WO2020134253A1 - 叠层结构及其制备方法、发光二极管及其制备方法 - Google Patents

叠层结构及其制备方法、发光二极管及其制备方法 Download PDF

Info

Publication number
WO2020134253A1
WO2020134253A1 PCT/CN2019/108156 CN2019108156W WO2020134253A1 WO 2020134253 A1 WO2020134253 A1 WO 2020134253A1 CN 2019108156 W CN2019108156 W CN 2019108156W WO 2020134253 A1 WO2020134253 A1 WO 2020134253A1
Authority
WO
WIPO (PCT)
Prior art keywords
metal oxide
layer
metal
oxide layer
emitting diode
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2019/108156
Other languages
English (en)
French (fr)
Inventor
张涛
向超宇
朱佩
罗植天
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
TCL Technology Group Co Ltd
Original Assignee
TCL Technology Group Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by TCL Technology Group Co Ltd filed Critical TCL Technology Group Co Ltd
Priority to US17/419,580 priority Critical patent/US12069887B2/en
Publication of WO2020134253A1 publication Critical patent/WO2020134253A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • H10K50/80—Constructional details
    • H10K50/84—Passivation; Containers; Encapsulations
    • H10K50/844—Encapsulations
    • H10K50/8445—Encapsulations multilayered coatings having a repetitive structure, e.g. having multiple organic-inorganic bilayers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • 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
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/301—Details of OLEDs
    • H10K2102/351—Thickness

Definitions

  • the present application belongs to the technical field of display, and particularly relates to a laminated structure and a preparation method thereof, a light emitting diode and a preparation method thereof.
  • Quantum dots have many advantages such as easy adjustment of luminous color, high color saturation, solution processing, and high stability. They are powerful competitors for next-generation display technology.
  • the quantum dot light-emitting diode (QLED) is prepared on a flexible substrate to achieve flexible display is currently an important direction of display development.
  • the realization of flexible QLED still faces many challenges, especially in the thin film packaging technology (TFE), because QLED is sensitive to water vapor in the air, the infiltrated water vapor is very likely to react with the active metal cathode or some transmission materials , Causing a decrease in device performance.
  • TFE thin film packaging technology
  • a polymer is usually used as a substrate. Such a substrate itself has poor barrier to external water vapor, which easily leads to the penetration of water vapor. Therefore, finding good TFE technology is of great significance for improving device stability and expanding the application prospects of flexible QLED.
  • the most commonly used TFE method is to form a barrier layer of encapsulation through a combination of organic and inorganic films, also known as Barix encapsulation technology.
  • the inorganic film is used as a real barrier layer, and the organic film is mainly used to improve the flatness and reduce the mechanical damage.
  • this technology can ensure a low water vapor permeability, it needs to ensure a large thickness of the organic film to fill the pinhole defects of the inorganic film, so the cost is high.
  • the ALD method developed in recent years to form a thin film package, although it can achieve a lower water vapor transmission rate in a thinner thickness, but due to the slow growth cycle, it is difficult to apply to large-scale production.
  • Embodiments of the present application provide a stacked structure and a method for manufacturing the same, a light emitting diode including the stacked structure and a method for manufacturing the same, to solve the existing combination of organic-inorganic thin film technology to form a packaged barrier layer, in order to To ensure the water vapor barrier effect, either the thickness of the organic film causes high cost, or the film is prepared by atomic layer deposition, which has the problem that the growth cycle is slow and it is difficult to apply to large-scale production.
  • a stacked structure which includes at least one stacked unit, and the stacked unit includes a first metal oxide layer and a second metal oxide layer disposed oppositely , And a third metal layer disposed between the first metal oxide layer and the second metal oxide layer, and between the first metal oxide layer and the third metal layer, and A third metal oxide thin film is formed between the second metal oxide layer and the third metal layer.
  • the laminated structure includes at least one laminated unit, and the laminated unit includes a first metal oxide layer and a second metal oxide layer disposed oppositely, And a third metal layer provided between the first metal oxide layer and the second metal oxide layer, and between the first metal oxide layer and the third metal layer, and the A third metal oxide film is formed between the second metal oxide layer and the third metal layer, and the preparation of the stacked structure includes the following steps:
  • the prefabricated lamination unit is subjected to heat treatment to prepare a lamination unit.
  • a light emitting diode including an anode and a cathode disposed oppositely, a light emitting layer disposed between the anode and the cathode, and a package disposed on a surface of the anode and/or the cathode Structure, the packaging structure is the laminated structure described in this application.
  • a method for manufacturing a light-emitting diode including the following steps:
  • a packaging structure is prepared on the surface of the anode or the cathode according to the method described in this application.
  • the stacked structure provided by the present application includes at least one stacked unit, and the stacked unit includes a first metal oxide layer and a second metal oxide layer disposed oppositely, and the first metal oxide layer and A third metal layer between the second metal oxide layers, and between the first metal oxide layer and the third metal layer, and between the second metal oxide layer and the third metal A third metal oxide film is formed between the layers. That is, the stacking unit is a stacking unit of M1O (first metal oxide layer)/Al2O3/Al/Al2O3/M2O (second metal oxide layer).
  • the third metal oxide film as a main barrier layer provides good water and oxygen barrier capacity, which can effectively block water and oxygen as a packaging structure; meanwhile, the thin film metal third metal layer has good extension
  • the property and uniformity can effectively fill in some defects of the third metal oxide film (intermediate layer), and further ensure the water-oxygen barrier property of the packaging structure.
  • the nano metal oxide in the metal oxide layer can absorb water, and a small amount of infiltrated water vapor is limited in the nano metal oxide to achieve a multi-layer water vapor isolation effect.
  • the stacked structure is used as a package for a heating device
  • the structure can effectively conduct the heat generated by the radiation inside the device to the external environment, and effectively improve the stability of the device.
  • the material of the stacked structure provided by the present application is compatible with conventional light-emitting device preparation materials, and has the advantage of low cost.
  • the preparation method of the stacked structure provided by the present application can be prepared by simply stacking the first metal oxide layer, the third metal layer, and the second metal oxide layer in sequence, followed by heat treatment. This method is compatible with the process of the conventional light-emitting device, has simple operation, and has the advantages of low cost, and is suitable for industrial production in a large area.
  • the light-emitting diode provided by the present application is provided with the above-mentioned packaging structure on the surface of the anode or the cathode.
  • the packaging structure can effectively block water and oxygen from entering the functional unit of the light-emitting diode, and at the same time other its thermal conductivity effect, thereby further improving the device of the light-emitting diode stability.
  • the preparation method of the light emitting diode provided by the present application only needs to further prepare the packaging structure on the basis of the conventional preparation method, the method is simple and controllable, and is suitable for industrial production in a large area.
  • FIG. 1 is a schematic diagram of a laminated structure including a prefabricated laminated unit provided by an embodiment of the present application;
  • FIG. 2 is a schematic diagram of a stacked structure including stacked units provided by an embodiment of the present application
  • FIG. 3 is a schematic flowchart of a method for manufacturing a laminated structure provided by an embodiment of the present application.
  • first and second are used for descriptive purposes only, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of indicated technical features.
  • the features defined as “first” and “second” may explicitly or implicitly include one or more of the features.
  • the meaning of “plurality” is two or more, unless otherwise specifically limited.
  • An embodiment of the present application provides a stacked structure, including at least one stacked unit, the stacked unit including a first metal oxide layer and a second metal oxide layer disposed oppositely, and the first metal A third metal layer between the oxide layer and the second metal oxide layer, and between the first metal oxide layer and the third metal layer, and the second metal oxide layer and the A third metal oxide film is formed between the third metal layers.
  • the third metal layer and the third metal in the third metal oxide film are metals that can react with oxygen to form a third metal oxide, such as Al, Mg, Ag, or the like.
  • a third metal oxide such as Al, Mg, Ag, or the like.
  • the third metal oxide film may be formed by the reaction of the first metal oxide layer and the third metal layer, or the second metal oxide layer and the third metal layer may also be formed by the reaction It is deposited directly between the first metal oxide layer and the third metal layer, or between the second metal oxide layer and the third metal layer.
  • the stacked structure provided in the embodiments of the present application includes at least one stacked unit, and the stacked unit includes a first metal oxide layer and a second metal oxide layer disposed oppositely, and the first metal oxide A third metal layer between the layer and the second metal oxide layer, and between the first metal oxide layer and the third metal layer, and between the second metal oxide layer and the first A third metal oxide film is formed between the three metal layers.
  • the stacking unit is M 1 O (first metal oxide layer)/Al 2 O 3 /Al/Al 2 O 3 /M 2 O (second metal oxide layer)
  • the third metal oxide film Al 2 O 3 may be formed by the reaction of the first metal oxide layer and the third metal layer Al, or the second metal oxide layer and the third metal layer Al It can be formed by reaction, or it can be deposited directly between the first metal oxide layer and the third metal layer, or between the second metal oxide layer and the third metal layer, that is, by chemical Deposited by deposition or physical deposition methods.
  • the third metal oxide film as a main barrier layer provides good water and oxygen barrier capacity, which can effectively block water and oxygen as a packaging structure; meanwhile, the thin film metal third metal layer has good extension
  • the property and uniformity can effectively fill in some defects of the third metal oxide film (intermediate layer), and further ensure the water-oxygen barrier property of the packaging structure.
  • the nano metal oxide in the metal oxide layer can absorb water, and a small amount of infiltrated water vapor is limited in the nano metal oxide to achieve a multi-layer water vapor isolation effect.
  • the stacked structure is used as a package for a heating device
  • the structure can effectively conduct the heat generated by the radiation inside the device to the external environment, and effectively improve the stability of the device.
  • the materials of the stacked structure provided by the embodiments of the present application are compatible with conventional materials for preparing light-emitting devices, and have the advantage of low cost.
  • the metal oxide layer serves as one of the functional layers, respectively as the two end faces of the laminated structure, on the one hand, it is used to provide oxygen vacancies, and reacts with the third metal layer of the intermediate metal layer to generate water-insulated oxygen
  • the third metal oxide film on the other hand, the metal oxide layer can absorb water, so that a small amount of infiltrated water vapor is limited to the metal oxide layer, further improving the effect of blocking water vapor.
  • the first metal oxide layer is selected from nano metal oxide and/or doped nano metal oxide; the material of the second metal oxide layer is selected from nano metal oxide and/or Doped nano metal oxide.
  • the material of the first metal oxide layer is at least one selected from the group consisting of nano zinc oxide, nano nickel oxide, doped nano nickel oxide, nano molybdenum oxide, and doped nano molybdenum oxide.
  • the material of the second metal oxide layer is selected from nano zinc oxide, doped nano zinc oxide, nano nickel oxide, doped nano nickel oxide, nano molybdenum oxide, doped nano molybdenum oxide At least one of them.
  • the preferred metal oxide material has good thermal conductivity and not only easily generates oxygen diffusion at the interface, but also facilitates the reaction with the third metal layer of the intermediate metal layer to form a third metal oxide film that is isolated from water and oxygen; moreover, the preferred metal oxide
  • the material itself can absorb water, further improving the effect of blocking water vapor.
  • the metal oxide material is easy to print and has good film-forming properties.
  • the metal oxide in the first metal oxide layer is the same as the metal oxide in the second metal oxide layer, so as to obtain a more stable stacked structure.
  • the doped nano metal oxide is selected from metal materials.
  • the metal material is selected from metals that are easily reacted with oxygen, and the metal oxide formed by the reaction has good water-oxygen barrier capability.
  • the doping material is selected from at least one of magnesium, aluminum, manganese, and silver. The magnesium, aluminum, manganese, and silver are easily reacted with oxygen, and the metal oxide formed by the reaction has good water-oxygen barrier capability.
  • the size of the metal oxide nanoparticles in the metal oxide layer is less than 5 nm, so as to ensure the density of the film layer.
  • the thickness of the first metal oxide layer is 10-30 nm.
  • the thickness of the second metal oxide layer is 10-20 nm. If the film layer of the metal oxide layer is too thin, the formed film layer is not dense enough, and there will be more pinhole defects; if the film layer of the metal oxide layer is too thick, it will waste material, and when the laminated structure is used as the encapsulation layer, Will reduce the light transmittance of the encapsulation layer.
  • the third metal layer can react with the oxygen vacancies of the metal oxide to form a third metal oxide film that is isolated from water and oxygen.
  • the third metal layer has good thermal conductivity and good ductility. When used as a package structure, it can not only effectively fill in some defects of the third metal oxide film (intermediate layer), and further ensure the package structure Water and oxygen barrier; and it is conducive to conduct the heat generated by radiation inside the device to the external environment, and effectively improve the stability of the device.
  • the third metal layer and the third metal in the third metal oxide film are selected from at least one of aluminum, magnesium, and silver.
  • the third metal oxide film as a main barrier layer provides good water and oxygen barrier capacity, which can effectively block water and oxygen as a packaging structure; at the same time, the third metal layer has good ductility With uniformity, it can effectively fill in some defects of the third metal oxide film (intermediate layer), and further guarantee the water-oxygen barrier property of the packaging structure.
  • the nano metal oxide in the metal oxide layer can absorb water, and a small amount of infiltrated water vapor is limited in the nano metal oxide to achieve a multi-layer water vapor isolation effect.
  • the thickness of the third metal layer is 10-20 nm. If the thickness of the third metal layer is too thin, the quality of the formed film layer is not good, and holes are likely to form water vapor permeation channels, which cannot play the role of filling defects of the metal oxide layer; if the thickness of the third metal layer If the thickness is too thick, the laminated structure will reduce the light transmittance of the encapsulation layer.
  • the third metal oxide film is actually a water-oxygen barrier functional layer formed by the reaction of the adjacent third metal layer and the metal oxide layer.
  • the thickness of the third metal oxide film is 2-5 nm. At this time, a better water-oxygen isolation effect can be achieved.
  • the laminated structure according to the embodiment of the present application includes at least one laminated unit, and the number of the laminated units is determined according to the thickness of the laminated unit and the moisture vapor transmission rate to be achieved by the packaged device. The better the tightness required by the device, the more the corresponding number of stacked units.
  • the laminate structure in the laminate unit, includes 1-10 repeatedly arranged laminate units. As a specific example, when the water vapor transmission rate to be achieved by the packaged device is 1 ⁇ 10 ⁇ 6 g/m 2 /day, at least three or more repeating lamination units are required.
  • the stacked structure includes two or more stacked units, and the materials of the first metal oxide layer and the second metal oxide layer are the same, adjacent The metal oxide layer can cooperate with one layer.
  • the thin layer structure described in the examples of this application can be prepared by the following method.
  • an embodiment of the present application provides a method for preparing a laminated structure.
  • the laminated structure includes at least one laminated unit 10 and the laminated layer
  • the cell includes a first metal oxide layer 11 and a second metal oxide layer 13 disposed oppositely, and a third metal layer disposed between the first metal oxide layer 11 and the second metal oxide layer 13 12, and a third metal oxide is formed between the first metal oxide layer 11 and the third metal layer 12, and between the second metal oxide layer 13 and the third metal layer 12
  • the film 121 shown in FIG. 3, is a schematic flow chart of a method for manufacturing a laminated structure according to an embodiment of the present application.
  • the preparation of the laminated structure includes the following steps:
  • the prefabricated lamination unit 10' is heat-treated to prepare the lamination unit 10.
  • the method for preparing the laminated structure provided by the embodiment of the present application can be prepared by simply laminating the first metal oxide layer, the third metal layer, and the second metal oxide layer in sequence, followed by heat treatment.
  • This method is compatible with the process of the conventional light-emitting device, has simple operation, and has the advantages of low cost, and is suitable for industrial production in a large area.
  • the substrate is a component that needs to prepare a packaging structure, such as a light emitting diode.
  • the first metal oxide layer 11 is prepared on the substrate, in some embodiments, it is realized by inkjet printing technology; the third metal layer 12 is prepared on the first metal oxide layer 11, in some embodiments It is realized by vacuum evaporation technology; the second metal oxide layer 13 is prepared on the third metal layer 12, which is realized by inkjet printing technology in some embodiments.
  • the prefabricated stacking unit 10' is heat-treated to oxidize the metal oxide of the first metal oxide layer 11 and the aluminum in the third metal layer 12 and the metal of the second metal oxide layer 13 And the aluminum in the third metal layer 12 reacts to form a third metal oxide film 121 between the metal oxide and the third metal layer to obtain a stacked structure including the stacked unit 10 as shown in FIG. 2.
  • the prefabricated lamination unit is heat-treated at a temperature of 100°C to 140°C, and the heat treatment time is 0.5h to 2h. Under this condition, not only the metal oxide of the first metal oxide layer 11 and the aluminum in the third metal layer 12 but also the metal oxide of the second metal oxide layer 13 and the aluminum in the third metal layer 12 can be effectively promoted Reaction, and will not affect the quality of each functional layer due to excessive temperature.
  • the method provided in the embodiments of the present application further includes: repeating the steps of preparing the third metal layer and the metal oxide layer on the surface of at least one metal oxide layer of the prefabricated stacking unit, and then obtaining the obtained stack
  • the structure is subjected to heat treatment to prepare a laminated structure having a plurality of laminated units.
  • the method for repeatedly preparing the third metal layer and the metal oxide layer is 20-40 nm, so as to ensure that sufficient metal oxide can react with the upper and lower third metal layers to form a third metal oxide film with an appropriate thickness.
  • An embodiment of the present application further provides a light emitting diode, including an anode and a cathode disposed oppositely, a light emitting layer disposed between the anode and the cathode, and a surface disposed on the surface of the anode and/or the cathode A packaging structure.
  • the packaging structure is the stacked structure described in the embodiments of the present application.
  • the light-emitting diode provided by the embodiment of the present application is provided with the above-mentioned packaging structure according to the embodiment of the present application on the surface of the anode or the cathode. Light-emitting diode device stability.
  • the light emitting diode is a quantum dot light emitting diode or an organic light emitting diode.
  • the light emitting diode further includes a substrate.
  • the substrate may be disposed at the anode end to form an upright light emitting diode; the substrate may be disposed at the cathode end to form an inverted light emitting diode.
  • the light emitting diode further includes at least one of a hole transport layer and a hole injection layer disposed between the anode and the light emitting layer. In some embodiments, the light emitting diode includes a hole transport layer disposed between the anode and the light emitting layer. In some embodiments, the light emitting diode includes a hole injection layer disposed between the anode and the light emitting layer. In some embodiments, the light emitting diode includes a hole transport layer disposed between the anode and the light emitting layer, and a hole injection layer disposed between the hole transport layer and the light emitting layer.
  • the light emitting diode further includes at least one of an electron transport layer and an electron injection layer disposed between the cathode and the light emitting layer.
  • the quantum dot light emitting diode includes an electron transport layer disposed between the cathode and the quantum dot light emitting layer.
  • the quantum dot light emitting diode includes an electron injection layer disposed between the cathode and the quantum dot light emitting layer.
  • the quantum dot light emitting diode includes an electron transport layer disposed between the cathode and the quantum dot light emitting layer, and an electron injection layer disposed between the electron transport layer and the light emitting layer.
  • the arrangement of the stacked structure in the light emitting diode includes several ways.
  • a package structure is provided on the surface of the cathode end, and the package structure is the laminated structure described in the embodiments of the present application;
  • a packaging structure is provided on the surface of the substrate facing away from the anode, and the packaging structure is the stacked structure described in the embodiments of the present application; in some embodiments, the packaging structure is provided on the surface of one end of the cathode, and at the same time, the substrate A packaging structure is provided on the surface facing away from the anode, and the packaging structure is the stacked structure described in the embodiments of the present application.
  • a packaging structure is provided on the surface of the anode end, the packaging structure is the stacked structure described in the embodiments of the present application; in some implementations
  • a packaging structure is provided on the surface of the substrate facing away from the cathode, and the packaging structure is a stacked structure as described in the embodiments of the present application; in some embodiments, a packaging structure is provided on the surface of one end of the anode, and at the same time, the substrate faces away
  • a package structure is provided on the surface of the cathode, and the package structure is the stacked structure described in the embodiments of the present application.
  • the light-emitting diodes described in the examples of this application can be prepared by the following method.
  • the embodiments of the present application provide a method for manufacturing a light emitting diode, including the following steps:
  • the packaging structure is prepared on the surface of the anode or the cathode according to the method described in the embodiment of the present application.
  • the preparation method of the light emitting diode provided by the embodiment of the present application only needs to further prepare the packaging structure on the basis of the conventional preparation method, the method is simple and controllable, and is suitable for industrial production in a large area.
  • the preparation method further includes preparing at least one of a hole transport layer and a hole injection layer between the anode and the light emitting layer. In some embodiments, the preparation method includes preparing a hole transport layer between the anode and the light emitting layer, and preparing a hole injection layer between the hole transport layer and the light emitting layer.
  • the preparation method further includes providing at least one of an electron transport layer and an electron injection layer between the cathode and the light emitting layer. In some embodiments, the preparation method includes preparing an electron transport layer between the cathode and the light emitting layer, and preparing an electron injection layer between the electron transport layer and the light emitting layer.
  • the preparation of the packaging structure on the surface of the anode or the cathode can be obtained by using the preparation method of the laminated structure described in the embodiments of the present application.
  • a preparation method of a light emitting diode includes the following steps:
  • a top-emitting light-emitting diode is provided, the top-emitting light-emitting diode includes at least a bottom electrode and a top electrode oppositely disposed, and a light-emitting layer disposed between the bottom electrode and the top electrode, and an encapsulation layer is prepared on the top electrode :
  • a first zinc oxide layer is prepared on the top electrode, the size of the zinc oxide nanoparticles is ⁇ 5 nm, and the thickness of the film layer is 10-30 nm;
  • a 10-20nm aluminum layer is evaporated on the first zinc oxide layer
  • the obtained laminated structure is heated at a temperature of 100 to 140°C for 0.5 to 2 hours to form an aluminum oxide barrier layer between the zinc oxide layer and the aluminum layer to form ZnO/Al 2 O 3 /Al/Al 2 O 3 /ZnO stack structure.
  • a preparation method of a light emitting diode includes the following steps:
  • a top-emitting light-emitting diode is provided, the top-emitting light-emitting diode includes at least a bottom electrode and a top electrode oppositely disposed, and a light-emitting layer disposed between the bottom electrode and the top electrode, and an encapsulation layer is prepared on the top electrode :
  • a first zinc oxide layer is prepared on the top electrode, the size of the zinc oxide nanoparticles is ⁇ 5 nm, and the thickness of the film layer is 10-30 nm;
  • a 10-20 nm first aluminum layer is evaporated on the first zinc oxide layer
  • a 10-20 nm second aluminum layer is evaporated on the second zinc oxide layer
  • the obtained laminated structure is heated at a temperature of 100 to 140°C for 0.5 to 2 hours to form an aluminum oxide barrier layer between the zinc oxide layer and the aluminum layer to form ZnO/Al 2 O 3 /Al/Al 2 O 3 /ZnO/Al 2 O 3 /Al/Al 2 O 3 /ZnO laminated structure.
  • a preparation method of a light emitting diode includes the following steps:
  • a top-emitting light-emitting diode is provided, the top-emitting light-emitting diode includes at least a bottom electrode and a top electrode oppositely disposed, and a light-emitting layer disposed between the bottom electrode and the top electrode, and an encapsulation layer is prepared on the top electrode :
  • a first molybdenum oxide layer on the top electrode the size of the molybdenum oxide nanoparticles is ⁇ 5nm, and the thickness of the film layer is 10-30nm;
  • the first silver layer of 10-20 nm is evaporated;
  • a 10-20 nm second silver layer is evaporated on the second molybdenum oxide layer
  • the obtained laminated structure is heated at a temperature of 100 to 140°C for 0.5 to 2 hours to form a silver oxide barrier layer between the molybdenum oxide layer and the silver layer to form MoO/Ag 2 O/Ag/Ag 2 O/MoO /Ag 2 O/Ag/Ag 2 O/MoO laminated structure.
  • a preparation method of a light emitting diode includes the following steps:
  • a top-emitting light-emitting diode is provided, the top-emitting light-emitting diode includes at least a bottom electrode and a top electrode oppositely disposed, and a light-emitting layer disposed between the bottom electrode and the top electrode, and an encapsulation layer is prepared on the top electrode :
  • a first zinc oxide layer is prepared on the top electrode, the size of the zinc oxide nanoparticles is ⁇ 5 nm, and the thickness of the film layer is 10-30 nm;
  • the obtained laminated structure is heated at a temperature of 100 to 140°C for 0.5 to 2 hours to form a magnesium oxide barrier layer between the zinc oxide layer and the magnesium layer to form ZnO/MgO/Mg/MgO/ZnO/MgO/Mg /MgO/ZnO stack structure.

Landscapes

  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Nanotechnology (AREA)
  • Electroluminescent Light Sources (AREA)
  • Laminated Bodies (AREA)

Abstract

一种叠层结构，至少包括一个叠层单元，所述叠层单元包括相对设置的第一金属氧化物层和第二金属氧化物层，以及设置在所述第一金属氧化物层和所述第二金属氧化物层之间的第三金属层，且所述第一金属氧化物层和所述第三金属层之间、以及所述第二金属氧化物层和所述第三金属层之间形成第三金属氧化物薄膜。

Description

叠层结构及其制备方法、发光二极管及其制备方法 技术领域
本申请属于显示技术领域，尤其涉及一种叠层结构及其制备方法、发光二极管及其制备方法。
 背景技术
量子点具有发光颜色易于调节、色彩饱和度高、可溶液加工、高稳定性等诸多优点，是下一代显示技术的有力竞争者。将量子点发光二极管（QLED）制备在柔性基底上，实现柔性显示是目前显示发展的一个重要方向。目前，实现柔性QLED仍面临着诸多挑战，特别是在薄膜封装技术（TFE）上，由于QLED对于空气中的水汽较敏感，渗透进来的水汽非常容易与活泼的金属阴极或是部分传输材料发生反应，引起器件性能的下降。而且，为了保证柔性QLED器件的柔韧性，通常会选用高分子聚合物作为基底，这类基底本身对外界的水汽阻挡能力较差，容易导致水汽的渗透。因此，寻找好的TFE技术，对提升器件稳定性，拓展柔性QLED的应用前景都具有重大意义。
目前，最常用的TFE方法是通过有机-无机薄膜的组合来形成封装的阻挡层，也叫Barix封装技术，其中，无机薄膜是作为真正的阻挡层，有机薄膜主要用于提高平整度，减少机械损伤。这种技术虽然能确保较低的水汽渗透率，但是需要保证有较大的有机薄膜厚度来填补无机薄膜的针孔缺陷，因此成本很高。而近些年来开发的通过原子层沉积（ALD）方法形成薄膜封装，虽然可以在较薄的厚度上实现较低水汽透过率，但是由于生长周期慢，难以应用于大面积生产。
 技术问题
本申请实施例提供了一种叠层结构及其制备方法、含有上述叠层结构的发光二极管及其制备方法，以解决现有有机-无机薄膜的组合来形成封装的阻挡层的技术中，为了保证水汽隔绝效果，要么有机薄膜厚度，导致成本高的问题，要么采用原子层沉积的方法制备薄膜，存在生长周期慢，难以应用于大面积生产的问题。
 技术解决方案
本申请实施例是这样实现的，第一方面，提供了一种叠层结构，至少包括一个叠层单元，所述叠层单元包括相对设置的第一金属氧化物层和第二金属氧化物层，以及设置在所述第一金属氧化物层和所述第二金属氧化物层之间的第三金属层，且所述第一金属氧化物层和所述第三金属层之间、以及所述第二金属氧化物层和所述第三金属层之间形成有第三金属氧化物薄膜。
第二方面，提供了一种叠层结构的制备方法，所述叠层结构至少包括一个叠层单元，所述叠层单元包括相对设置的第一金属氧化物层和第二金属氧化物层，以及设置在所述第一金属氧化物层和所述第二金属氧化物层之间的第三金属层，且所述第一金属氧化物层和所述第三金属层之间、以及所述第二金属氧化物层和所述第三金属层之间形成有第三金属氧化物薄膜，所述叠层结构的制备包括以下步骤：
提供基底，在所述基底上制备第一金属氧化物层，在所述第一金属氧化物层上制备第三金属层，在所述第三金属层上制备第二金属氧化物层，得到预制叠层单元；
将所述预制叠层单元进行加热处理，制备得到叠层单元。
第三方面，提供了一种发光二极管，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，以及设置在所述阳极和/或所述阴极的表面的封装结构，所述封装结构为本申请所述的叠层结构。
第四方面，提供了一种发光二极管的制备方法，包括以下步骤：
制备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；
按照本申请所述方法在所述阳极或所述阴极表面制备封装结构。
 有益效果
本申请提供的叠层结构，至少包括一个叠层单元，所述叠层单元包括相对设置的第一金属氧化物层和第二金属氧化物层，以及设置在所述第一金属氧化物层和所述第二金属氧化物层之间的第三金属层，且所述第一金属氧化物层和所述第三金属层之间、以及所述第二金属氧化物层和所述第三金属层之间形成第三金属氧化物薄膜。即所述叠层单元为M1O(第一金属氧化物层)/Al2O3/Al/Al2O3/M2O(第二金属氧化物层)的叠层单元。
首先，所述叠层单元中，第三金属氧化物薄膜作为主要的阻挡层提供良好的水氧阻隔能力，可以作为封装结构有效阻隔水氧；同时，薄膜金属第三金属层由于具有良好的延展性与均匀性，可以有效填补第三金属氧化物薄膜（中间层）的部分缺陷，进一步保证所述封装结构的水氧阻隔性。而金属氧化物层中的纳米金属氧化物可以吸水，将渗入的少量水汽限定在纳米金属氧化物中，实现多层水汽隔绝的效果。
其次，由于所述叠层结构中的材料如第三金属层、金属氧化物层、第三金属氧化物薄膜均具有较好的导热效果，因此，将所述叠层结构用作发热器件的封装结构时，能有效将器件内部由于辐射产生的热量传导到外部环境中，有效提高器件稳定性。
此外，本申请提供的叠层结构的材料与常规的发光器件制备材料兼容，具有成本低廉的优点。
本申请提供的叠层结构的制备方法，只需将依次层叠制备第一金属氧化物层、第三金属层、第二金属氧化物层后，进行加热处理即可制备。该方法与常规的发光器件的工艺兼容，且操作简单，具有成本低廉的优点，适合应用于大面积的工业生产。
本申请提供的发光二极管，在阳极或阴极的表面设置有本申请上述的封装结构，所述封装结构可以有效隔绝水氧进入发光二极管的功能单元，同时其他其导热效果，进而提高发光二极管的器件稳定性。
本申请提供的发光二极管的制备方法，只需在常规的制备方法的基础上，进一步制备封装结构，方法简单可控，且适合应用于大面积的工业生产。
 附图说明
图1是本申请实施例提供的含有预制叠层单元的叠层结构的示意图；
图2是本申请实施例提供的含有叠层单元的叠层结构的示意图；
图3是本申请实施例提供的一种叠层结构的制备方法流程示意图。
 本发明的实施方式
为了使本申请的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本申请进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本申请，并不用于限定本申请。
在本申请的描述中，需要理解的是，术语“第一”、“第二”仅用于描述目的，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。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。在本申请的描述中，“多个”的含义是两个或两个以上，除非另有明确具体的限定。
本申请实施例提供了一种叠层结构，至少包括一个叠层单元，所述叠层单元包括相对设置的第一金属氧化物层和第二金属氧化物层，以及设置在所述第一金属氧化物层和所述第二金属氧化物层之间的第三金属层，且所述第一金属氧化物层和所述第三金属层之间、以及所述第二金属氧化物层和所述第三金属层之间形成有第三金属氧化物薄膜。
可选地，所述第三金属层以及所述第三金属氧化物薄膜中的第三金属为能够与氧反应形成第三金属氧化物，例如Al、Mg、Ag等金属。需要说明的是，第三金属氧化物薄膜可以是第一金属氧化物层和所述第三金属层反应形成的，或第二金属氧化物层和所述第三金属层反应形成的，也可以是直接在是第一金属氧化物层和所述第三金属层之间沉积的，或第二金属氧化物层和所述第三金属层之间沉积的。
本申请实施例提供的叠层结构，至少包括一个叠层单元，所述叠层单元包括相对设置的第一金属氧化物层和第二金属氧化物层，以及设置在所述第一金属氧化物层和所述第二金属氧化物层之间的第三金属层，且所述第一金属氧化物层和所述第三金属层之间、以及所述第二金属氧化物层和所述第三金属层之间形成有第三金属氧化物薄膜。以第三金属层为Al示例，所述叠层单元为M 1O(第一金属氧化物层)/Al 2O 3/Al/Al 2O 3/M 2O(第二金属氧化物层)的叠层单元，第三金属氧化物薄膜Al 2O 3可以是第一金属氧化物层和所述第三金属层Al反应形成的，或第二金属氧化物层和所述第三金属层Al反应形成的，也可以是直接在是第一金属氧化物层和所述第三金属层之间沉积的，或第二金属氧化物层和所述第三金属层之间沉积的，即通过化学沉积或物理沉积方法沉积的。
首先，所述叠层单元中，第三金属氧化物薄膜作为主要的阻挡层提供良好的水氧阻隔能力，可以作为封装结构有效阻隔水氧；同时，薄膜金属第三金属层由于具有良好的延展性与均匀性，可以有效填补第三金属氧化物薄膜（中间层）的部分缺陷，进一步保证所述封装结构的水氧阻隔性。而金属氧化物层中的纳米金属氧化物可以吸水，将渗入的少量水汽限定在纳米金属氧化物中，实现多层水汽隔绝的效果。
其次，由于所述叠层结构中的材料如第三金属层、金属氧化物层、第三金属氧化物薄膜均具有较好的导热效果，因此，将所述叠层结构用作发热器件的封装结构时，能有效将器件内部由于辐射产生的热量传导到外部环境中，有效提高器件稳定性。
此外，本申请实施例提供的叠层结构的材料与常规的发光器件制备材料兼容，具有成本低廉的优点。
具体的，所述叠层结构中，金属氧化物层作为功能层之一，分别作为叠层结构的两端面，一方面用于提供氧空位，与中间金属层第三金属层反应生成隔绝水氧的第三金属氧化物薄膜；另一方面，金属氧化物层可以吸水，使渗入的少量水汽被限定在金属氧化物层，进一步提高阻隔水汽的效果。
本申请实施例中，所述第一金属氧化物层选自纳米金属氧化物和/或掺杂的纳米金属氧化物；所述第二金属氧化物层的材料选自纳米金属氧化物和/或掺杂的纳米金属氧化物。
在一些实施例中，所述第一金属氧化物层的材料选自纳米氧化锌、纳米氧化镍、掺杂的纳米氧化镍、纳米氧化钼、掺杂的纳米氧化钼中的至少一种。在一些实施例中，所述第二金属氧化物层的材料选自纳米氧化锌、掺杂的纳米氧化锌、纳米氧化镍、掺杂的纳米氧化镍、纳米氧化钼、掺杂的纳米氧化钼中的至少一种。优选的金属氧化物材料，导热性较好，且不仅容易在界面产生氧扩散，有利于与中间金属层第三金属层反应生成隔绝水氧的第三金属氧化物薄膜；而且，优选的金属氧化物材料本身可以吸水，进一步提高阻隔水汽的效果。此外，所述金属氧化物材料容易易于打印，具有较好的成膜性。
在优选实施例中，所述第一金属氧化物层中的金属氧化物与所述第二金属氧化物层中的金属氧化物相同，从而获得稳定性更强的叠层结构。
在上述实施例的基础上，所述掺杂的纳米金属氧化物，掺杂材料选自金属材料。具体的，所述金属材料选自易于与氧反应，且反应生成的金属氧化物具有良好的水氧阻隔能力的金属。在优选实施例中，所述掺杂材料选自镁、铝、锰、银中的至少一种。所述镁、铝、锰、银易于与氧反应，且反应生成的金属氧化物具有良好的水氧阻隔能力。
本申请实施例中，金属氧化物层（包括所述第一金属氧化物层、所述第二金属氧化物层）中的金属氧化物纳米颗粒大小小于5nm，从而保证膜层致密度。
本申请实施例中，优选的，所述第一金属氧化物层的厚度为10~30nm。优选的，所述第二金属氧化物层的厚度为10~20nm。若金属氧化物层的膜层太薄，形成的膜层不够致密，会有较多针孔缺陷；若金属氧化物层的膜层太厚，会浪费材料，同时叠层结构作为封装层时，会降低封装层的透光率。
第三金属层作为又一功能层，可以与金属氧化物的氧空位反应，生成隔绝水氧的第三金属氧化物薄膜。同时，第三金属层具有较好的导热系数和良好的延展性，作为封装结构使用时，不仅可以可以有效填补第三金属氧化物薄膜（中间层）的部分缺陷，进一步保证所述封装结构的水氧阻隔性；而且有利于将器件内部由于辐射产生的热量传导到外部环境中，有效提高器件稳定性。
在一些实施例中，所述第三金属层以及所述第三金属氧化物薄膜中的第三金属选自铝、镁、银中的至少一种。此时，所述叠层单元中，第三金属氧化物薄膜作为主要的阻挡层提供良好的水氧阻隔能力，可以作为封装结构有效阻隔水氧；同时，第三金属层由于具有良好的延展性与均匀性，可以有效填补第三金属氧化物薄膜（中间层）的部分缺陷，进一步保证所述封装结构的水氧阻隔性。而金属氧化物层中的纳米金属氧化物可以吸水，将渗入的少量水汽限定在纳米金属氧化物中，实现多层水汽隔绝的效果。
在一些实施例中，所述第三金属层的厚度为10~20nm。若所述第三金属层的厚度过薄，则形成的膜层质量不佳，容易出现孔洞形成水汽渗透通道，无法起到填充金属氧化物层缺陷的作用；若所述第三金属层的厚度过厚，叠层结构作为封装层时，会降低封装层的透光率。
本申请实施例中，所述第三金属氧化物薄膜实际为相邻的第三金属层与金属氧化物层反应生成的水氧阻隔功能层。在一些实施例中，所述第三金属氧化物薄膜的厚度为2~5nm，此时，能够实现较好的水氧隔绝效果。
本申请实施例所述叠层结构中至少包括一个叠层单元，所述叠层单元的数量，根据叠层单元的厚度和被封装器件要达到的水汽透过率决定。器件要求的密封性越好，对应的叠层单元个数越多。在一些实施例中，，所述叠层单元中，所述叠层结构包括1-10个重复设置的叠层单元。作为一个具体实施例，当被封装器件要达到的水汽透过率为1×10 -6 g/m 2/天时，至少需要有3个以上的重复叠层单元。
值得注意的是，当所述叠层结构中包括两个或两个以上的叠层单元时，且所述第一金属氧化物层、所述第二金属氧化物层的材料相同时，相邻的金属氧化物层可以合作一层。
本申请实施例所述薄层结构，可以通过下述方法制备获得。
相应的，如图1、图2所示，本申请实施例提供了一种叠层结构的制备方法，所述叠层结构如图2所示，至少包括一个叠层单元10，所述叠层单元包括相对设置的第一金属氧化物层11和第二金属氧化物层13，以及设置在所述第一金属氧化物层11和所述第二金属氧化物层13之间的第三金属层12，且所述第一金属氧化物层11和所述第三金属层12之间、以及所述第二金属氧化物层13和所述第三金属层12之间形成有第三金属氧化物薄膜121，参照图3示出的，本申请实施例的一种叠层结构的制备方法流程示意图，所述叠层结构的制备包括以下步骤：
S01.提供基底，在所述基底上制备第一金属氧化物层11，在所述第一金属氧化物层11上制备第三金属层12，在所述第三金属层12上制备第二金属氧化物层13，得到预制叠层单元10’，如图1所示；
S02.将所述预制叠层单元10’进行加热处理，制备得到叠层单元10。
本申请实施例提供的叠层结构的制备方法，只需将依次层叠制备第一金属氧化物层、第三金属层、第二金属氧化物层后，进行加热处理即可制备。该方法与常规的发光器件的工艺兼容，且操作简单，具有成本低廉的优点，适合应用于大面积的工业生产。
具体的，上述步骤S01中，所述基底为需要制备封装结构的元器件，如发光二极管。在所述基底上制备第一金属氧化物层11，在一些实施例中，采用喷墨打印技术实现；在所述第一金属氧化物层11上制备第三金属层12，在一些实施例中采用真空蒸镀技术实现；在所述第三金属层12上制备第二金属氧化物层13，在一些实施例中采用喷墨打印技术实现。通过依次在所述基底上制备第一金属氧化物层11、第三金属层12和第二金属氧化物层13，得到如图1所示的含有预制叠层单元10’的结构。此时得到的结构，还不具备较好的水氧阻隔性能。
上述步骤S02中，将所述预制叠层单元10’进行加热处理，使第一金属氧化物层11的金属氧化物和第三金属层12中的铝、第二金属氧化物层13的金属氧化物和第三金属层12中的铝发生反应，在金属氧化物和第三金属层之间形成第三金属氧化物薄膜121，得到如图2所示的含有叠层单元10的叠层结构。
在一些实施例中，将所述预制叠层单元进行加热处理在温度为100℃~140℃的条件下进行，且所述加热处理的时间为0.5h~2h。在该条件下，不仅能够有效促进第一金属氧化物层11的金属氧化物和第三金属层12中的铝、第二金属氧化物层13的金属氧化物和第三金属层12中的铝的反应，而且也不会由于温度过高而影响各功能层的质量。
根据实际需要，本申请实施例提供的所述方法还包括：在所述预制叠层单元的至少一金属氧化物层表面重复制备第三金属层和金属氧化物层的步骤，将得到的叠层结构进行加热处理，制备得到具有多个叠层单元的叠层结构。
值得注意的时，当在所述预制叠层单元的至少一金属氧化物层表面重复制备第三金属层和金属氧化物层的步骤时，用于重复制备第三金属层和金属氧化物层的金属氧化物层的厚度为20-40nm，以保证足够的金属氧化物能够同时与上下两层的第三金属层反应色生成合适厚度的第三金属氧化物薄膜。
本申请实施例还提供了一种发光二极管，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，以及设置在所述阳极和/或所述阴极的表面的封装结构，所述封装结构为本申请实施例所述的叠层结构。
本申请实施例提供的发光二极管，在阳极或阴极的表面设置有本申请实施例上述的封装结构，所述封装结构可以有效隔绝水氧进入发光二极管的功能单元，同时其他其导热效果，进而提高发光二极管的器件稳定性。
本申请实施例中，所述发光二极管为量子点发光二极管或有机发光二极管。
具体的，所述发光二极管还包括衬底，衬底可以设置在阳极一端，形成正置发光二极管；衬底可以设置在阴极一端，形成倒置发光二极管。
在一些实施例中，所述发光二极管还包括设置在阳极和发光层之间的空穴传输层、空穴注入层中的至少一层。在一些实施例中，所述发光二极管包括设置在阳极和发光层之间的空穴传输层。在一些实施例中，所述发光二极管包括设置在阳极和发光层之间的空穴注入层。在一些实施例中，所述发光二极管包括设置在阳极和发光层之间的空穴传输层，以及设置在空穴传输层和发光层之间的空穴注入层。
在一些实施例中，所述发光二极管还包括设置在阴极和发光层之间的电子传输层、电子注入层中的至少一层。在一些实施例中，所述量子点发光二极管包括设置在阴极和量子点发光层之间的电子传输层。在一些实施例中，所述量子点发光二极管包括设置在阴极和量子点发光层之间的电子注入层。在一些实施例中，所述量子点发光二极管包括设置在阴极和量子点发光层之间的电子传输层，以及设置在电子传输层和发光层之间的电子注入层。
所述叠层结构在发光二极管中的设置包括几种方式。
当衬底设置在阳极一端，即发光二极管为正置发光二极管时，在一些实施例中，在阴极一端表面设置封装结构，所述封装结构为本申请实施例所述的叠层结构；在一些实施例中，在衬底背离阳极的表面设置封装结构，所述封装结构为本申请实施例所述的叠层结构；在一些实施例中，在阴极一端表面设置封装结构，同时，在衬底背离阳极的表面设置封装结构，所述封装结构为本申请实施例所述的叠层结构。
当衬底可以设置在阴极一端，形成倒置量子点发光二极管时，在一些实施例中，在阳极一端表面设置封装结构，所述封装结构为本申请实施例所述的叠层结构；在一些实施例中，在衬底背离阴极的表面设置封装结构，所述封装结构为本申请实施例所述的叠层结构；在一些实施例中，在阳极一端表面设置封装结构，同时，在衬底背离阴极的表面设置封装结构，所述封装结构为本申请实施例所述的叠层结构。
本申请实施例所述发光二极管，可以通过下述方法制备获得。
相应的，本申请实施例提供了一种发光二极管的制备方法，包括以下步骤：
制备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；
按照本申请实施例所述方法在所述阳极或所述阴极的表面制备封装结构。
本申请实施例提供的发光二极管的制备方法，只需在常规的制备方法的基础上，进一步制备封装结构，方法简单可控，且适合应用于大面积的工业生产。
所述阳极、阴极和发光层的制备，可以采用常规方法。
在一些实施例中，所述制备方法还包括在阳极和发光层之间制备空穴传输层、空穴注入层中的至少一层。在一些实施例中，所述制备方法包括在阳极和发光层之间制备空穴传输层，以及在空穴传输层和发光层之间制备空穴注入层。
在一些实施例中，所述制备方法还包括设置在阴极和发光层之间制备电子传输层、电子注入层中的至少一层。在一些实施例中，所述制备方法包括在阴极和发光层之间制备电子传输层，以及在电子传输层和发光层之间制备电子注入层。
在所述所述阳极或所述阴极的表面制备封装结构，可以采用本申请实施例所述叠层结构的制备方法制备获得。
下面结合具体实施例进行说明。
实施例1
一种发光二极管的制备方法，包括以下步骤：
提供顶发射发光二极管，所述顶发射发光二极管至少包括相对设置的底电极和顶电极，以及设置在所述底电极和所述顶电极之间的发光层，在所述顶电极上制备封装层：
利用喷墨打印或旋涂方法，在所述顶电极上制备第一氧化锌层，氧化锌纳米颗粒大小< 5nm，膜层厚度10~30nm；
在第一层氧化锌层上蒸镀10-20nm的铝层；
在铝层上喷墨打印或旋涂一层10~20nm的第二氧化锌层；
将得到的叠层结构在温度为100~140℃的条件下加热0.5~2h，在氧化锌层和铝层之间生成三氧化二铝阻挡层，形成ZnO/Al 2O 3/Al/Al 2O 3/ZnO的叠层结构。
实施例2
一种发光二极管的制备方法，包括以下步骤：
提供顶发射发光二极管，所述顶发射发光二极管至少包括相对设置的底电极和顶电极，以及设置在所述底电极和所述顶电极之间的发光层，在所述顶电极上制备封装层：
利用喷墨打印或旋涂方法，在所述顶电极上制备第一氧化锌层，氧化锌纳米颗粒大小< 5nm，膜层厚度10~30nm；
在第一层氧化锌层上蒸镀10-20nm的第一铝层；
在第一铝层上喷墨打印或旋涂一层20~40nm的第二氧化锌层；
在第二层氧化锌层上蒸镀10-20nm的第二铝层；
在第二铝层上喷墨打印或旋涂一层10~20nm的第三氧化锌层；
将得到的叠层结构在温度为100~140℃的条件下加热0.5~2h，在氧化锌层和铝层之间生成三氧化二铝阻挡层，形成ZnO/Al 2O 3/Al/Al 2O 3/ZnO/Al 2O 3/Al/Al 2O 3/ZnO的叠层结构。
实施例3
一种发光二极管的制备方法，包括以下步骤：
提供顶发射发光二极管，所述顶发射发光二极管至少包括相对设置的底电极和顶电极，以及设置在所述底电极和所述顶电极之间的发光层，在所述顶电极上制备封装层：
利用喷墨打印或旋涂方法，在所述顶电极上制备第一氧化钼层，氧化钼纳米颗粒大小< 5nm，膜层厚度10~30nm；
在第一层氧化钼层上蒸镀10-20nm的第一银层；
在第一银层上喷墨打印或旋涂一层20~40nm的第二氧化钼层；
在第二层氧化钼层上蒸镀10-20nm的第二银层；
在第二银层上喷墨打印或旋涂一层10~20nm的第三氧化钼层；
将得到的叠层结构在温度为100~140℃的条件下加热0.5~2h，在氧化钼层和银层之间生成氧化银阻挡层，形成MoO/Ag 2O/Ag/Ag 2O/MoO/Ag 2O/Ag/Ag 2O/MoO的叠层结构。
实施例4
一种发光二极管的制备方法，包括以下步骤：
提供顶发射发光二极管，所述顶发射发光二极管至少包括相对设置的底电极和顶电极，以及设置在所述底电极和所述顶电极之间的发光层，在所述顶电极上制备封装层：
利用喷墨打印或旋涂方法，在所述顶电极上制备第一氧化锌层，氧化锌纳米颗粒大小< 5nm，膜层厚度10~30nm；
在第一层氧化锌层上蒸镀10-20nm的镁层；
在镁层上喷墨打印或旋涂一层20~40nm的第二氧化锌层；
将得到的叠层结构在温度为100~140℃的条件下加热0.5~2h，在氧化锌层和镁层之间生成氧化镁阻挡层，形成ZnO/MgO/Mg/MgO/ZnO/MgO/Mg/MgO/ZnO的叠层结构。
以上所述实施例仅用以说明本申请的技术方案，而非对其限制；尽管参照前述实施例对本申请进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本申请各实施例技术方案的精神和范围，均应包含在本申请的保护范围之内。

Claims (20)

  1. 一种叠层结构，其特征在于，至少包括一个叠层单元，所述叠层单元包括相对设置的第一金属氧化物层和第二金属氧化物层，以及设置在所述第一金属氧化物层和所述第二金属氧化物层之间的第三金属层，且所述第一金属氧化物层和所述第三金属层之间、以及所述第二金属氧化物层和所述第三金属层之间形成有第三金属氧化物薄膜。
  2. 如权利要求1所述的叠层结构，其特征在于，所述第三金属层以及所述第三金属氧化物薄膜中的第三金属为能够与氧反应形成第三金属氧化物。
  3. 如权利要求1所述的叠层结构，其特征在于，所述第三金属氧化物薄膜由第一金属氧化物层中的第一金属氧化物与所述第三金属层反应制得；和/或，
    所述第三金属氧化物薄膜由第二金属氧化物层中的第二金属氧化物与第三金属层反应制得。
  4. 如权利要求1所述的叠层结构，其特征在于，所述第一金属氧化物的厚度为10~30nm；和/或
    所述第二金属氧化物层的厚度为10~20nm；和/或
    所述第三金属层的厚度为10~20nm；和/或
    所述第三金属氧化物薄膜的厚度为2~5nm。
  5. 如权利要求1所述的叠层结构，其特征在于，所述第一金属氧化物层选自纳米金属氧化物和/或掺杂的纳米金属氧化物；和/或
    所述第二金属氧化物层的材料选自纳米金属氧化物和/或掺杂的纳米金属氧化物；和/或
    所述第三金属层以及所述第三金属氧化物薄膜中的第三金属选自铝、镁、银中的至少一种。
  6. 如权利要求5所述的叠层结构，其特征在于，所述第一金属氧化物层的材料选自纳米氧化锌、纳米氧化镍、掺杂的纳米氧化镍、纳米氧化钼、掺杂的纳米氧化钼中的至少一种；和/或
    所述第二金属氧化物层的材料选自纳米氧化锌、掺杂的纳米氧化锌、纳米氧化镍、掺杂的纳米氧化镍、纳米氧化钼、掺杂的纳米氧化钼中的至少一种。
  7. 如权利要求5所述的叠层结构，其特征在于，所述第一金属氧化物层中的金属氧化物与所述第二金属氧化物层中的金属氧化物相同。
  8. 如权利要求5所述的叠层结构，其特征在于，所述掺杂的纳米金属氧化物，掺杂材料选自与氧反应后生成的金属氧化物具有水氧阻隔能力的金属。
  9. 如权利要求8所述的叠层结构，其特征在于，所述掺杂的纳米金属氧化物，掺杂材料选自镁、铝、锰、银中的至少一种。
  10. 如权利要求1所述的叠层结构，其特征在于，所述第一金属氧化物层中的金属氧化物纳米颗粒大小小于5nm；和/或
    所述第二金属氧化物层中的金属氧化物纳米颗粒大小小于5nm。
  11. 如权利要求1所述的叠层结构，其特征在于，所述叠层结构包括1-10个重复设置的叠层单元。
  12. 如权利要求11所述的叠层结构，其特征在于，被封装器件的水汽透过率为1×10 -6 g/m 2/天以上时，所述叠层结构至少包括有3个重复叠层单元。
  13. 一种叠层结构的制备方法，其特征在于，所述叠层结构至少包括一个叠层单元，所述叠层单元包括相对设置的第一金属氧化物层和第二金属氧化物层，以及设置在所述第一金属氧化物层和所述第二金属氧化物层之间的第三金属层，且所述第一金属氧化物层和所述第三金属层之间、以及所述第二金属氧化物层和所述第三金属层之间形成有第三金属氧化物薄膜，所述叠层结构的制备包括以下步骤：
    提供基底，在所述基底上制备第一金属氧化物层，在所述第一金属氧化物层上制备第三金属层，在所述第三金属层上制备第二金属氧化物层，得到预制叠层单元；
    将所述预制叠层单元进行加热处理，制备得到叠层单元。
  14. 如权利要求13所述的叠层结构的制备方法，其特征在于，将所述预制叠层单元进行加热处理在温度为100℃~140℃的条件下进行，且所述加热处理的时间为0.5h~2h。
  15. 如权利要求13所述的叠层结构的制备方法，其特征在于，还包括：在所述预制叠层单元的至少一金属氧化物层表面重复制备第三金属层和金属氧化物层的步骤，将得到的叠层结构进行加热处理。
  16. 如权利要求15所述的叠层结构的制备方法，其特征在于，在所述预制叠层单元的至少一金属氧化物层表面重复制备第三金属层和金属氧化物层的步骤时，用于重复制备第三金属层和金属氧化物层的金属氧化物层的厚度为20-40nm。
  17. 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，以及设置在所述阳极和/或所述阴极的表面的封装结构，所述封装结构为权利要求1所述的叠层结构。
  18. 如权利要求17所述的发光二极管，其特征在于，所述发光二极管为量子点发光二极管或有机发光二极管。
  19. 如权利要求17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阳极和发光层之间的空穴传输层、空穴注入层中的至少一层；和/或
    所述发光二极管还包括设置在阴极和发光层之间的电子传输层、电子注入层中的至少一层。
  20. 一种发光二极管的制备方法，其特征在于，包括以下步骤：
    制备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；
    按照权利要求13所述方法在所述阳极或所述阴极的表面制备封装结构。
PCT/CN2019/108156 2018-12-29 2019-09-26 叠层结构及其制备方法、发光二极管及其制备方法 Ceased WO2020134253A1 (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US17/419,580 US12069887B2 (en) 2018-12-29 2019-09-26 Laminated structure and preparation method thereof, LED and preparation method thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201811633012.2A CN111384283B (zh) 2018-12-29 2018-12-29 叠层结构及其制备方法、发光二极管及其制备方法
CN201811633012.2 2018-12-29

Publications (1)

Publication Number Publication Date
WO2020134253A1 true WO2020134253A1 (zh) 2020-07-02

Family

ID=71126132

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2019/108156 Ceased WO2020134253A1 (zh) 2018-12-29 2019-09-26 叠层结构及其制备方法、发光二极管及其制备方法

Country Status (3)

Country Link
US (1) US12069887B2 (zh)
CN (1) CN111384283B (zh)
WO (1) WO2020134253A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12069887B2 (en) 2018-12-29 2024-08-20 Tcl Technology Group Corporation Laminated structure and preparation method thereof, LED and preparation method thereof

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111710801A (zh) * 2020-07-09 2020-09-25 浩物电子科技(苏州)有限公司 一种顶发射oled的复合薄膜封装方法
CN117766613B (zh) * 2023-12-27 2024-08-23 天合光能股份有限公司 太阳能电池及其制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102209628A (zh) * 2008-11-11 2011-10-05 旭硝子株式会社 导电性层叠体及等离子显示器用保护板
US20130045374A1 (en) * 2011-08-17 2013-02-21 National Applied Research Laboratories Nano-laminated film with transparent conductive property and water-vapor resistance function and method thereof
CN106784380A (zh) * 2016-12-29 2017-05-31 固安翌光科技有限公司 一种封装结构及其制备方法和应用
CN107658389A (zh) * 2017-09-28 2018-02-02 武汉华星光电半导体显示技术有限公司 无机膜及封装薄膜

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10275680A (ja) * 1997-03-31 1998-10-13 Toyota Central Res & Dev Lab Inc 有機ｅｌ素子
KR20100111117A (ko) * 2009-04-06 2010-10-14 삼성전기주식회사 박막소자의 제조방법 및 이로부터 제조된 박막소자
CN102299265A (zh) * 2011-08-18 2011-12-28 电子科技大学 有机发光二极管照明器件及其散热封装层以及制备方法
CN103178077B (zh) * 2011-12-21 2016-08-24 昆山工研院新型平板显示技术中心有限公司 有机电致发光显示器件及其封装方法
CN104183747A (zh) * 2013-05-22 2014-12-03 海洋王照明科技股份有限公司 一种有机电致发光器件及其制备方法
JP2017111886A (ja) * 2015-12-14 2017-06-22 コニカミノルタ株式会社 照明装置
CN111384283B (zh) 2018-12-29 2021-07-02 Tcl科技集团股份有限公司 叠层结构及其制备方法、发光二极管及其制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102209628A (zh) * 2008-11-11 2011-10-05 旭硝子株式会社 导电性层叠体及等离子显示器用保护板
US20130045374A1 (en) * 2011-08-17 2013-02-21 National Applied Research Laboratories Nano-laminated film with transparent conductive property and water-vapor resistance function and method thereof
CN106784380A (zh) * 2016-12-29 2017-05-31 固安翌光科技有限公司 一种封装结构及其制备方法和应用
CN107658389A (zh) * 2017-09-28 2018-02-02 武汉华星光电半导体显示技术有限公司 无机膜及封装薄膜

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12069887B2 (en) 2018-12-29 2024-08-20 Tcl Technology Group Corporation Laminated structure and preparation method thereof, LED and preparation method thereof

Also Published As

Publication number Publication date
CN111384283B (zh) 2021-07-02
US20220069256A1 (en) 2022-03-03
US12069887B2 (en) 2024-08-20
CN111384283A (zh) 2020-07-07

Similar Documents

Publication Publication Date Title
CN107768529A (zh) 钙钛矿发光二极管及其制作方法
CN102437288A (zh) 有机电致发光器件的封装结构
CN110148684B (zh) 一种显示面板及显示装置
JP2016537793A (ja) 有機電子素子用基板およびこの製造方法
TWI375346B (en) Metal compound-metal multilayer electrodes for organic electronic devices
CN110571347B (zh) 一种显示面板及其制备方法
CN1691852B (zh) 有机电致发光装置及其制法
CN109427992A (zh) 薄膜封装结构及具有其的显示装置
CN111384283B (zh) 叠层结构及其制备方法、发光二极管及其制备方法
WO2020206980A1 (zh) 柔性oled显示装置及制备方法
CN106206992A (zh) 一种薄膜封装结构及有机发光二极管器件
KR20200075796A (ko) 유기광전자소자의 봉지필름 및 그 제조방법
CN113130778A (zh) 量子点发光二极管及其制备方法
CN102751443B (zh) 有机电致发光装置及其制作方法
CN118765120A (zh) 一种封装的钙钛矿太阳能电池组件及制备方法
KR102159993B1 (ko) 유기광전자소자의 봉지필름 및 그 제조방법
CN108461640A (zh) 晶态有机电致发光二极管及其应用
CN103730586A (zh) 层叠式有机发光二极体及其制备方法
CN111584751A (zh) 封装结构及封装方法、电致发光器件、显示设备
CN117560948A (zh) 钙钛矿发光晶体管及其制备方法
WO2020134244A1 (zh) 封装薄膜及其制备方法和发光显示装置
CN111162188A (zh) 薄膜封装结构及其制备方法和显示面板
CN115458699A (zh) 封装薄膜、光电器件的封装结构及封装方法
US20230117011A1 (en) Display panel, preparation method, and display device
CN108365125B (zh) 一种显示面板、其制备方法及显示装置

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19905192

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19905192

Country of ref document: EP

Kind code of ref document: A1