，不会造成成膜较差而影响电学性能的问题。
本申请实施例提供的发光二极管的制备方法的有益效果在于：该方法只需要在常规的发光二极管的制备方法的基础上，在电子传输层和阴极之间制备三氧化二铝薄膜与纳米金属氧化物薄膜形成的复合薄膜或三氧化二铝薄膜与氮化硅薄膜形成的复合薄膜，并使得三氧化二铝薄膜邻近电子传输层设置即可。该方法操作简单，工艺成熟，具有较好的应用前景。
附图说明
为了更清楚地说明本申请实施例中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本申请的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动性的前提下，还可以根据这些附图获得其他的附图。
图1是本申请实施例提供的发光二极管的结构示意图；
图2是本申请实施例提供的发光二极管的制备工艺流程图；
图3是本申请实施例提供的正置型结构发光二极管的结构示意图；
图4是本申请实施例提供的正置型结构发光二极管的结构示意图。
本发明的实施方式
为了使本申请要解决的技术问题、技术方案及有益效果更加清楚明白，以下结合实施例，对本申请进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本申请，并不用于限定本申请。
本申请权利要求和具体实施方式中，术语“和/或”，描述关联对象的关联关系，表示可以存在三种关系。例如，A和/或B，可以表示：单独存在A，同时存在A和B，单独存在B的三种情况。其中A，B可以是单数或者复数。字符“/”一般表示前后关联对象是一种“或”的关系。
本申请中，“至少一个”是指一个或者多个，“多个”是指两个或两个以上。“以下至少一项(个)”或其类似表达，是指的这些项中的任意组合，包括单项(个)或复数项(个)的任意组合。例如，“a,b,或c中的至少一项(个)”，或，“a,b,和c中的至少一项(个)”，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。
应理解，在本申请的各种实施例中，上述各过程的序号的大小并不意味着执行顺序的先后，部分或全部步骤可以并行执行或先后执行，各过程的执行顺序应以其功能和内在逻辑确定，而不应对本申请实施例的实施过程构成任何限定。
在本申请实施例中使用的术语是仅仅出于描述特定实施例的目的，而非旨在限制本申请。在本申请实施例和所附权利要求书中所使用的单数形式的“一种”、“所述”和“该”也旨在包括多数形式，除非上下文清楚地表示其他含义。
术语“第一”、“第二”仅用于描述目的，用来将目的如物质、界面、消息、请求和终端彼此区分开，而不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量。例如，在不脱离本申请实施例范围的情况下，第一XX也可以被称为第二XX，类似地，第二XX也可以被称为第一XX。由此，限定有“第一”、“第二”的特征可以明示或者隐含地包括一个或者更多个该特征。
QLED器件使用过程中，电学性能的环境稳定性(尤其高湿度RH>75％)始终是无法解决的难题。具体的，环境中的水分子进入QLED器件后，对电子传输层及电极层之间的界面层产生一定的正向老化作用，虽然短时间内QLED器件的电学性能及寿命得到提升，但也会导致QLED器件快速地进入衰减期，器件老化导致漏电流提升及寿命大幅衰减。这种老化现象原因有可能是渗入QLED器件的水氧对阴极与电子传输层之间的界面层产生了一定的氧化效果，或水与电子传输层材料表面的缺陷位发生了附着或配位导致。当环境相对湿度(RH)大于75％的时候，这种现象更为显著。有鉴于此，本申请实施例提供了一种新的发光二极管及其制备方法。
第一方面，结合图1，本申请实施例提供一种发光二极管，包括相对设置的阳极1和阴极7，设置在阳极1和阴极7之间的发光层4，设置在阴极7和发光层4之间的电子传输层5，以及设置在阴极7和电子传输层5之间的复合薄膜6，其中，复合薄膜6包括邻近电子传输层设置的三氧化二铝薄膜61，以及远离电子传输层5设置的纳米金属氧化物薄膜621或氮化硅薄膜622。
本申请实施例提供的发光二极管，在发光二极管的阴极与电子传输层之间引入复合薄膜6作为过渡层，该过渡层选择三氧化二铝薄膜61与纳米金属氧化物薄膜621形成复合薄膜6或选择三氧化二铝薄膜61与氮化硅薄膜622形成复合薄膜6，以提高水氧环境稳定性。具体如下：
首先，三氧化二铝、纳米金属氧化物材料和氮化硅本身，在成膜后具有较好的气体阻隔性能，且热稳定性较好，在相对湿度及温度不友好的环境中，依然可以为电子传输层及电极之间起到良好的防老化作用，提高器件整体的稳定性。同时，这些材料的光学透射率较高，不会过多影响器件本身的出光而使得光学性能衰减。应当注意的是，单纯的三氧化二铝薄膜，由于成膜结晶不规则，导致化学稳定性差，因此在高湿度(RH>75％)的环境下，气体阻隔性能并不好。正是基于此，本申请实施例采用复合薄膜6，通过引入纳米金属氧化物薄膜62，来避免三氧化二铝薄膜61成膜结晶不规则，导致化学稳定性差的问题。通过三氧化二铝薄膜61与纳米金属氧化物薄膜621或氮化硅薄膜622的协同作用，有效提高发光二极管的稳定性，特别是高湿度(RH>75％)的环境下的稳定性。
其次，本申请实施例将导带为3.2eV的三氧化二铝薄膜61设置在靠近电子传输层5的位置，同时将纳米金属氧化物薄膜621或氮化硅薄膜622设置在靠近阴极7的位置，可以 使得电子传输层5-三氧化二铝薄膜61-纳米金属氧化物薄膜621或氮化硅薄膜622-阴极7之间的能级更为匹配，从而避免复合薄膜6的引入对载流子的注入带来明显的影响，从而使得本申请通过引入复合薄膜6可以在保持器件良好的电学性能的前提下，具有较好的稳定性，特别是具有较好的水氧环境稳定性。
再次，三氧化二铝和纳米金属氧化物材料在各类电子传输材料和阴极材料上具有较好的沉积附着性，成膜性能好，适合各类电子传输层基板或阴极基板，不会造成成膜较差而影响电学性能的问题。
本申请实施例中，复合薄膜6设置在阴极7和电子传输层5的界面处，用于改善外界的水氧对封装后的发光二极管产生的负面影响。具体的，本申请实施例通过三氧化二铝薄膜61和纳米金属氧化物薄膜621形成的复合薄膜6或三氧化二铝薄膜61和纳米金属氧化物薄膜622形成的复合薄膜6来改善封装后的发光二极管的环境稳定性，特别是提高封装后的发光二极管在高湿度(RH>75％)的环境下的稳定性。
其中，三氧化二铝本身不具有电子传输作用，但是具有较好的空气隔绝性能特别是水氧阻隔性能和良好的成膜附着性。作为过渡层材料，三氧化二铝导带与电子传输层以及电极相匹配，因此，通过薄膜方式引入，可以在提高发光二极管的环境稳定性的基础上，不明显影响载流子传输。单独将三氧化二铝薄膜61设置在阴极7和电子传输层5之间，会加速发光二极管的正向老化效率，在正向老化过程中，虽然能提高器件的发光效率，但由于正向老化速度过快，导致器件发光效率不稳定，并快速进入衰减阶段，最终不利于获得具有较好稳定性的发光二极管。
本申请实施例中，纳米金属氧化物薄膜621中的纳米金属氧化物和氮化硅薄膜622中的氮化硅(SiN 4)具有一定的水氧阻隔性能。在一种可能的实施方式中，纳米金属氧化物薄膜621的材料选自TiO 2、ZrO 2、SiO 2中的至少一种。在这种情况下，成膜后的纳米金属氧化物薄膜621本身不仅具有良好的气体阻隔性能和热稳定性，而且可以提高三氧化二铝薄膜61的成膜结晶性，进一步提高三氧化二铝薄膜61的空气隔绝性能特别是水氧隔绝性能，使发光二极管在相对湿度及温度不友好的环境中，依然可以为电子传输层5及阴极7之间起到良好的防老化作用，提高器件整体的稳定性。
在一些实施例中，复合薄膜6的厚度小于或等于25nm。若复合薄膜6的厚度过高，会影响载流子的传输效率，进而低电学性能。在一些实施例中，复合薄膜6的厚度为15～25nm。在这种情况下，复合薄膜6具有合适的厚度，不仅能够有效发挥空气隔绝作用，而且对载流子的传输效率不会造成显著影响。示例性的，复合薄膜6的厚度为15nm、16nm、17nm、18nm、19nm、20nm、21nm、22nm、23nm、24nm、25nm。
在一些实施例中，复合薄膜6中，三氧化二铝薄膜61和纳米金属氧化物薄膜621的厚度比为3:1～1:3。在一些实施例中，复合薄膜6中，三氧化二铝薄膜61和氮化硅薄膜622的厚度比为3:1～1:3。在这种情况下，三氧化二铝薄膜61的厚度占复合薄膜6总厚度的25％～75％，发挥空气隔绝作用特别是水氧阻隔作用，并通过剩余厚度的纳米金属氧化物薄膜621或氮化硅薄膜622，来提高三氧化二铝薄膜61的成膜结晶性，从而保证三氧化二铝 薄膜61的空气隔绝作用特别是水氧阻隔作用。此外，发光二极管引入的一定厚度的纳米金属氧化物薄膜621或氮化硅薄膜622，本身也具有空气隔绝作用，从而可以进一步提高发光二极管的空气隔绝作用特别是水氧阻隔作用。若三氧化二铝薄膜61的厚度过厚，三氧化二铝薄膜61的成膜结晶不规则，化学稳定性更差，则会影响三氧化二铝薄膜61的空气阻隔作用；若纳米金属氧化物薄膜621或氮化硅薄膜622的厚度过厚，则会影响复合薄膜6的电学传输性能，可能让发光二极管器件最终整体亮度降低。在一些实施例中，复合薄膜6中，三氧化二铝薄膜61和纳米金属氧化物薄膜62的厚度比为1:3、1:2、1:1、2:1、3:1，但不限于此。在一些实施例中，复合薄膜6中，三氧化二铝薄膜61和氮化硅薄膜622的厚度比为1:3、1:2、1:1、2:1、3:1，但不限于此。
在一些实施例中，复合薄膜6的厚度小于或等于25nm，且三氧化二铝薄膜61和纳米金属氧化物薄膜621的厚度比为3:1～1:3。在一些实施例中，复合薄膜6的厚度小于或等于25nm，且三氧化二铝薄膜61和氮化硅薄膜622的厚度比为3:1～1:3。示例性的，三氧化二铝薄膜61和纳米金属氧化物薄膜621的厚度比为1:3、1:2、1:1、2:1、3:1。示例性的，三氧化二铝薄膜61和氮化硅薄膜621的厚度比为1:3、1:2、1:1、2:1、3:1。在一些实施例中，复合薄膜6的厚度为20nm，三氧化二铝薄膜61和纳米金属氧化物薄膜621的厚度均为10nm。在一些实施例中，复合薄膜6的厚度为20nm，三氧化二铝薄膜61和氮化硅薄膜622的厚度均为10nm。
在一些实施例中，发光二极管还包括在阳极1和发光层3之间设置的空穴功能层。其中，空穴功能层包括空穴注入层、空穴传输层、空穴阻挡层中的至少一种。
本申请实施例中，发光二极管还可以包括衬底，阳极1或阴极7设置在衬底上。本申请实施例提供的发光二极管根据分为正置结构发光二极管和倒置结构发光二极管。
在一种实施方式中，正置结构发光二极管包括相对设置的阳极1和阴极7，设置在阳极1和阴极7之间的发光层4，设置在阴极7和发光层4之间的电子传输层5，以及设置在阴极7和电子传输层5之间的复合薄膜6，其中，复合薄膜6包括邻近电子传输层设置的三氧化二铝薄膜61和远离电子传输层5设置的纳米金属氧化物薄膜62，且阳极1设置在衬底上。进一步的，在阳极1和发光层4之间可以设置空穴传输层、空穴注入层和电子阻挡层等空穴功能层。当发光二极管为正置结构发光二极管时，可以通过引入复合薄膜6来提高发光二极管的水氧环境稳定性；同时，通过调控电子传输层5(此时，已经完成阳极1、发光层4等的制备)的退火处理温度，使电子传输材料的老化在低水氧的环境下进行，以提高发光二极管的稳定性。在一些实施例中，通过调控电子传输层5的退火温度为30℃～50℃，来调节电子传输材料的老化程度在合适水平，可以防止或延缓电子传输层5与阴极7界面发生过多氧化，降低电子传输层5与阴极7界面发生的氧化水平，提高发光二极管寿命，并在此基础上，保证了较高的外量子效率。
示例性的，如图3所示，在一些正置结构发光二极管的实施例中，发光二极管包括衬底10，设置在衬底10表面的阳极1，设置在阳极1表面的空穴注入层2，设置在空穴注入层2表面的空穴传输层3，设置在空穴传输层3表面的发光层4，设置在发光层4表面的电 子传输层5，设置在电子传输层5表面的复合薄膜6和设置在复合薄膜6表面的阴极7，其中，复合薄膜6包括邻近电子传输层设置的三氧化二铝薄膜61和远离电子传输层5设置的纳米金属氧化物薄膜621或氮化硅薄膜622。
在一种实施方式中，倒置结构发光二极管包括相对设置的阳极1和阴极7，设置在阳极1和阴极7之间的发光层4，设置在阴极7和发光层4之间的电子传输层5，以及设置在阴极7和电子传输层5之间的复合薄膜6，其中，复合薄膜6包括邻近电子传输层设置的三氧化二铝薄膜61和远离电子传输层5设置的纳米金属氧化物薄膜62或氮化硅薄膜622，且阴极7设置在衬底上。进一步的，在阳极1和发光层4之间可以设置空穴传输层、空穴注入层和电子阻挡层等空穴功能层。
示例性的，如图4所示，在一些倒置结构发光二极管的实施例中，发光二极管包括衬底10，设置在衬底10表面的阴极7，设置在阴极7表面设置的复合薄膜6，设置在复合薄膜6表面的电子传输层5，设置在电子传输层5表面的发光层4，设置在发光层4表面的空穴传输层3，设置在空穴传输层3表面的空穴注入层3，设置在空穴注入层2表面的阳极1。
在一些实施例中，发光层为量子点发光层或有机发光层。本申请实施例提供的发光二极管，根据发光材料的类型，可以分为有机发光二极管和量子点发光二极管。
上述实施例中，衬底10可包括刚性衬底如玻璃、硅晶片、金属箔片等刚性衬底，或柔性衬底如聚酰亚胺(PI)、聚碳酸酯(PC)、聚苯乙烯(PS)、聚乙烯(PE)、聚氯乙烯(PV)、聚乙烯吡咯烷酮(PVP)、聚甲基丙烯酸甲酯、聚对苯二甲酸乙二醇酯(PET)、聚萘二甲酸乙二醇酯、聚酰胺、聚醚砜中的一种或多种形成的组合。
阳极1可以采用常见的阳极材料和厚度，本申请实施例不作限定。在一些实施例中，阳极材料选自铟掺杂的氧化锡(ITO)。
空穴注入层2的材料可选自具有良好空穴注入性能的材料。在一些实施例中，空穴注入层2的材料选自聚(3,4-亚乙二氧基噻吩)-聚(苯乙烯磺酸)(PEDOT:PSS)及其掺有s-MoO 3的衍生物(PEDOT:PSS:s-MoO 3)中的一种。
空穴传输层3的材料可采用常规的空穴传输材料。在一些实施例中，空穴传输层3的材料选自聚[(9,9-二辛基芴基-2,7-二基)-co-(4,4'-(N-(对丁基苯基))二苯胺)](TFB)、聚(9-乙烯基咔唑)(PVK)、聚(N,N'双(4-丁基苯基)-N,N'-双(苯基)联苯胺)(Poly-TPD)、N,N’-二苯基-N,N’-(1-萘基)-1,1’-联苯-4,4’-二胺(NPB)中的一种。
当发光二极管为有机发光二极管时，发光层4的材料为有机发光材料。
当发光二极管为量子点发光二极管时，发光层4的材料为量子点。当发光二极管为量子点发光二极管时，通过引入复合薄膜6来提高发光二极管的水氧阻隔性能，从而提高器件的稳定性的作用更加显著。
量子点发光层的量子点为具备发光能力的直接带隙化合物半导体，可以按照常规的量子点类型，选择常规的量子点材料。如量子点发光层的量子点可以II-VI族化合物、III-V族化合物、II-IV-VI族化合物中的一种或多种，且量子点可以为单组分量子点，也可以为核壳结构量子点，还可以为合金结构量子点或有机-无机杂化钙钛矿量子点、全无机量子点材 料中的至少一种。示例性的，II-VI族化合物形成的量子点包括但不限于：CdSe、CdS、ZnSe、CdS、PbS、PbSe；III-V族化合物形成的量子点包括但不限于：InP、InAs；II-IV-VI族化合物形成的量子点包括但不限于：CuInS 2、AgInS 2。
电子传输层5的材料可采用常规的电子传输材料。在一些实施例中，电子传输层5的材料选自ZnO、掺铝氧化锌(AZO)、掺锂氧化锌(LZO)、掺镁氧化锌(MZO)中的一种。
复合薄膜6的组成及其材料选择如上文所述，为了节约篇幅，此处不再赘述。
本申请实施例中，阴极7可以采用常见的阴极材料和厚度，本申请实施例不作限定。在一些实施例中，阴极7的材料选自金属材料铝或银。以铝或银作为阴极材料，配合复合薄膜的设置，得到的发光二极管具有较好的稳定性，特别是水氧稳定性。
本申请实施例提供的正置结构的发光二极管，可以通过下述方法制备得到。
第二方面，本申请实施例提供一种发光二极管的制备方法，包括以下步骤：
S10.提供预制器件，预制器件包括阳极基板，设置在阳极基板的阳极表面的发光层。
本申请实施例中，预制器件为已经具有阳极基板，且制备好发光层之后的局部器件。在一些实施例中，预制器件还包括在阳极和发光层之间的空穴功能层。其中，空穴功能层包括空穴注入层、空穴传输层和电子阻挡层中的至少一层。
本申请实施例中，预制器件的制备没有严格限定，可以采用常规方法制备。在一些实施例中，预制器件的制备方法包括：在阳极基板上制备空穴注入层，在空穴注入层上制备空穴传输层，在空穴传输层上制备发光层，得到预制器件。
预制器件中，各层材料的选择如上文所述，为了节约篇幅，此处不再赘述。
S20.在发光层背离阳极基板的一侧表面形成电子传输材料，退火处理，制备电子传输层。
在一些实施例中，通过溶液加工法在发光层背离阳极基板的一侧表面形成电子传输材料，退火成膜，制备得到电子传输层。通过退火处理，可以提高电子传输层的致密性。在一些实施例中，退火处理的温度为30℃-120℃。在这种情况下，退火处理过程中，随着温度的提高，电子传输材料形成的薄膜会出现一定的钝化效果，使电子传输材料的水氧附着能力渐弱，从而使得到的发光二极管老化所需要的放置时间加长或向后推移。在一些实施例中，退火处理的温度为30℃-50℃。在这种情况下，退火处理的温度控制在较低的温度水平，电子传输材料的老化程度控制在合适水平，降低电子传输层与阴极界面发生的氧化水平，正向老化使得发光二极管达到更优的性能，提高发光二极管寿命，并在此基础上，通过低温退火，赋予发光二极管较高的外量子效率。在这个基础上，通过引入复合薄膜和对发光二极管进行封装处理，使发光二极管同时具有较好的外量子效率和极强的稳定性。
S30.在电子传输层背离发光层的一侧表面制备三氧化二铝薄膜，在三氧化二铝薄膜背离电子传输层的一侧表面制备纳米金属氧化物薄膜或氮化硅薄膜，得到复合薄膜。
在一些实施例中，三氧化二铝薄膜、纳米金属氧化物薄膜、氮化硅薄膜通过等离子增强原子层沉积法(PEALD)制备获得。在这种情况下，可以通过稳定、低温的PEALD，在 不破坏器件结构的基础上制备得到复合薄膜。特别是当电子传输层采用低温退火处理制备得到时，可以避免高温对电子传输层的影响，保留低温退火时电子传输材料的老化程度。
S40.在复合薄膜背离电子传输层的一侧表面制备阴极，得到发光二极管。
在一些实施例中，通过蒸镀处理，在复合薄膜背离电子传输层的一侧表面制备阴极。
进一步的，还可以对得到的发光二极管进行封装处理。
本申请实施例提供的发光二极管的制备方法，只需要在常规的发光二极管的制备方法的基础上，在电子传输层和阴极之间制备三氧化二铝薄膜与纳米金属氧化物薄膜形成的复合薄膜或三氧化二铝薄膜与氮化硅薄膜形成的复合薄膜，并使得三氧化二铝薄膜邻近电子传输层设置即可。该方法操作简单，工艺成熟，具有较好的应用前景。
下面结合具体实施例进行说明。
实施例1
一种正置结构的量子点发光二极管，通过下述方法制备获得：
在ITO衬底上旋涂PEDOT:PSS:s-MoO 3，并在空气中进行退火，制备厚度为30nm的空穴注入层；
于氮气气氛中，在空穴注入层上旋涂PVK，并在140℃退火，制备厚度为20nm的空穴传输层；
在空穴传输层上旋涂CdSe@ZnS量子点，制备厚度为40nm的量子点发光层；
在量子点发光层上旋涂MZO，并在温度为90℃的条件下退火30分钟，制备厚度为50nm的电子传输层；
在电子传输层上以等离子增强原子层沉积(PEALD)的方式先后沉积10nm的Al 2O 3薄膜和10nm的TiO 2薄膜，得到复合薄膜；
在复合薄膜上蒸镀厚度为85nm的Al电极；
封装后得到正置结构量子点发光二极管器件。
实施例2
与实施例1的不同之处在于：10nm的TiO 2薄膜替换为10nm的ZrO 2薄膜。
实施例3
与实施例1的不同之处在于：10nm的TiO 2薄膜替换为10nm的SiO 2薄膜。
实施例4
与实施例1的不同之处在于：10nm的TiO 2薄膜替换为10nm的SiN 4。
实施例5
与实施例1的不同之处在于：“在量子点发光层上旋涂MZO，并在温度为90℃的条件下退火30分钟”的步骤中，退火温度由90℃调整为40℃。
对比例1
与实施例1的不同之处在于：省略“在电子传输层上以等离子增强原子层沉积(PEALD)的方式先后沉积10nm的Al 2O 3薄膜和10nm的TiO 2薄膜，得到复合薄膜”的步骤，直接在电子传输层退火后，蒸镀厚度为85nm的Al电极。
对比例2
与实施例1的不同之处在于：将实施例1中“在电子传输层上以等离子增强原子层沉积(PEALD)的方式先后沉积10nm的Al 2O 3薄膜和10nm的TiO 2薄膜，得到复合薄膜”调整为“在电子传输层上以等离子增强原子层沉积(PEALD)的方式沉积20nm的Al 2O 3薄膜”。
将实施例1-5、对比例1-2制备得到的量子点发光二极管器件置于相对湿度为80％、温度为40℃的恒湿恒温环境中保存，每隔七天进行一次亮度-电压-电流测试以及寿命测试，观察每次的外量子效率以及器件寿命数值。结果如下表1所示。
表1
Figure PCTCN2021140130-appb-000001
由上表1可见，相较于对比例1，本申请实施例1-5提供的量子点发光二极管的在相对湿度为80％、温度为40℃的恒湿恒温环境中保存22天后的外量子效率和器件寿命的稳定性明显提高(从第1天到第22天，外量子效率上涨未超过2％)。这可能归因于，对比例1没有设置复合薄膜，使得发光二极管器件在相对湿度为80％、温度为40℃的恒湿恒温环境中先进入正向老化(EQE快速提升且寿命增加)，再迅速进入负向老化(快速淬灭，寿命降低)的状态；而本申请实施例1-5提供的量子点发光二极管，在电子传输层和阴极之间引入了三氧化二铝薄膜和纳米金属氧化物薄膜形成的复合薄膜，提高了发光二极管在相对湿度为80％、温度为40℃的恒湿恒温环境中的水氧环境的稳定性，但实施例2-4的纳米金属氧化物材料的导带较高(氧化钛也是3.2eV的导带)，一定程度影响量子点发光二极管的电学性能。
相较于对比例2，本申请实施例1提供的量子点发光二极管的在相对湿度为80％、温度为40℃的恒湿恒温环境中保存22天后的外量子效率和器件寿命具有较高的稳定性。这可能归因于，本申请实施例1提供的量子点发光二极管，在电子传输层和阴极之间引入了的复合薄膜中含有纳米金属氧化物薄膜，纳米金属氧化物薄膜改善了三氧化二铝薄膜的结晶性，从而显著提高了发光二极管的水氧环境的稳定性。对比例2为单独使用氧化铝作为过渡层薄膜，虽然外量子效率和器件寿命相对较高，但波动明显，正是因为正向老化速度 过快导致(这是我们不希望的)。剧烈的正老化效率使器件迎来发光效率的快速提升后，器件将快速进入衰减期，器件外量子效率和寿命都衰退得非常快，器件的稳定性变差。
对比本申请实施例1和实施例5，实施例5将电子传输层的退火温度降低，正老化速度减缓，使得氧化锌层的“钝化”效果减弱，实施例5最终在保证了稳定性的情况下，提高了器件的电学性能。
以上仅为本申请的较佳实施例而已，并不用以限制本申请，凡在本申请的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本申请的保护范围之内。

Claims (15)

  1. 一种发光二极管，其特征在于，包括相对设置的阳极和阴极，设置在所述阳极和所述阴极之间的发光层，设置在所述阴极和所述发光层之间的电子传输层，以及设置在所述阴极和所述电子传输层之间的复合薄膜，其中，所述复合薄膜包括邻近所述电子传输层设置的三氧化二铝薄膜，以及远离所述电子传输层设置的纳米金属氧化物薄膜或氮化硅薄膜。
  2. 如权利要求1所述的发光二极管，其特征在于，所述纳米金属氧化物薄膜的材料选自TiO 2、ZrO 2、SiO 2中的至少一种。
  3. 如权利要求1所述的发光二极管，其特征在于，所述复合薄膜的厚度小于或等于25nm。
  4. 如权利要求3所述的发光二极管，其特征在于，所述复合薄膜的厚度为15～25nm。
  5. 如权利要求3或4所述的发光二极管，其特征在于，当所述复合薄膜包括所述纳米金属氧化物薄膜时，所述三氧化二铝薄膜和所述纳米金属氧化物薄膜的厚度比为3:1～1:3。
  6. 如权利要求5所述的发光二极管，其特征在于，所述复合薄膜中，所述三氧化二铝薄膜和所述纳米金属氧化物薄膜的厚度比为1:3、1:2、1:1、2:1、3:1。
  7. 如权利要求3或4所述的发光二极管，其特征在于，当所述复合薄膜包括所述三氧化二铝薄膜时，所述三氧化二铝薄膜和所述氮化硅薄膜的厚度比为3:1～1:3。
  8. 如权利要求7所述的发光二极管，其特征在于，所述三氧化二铝薄膜和所述氮化硅薄膜的厚度比为1:3、1:2、1:1、2:1、3:1。
  9. 如权利要求1至8任一项所述的发光二极管，其特征在于，所述发光二极管还包括设置在所述阳极和所述发光层之间的空穴功能层。
  10. 如权利要求9所述的发光二极管，其特征在于，所述空穴功能层包括空穴注入层、空穴传输层、空穴阻挡层中的至少一种。
  11. 如权利要求1至8任一项所所述的发光二极管，其特征在于，所述发光二极管为正置结构发光二极管，所述阳极设置在衬底上。
  12. 如权利要求1至8任一项所述的发光二极管，其特征在于，所述发光层为量子点发光层或有机发光层。
  13. 一种发光二极管的制备方法，其特征在于，包括以下步骤：
    提供预制器件，所述预制器件包括阳极基板，设置在阳极基板的阳极表面的发光层；
    在所述发光层背离所述阳极基板的一侧表面形成电子传输材料，退火处理，制备电子传输层；
    在所述电子传输层背离所述发光层的一侧表面制备三氧化二铝薄膜，在所述三氧化二铝薄膜背离所述电子传输层的一侧表面制备纳米金属氧化物薄膜或氮化硅薄膜，得到复合薄膜；
    在所述复合薄膜背离所述电子传输层的一侧表面制备阴极，得到所述发光二极管。
  14. 如权利要求13所述的发光二极管的制备方法，其特征在于，所述退火处理的温度为30℃～120℃。
  15. 如权利要求14所述的发光二极管的制备方法，其特征在于，所述退火处理的温度为30℃～50℃。
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