WO2020134162A1 - Quantum dot light-emitting diode and preparation method thereof - Google Patents

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

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Publication number
WO2020134162A1
WO2020134162A1 PCT/CN2019/104011 CN2019104011W WO2020134162A1 WO 2020134162 A1 WO2020134162 A1 WO 2020134162A1 CN 2019104011 W CN2019104011 W CN 2019104011W WO 2020134162 A1 WO2020134162 A1 WO 2020134162A1
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layer
quantum dot
dot light
emitting diode
interface layer
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PCT/CN2019/104011
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French (fr)
Chinese (zh)
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苏亮
谢相伟
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Tcl科技集团股份有限公司
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • 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
    • H10K50/15—Hole transporting layers
    • H10K50/156—Hole transporting layers comprising a multilayered structure
    • 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
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating

Definitions

  • the present application belongs to the technical field of photoelectric display, and in particular relates to a quantum dot light-emitting diode and a preparation method thereof.
  • QLEDs quantum dot-based electroluminescent diodes
  • the root cause of the QLED electron hole imbalance is that the bottom energy level of the conduction band of the metal oxide electron transport layer (especially ZnO) is close to the bottom energy level of the conduction band of quantum dots, and the electron injection barrier is very small;
  • the gap between the HOMO energy level of the hole transport layer and the top energy level of the quantum dot valence band is large, generally >0.5eV or more; mismatches in the energy levels result in easier injection of electrons into the quantum dot light-emitting layer.
  • the electron mobility of metal oxides is generally greater than the hole mobility of organic hole transport materials, which exacerbates this phenomenon. Therefore, it is important to reduce the energy gap between the hole transport layer and the quantum dot light-emitting layer.
  • transition metal oxides are widely used as hole injection materials because of their unique high work function characteristics. It can form an effective ohmic contact at the anode/hole transport layer interface, greatly improving the hole from anode to hole Transport layer injection efficiency.
  • M refers to metal
  • C2p-M3d orbital hybridization M refers to metal
  • the HOMO energy level of the organic matter close to the Fermi energy level of the transition metal oxide
  • the embodiments of the present application provide a quantum dot light emitting diode and a preparation method thereof to solve the problem that there is a strong C 2p -M 3d orbital hybridization between the existing quantum dot light emitting diode transition metal atom and the organic hole transport material, which is difficult Continue to improve the HOMO energy level of organic hole transport materials.
  • a quantum dot light emitting diode including an anode and a cathode disposed oppositely, a quantum dot light emitting layer disposed between the anode and the cathode, and a A hole function stack between the anode and the quantum dot light-emitting layer, the hole function stack includes a hole injection layer, a hole transport layer provided on the hole injection layer, and a An interface layer between the hole injection layer and the hole transport layer, wherein the hole injection layer is disposed adjacent to the anode, and the material of the hole injection layer contains a transition metal oxide; the void The hole transport layer is disposed adjacent to the quantum dot light-emitting layer, and the material of the hole transport layer contains an organic hole transport material; the material of the interface layer is a graphene-based material.
  • a method for manufacturing a quantum dot light-emitting diode including the following steps:
  • An interface layer is prepared between the hole transport layer and the hole injection layer, wherein the hole injection layer is disposed adjacent to the anode, and the material of the hole injection layer contains a transition metal oxide; the hole transport The layer is disposed adjacent to the quantum dot light-emitting layer, and the material of the hole transport layer contains an organic hole transport material; the material of the interface layer is a graphene-based material.
  • an interface layer is provided between the hole injection layer and the hole transport layer, and the material of the interface layer is a graphene-based material.
  • the arrangement of the interface layer can weaken or even break the strong C 2p -M 3d orbital hybridization between the organic hole transport material molecule and the transition metal oxide; meanwhile, compared with the organic hole transport material
  • the molecular orientation of the transition metal oxide surface is "upright"
  • the molecular orientation of the organic hole transport material molecules at the interface layer changes to "poured type", thereby The molecular orientation angle is greatly reduced.
  • the outermost layer of the organic hole transport material molecule is mainly the ⁇ orbital, which has a shielding effect on the ⁇ (CH) orbital, thereby increasing the HOMO energy level of the organic hole transport material and reducing the space.
  • the hole injection barrier between the hole transport layer/quantum dot light emitting layer improves the number of holes and injection efficiency, promotes charge balance, and further improves the performance of QLED.
  • the preparation method of the quantum dot light-emitting diode provided by the present application can be realized only by preparing the interface layer between the hole transport layer and the hole injection layer on the basis of the preparation method of the conventional quantum dot light-emitting diode, and the method is simple and controllable .
  • FIG. 1 is a schematic structural diagram of a hole function stack provided by an embodiment of the present application.
  • FIG. 2 is a schematic structural diagram of a quantum dot light emitting diode provided by an embodiment of the present application
  • FIG. 3 is a schematic flow chart of a method for manufacturing a quantum dot light emitting diode 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.
  • a first aspect of an embodiment of the present application provides a quantum dot light emitting diode, including an anode 1 and a cathode 5 disposed oppositely, a quantum dot light emitting layer 3 disposed between the anode 1 and the cathode 5, and disposed at A hole function stack 2 between the anode 1 and the quantum dot light emitting layer 3,
  • the hole function stack 2 includes a hole injection layer 21, a hole transport layer 23 provided on the hole injection layer 21, and a hole injection An interface layer 22 between the layer 21 and the hole transport layer 23, wherein the hole injection layer 21 is disposed adjacent to the anode 1, and the material of the hole injection layer 21 contains a transition metal oxide; the hole transport layer 23 is adjacent to quantum
  • the point light emitting layer 3 is provided, and the material of the hole transport layer 23 contains an organic hole transport material; the material of the interface layer 22 is a graphene-based material.
  • an interface layer is provided between the hole injection layer and the hole transport layer, and the material of the interface layer is a graphene-based material.
  • the arrangement of the interface layer can weaken or even break the strong C 2p -M 3d orbital hybridization between the organic hole transport material molecule and the transition metal oxide; meanwhile, compared with the organic hole transport material
  • the molecular orientation of the transition metal oxide surface is "upright"
  • the molecular orientation of the organic hole transport material molecules at the interface layer changes to "poured type", thereby The molecular orientation angle is greatly reduced.
  • the outermost layer of the organic hole transport material molecule is mainly the ⁇ orbital, which has a shielding effect on the ⁇ (CH) orbital, thereby improving the HOMO energy level of the organic hole transport material and reducing
  • the hole injection barrier between the hole transport layer/quantum dot light emitting layer improves the number of holes and injection efficiency, promotes charge balance, and further improves the performance of QLED.
  • the quantum dot light emitting diode may further include a substrate 10.
  • the substrate 10 may be selected from conventional substrate materials, including flexible substrates and hard substrates, such as glass substrates.
  • the quantum dot light-emitting diodes can be classified into an upright type quantum dot light-emitting diode and an inverted type quantum dot light-emitting diode.
  • the anode 1 is provided on the substrate 10; in the upside down type quantum dot light emitting diode, the cathode 5 is provided on the substrate 10.
  • the quantum dot light-emitting diode includes an anode 1 and a cathode 5 disposed oppositely.
  • the material selection and thickness range of the anode 1 and the cathode 5 can be set with reference to a conventional quantum dot light-emitting diode.
  • the quantum dot light emitting layer 3 provided between the anode 1 and the cathode 5 contains at least quantum dots.
  • the quantum dot may be a single-core structure of a group II-VI compound semiconductor or a core-shell quantum dot formed by a group II-VI, specifically including but not limited to CdSe, ZnCdS, CdSeS, ZnCdSeS, CdSe/ZnS, CdSeS/ZnS, CdSe/CdS, CdSe/CdS/ZnS, ZnCdS/ZnS, CdS/ZnS or ZnCdSeS/ZnS.
  • the quantum dot may be a single-core structure of a group III-V compound semiconductor or a core-shell quantum dot formed by a group III-V, specifically including but not limited to GaAs, GaN, InP, InP/ ZnS.
  • the quantum dots may be I-III-VI
  • the single-core structure of the group compound semiconductor may also be a core-shell quantum dot formed by the group I-III-VI, specifically including but not limited to CuInS, AgInS, CuInS/ZnS, AnInS/ZnS.
  • the quantum dots may be group IV element semiconductors, such as Si, C, Graphene, and the like.
  • the quantum dots may be perovskite quantum dots or the like.
  • the thickness of the quantum dot light emitting layer 3 can be set with reference to the thickness of the quantum dot light emitting layer in a conventional quantum dot light emitting diode.
  • the material of 21 contains transition metal oxides.
  • the material of the hole injection layer 21 contains at least a transition metal oxide.
  • the material of the hole injection layer 21 is a transition metal oxide.
  • the transition metal oxide includes, but is not limited to, at least one of MoO 3 , WO 3 , V 2 O 5 , and Rb 2 O.
  • the transition metal oxide includes a component, such as one of MoO 3 , WO 3 , V 2 O 5 , and Rb 2 O; in some embodiments, the transition metal oxide Including two components, such as MoO 3 and WO 3 , MoO 3 and V 2 O 5 , WO 3 and Rb 2 O, WO 3 and V 2 O 5 ; in some embodiments, the transition metal oxide includes three Components such as MoO 3 and WO 3 and V 2 O 5 , MoO 3 and V 2 O 5 and Rb 2 O.
  • the thickness of the hole injection layer 21 can be set with reference to the thickness of the hole injection layer in the quantum dot light emitting diode.
  • the material of the hole transport layer 23 contains at least an organic hole transport material.
  • the material of the hole transport layer 23 is an organic hole transport material.
  • the organic hole-transporting material is an organic substance having a hole-transporting capability, which may be a small molecule and/or a polymer, including but not limited to at least one of CBP, TCTA, NPB, NPD, PVK, TFB .
  • the organic hole transport material includes a component, such as one of CBP, TCTA, NPB, NPD, PVK, and TFB; in some embodiments, the organic hole transport material includes Two components, such as CBP and TCTA, CBP and NPB, TCTA and NPD, PVK and TFB; in some embodiments, the organic hole transport material includes three components, such as CBP and TCTA and TFB, CBP and NPB and NPD, TCTA and NPD and PVK.
  • the thickness of the hole transport layer 23 can be set with reference to the thickness of the hole injection layer in the quantum dot light emitting diode.
  • an interface layer 22 is provided between the hole injection layer 21 and the hole transport layer 23.
  • the setting of the interface layer can block the direct contact between the transition metal oxide in the hole injection layer 21 and the organic hole transport material in the hole transport layer 23, thereby weakening or even breaking the molecules of the organic hole transport material and the transition metal Strong C 2p -M 3d orbital hybridization between oxides.
  • the molecular orientation of the organic hole transport material molecule on the transition metal oxide surface is "upright”
  • the molecular orientation of the organic hole transport material molecule at the interface layer 22 Transformed into "pour-over type", which greatly reduces the molecular orientation angle.
  • the outermost layer of the organic hole transport material molecule is mainly the ⁇ orbital, which has a shielding effect on the ⁇ (CH) orbital, thereby improving the organic hole transport The HOMO energy level of the material.
  • the material of the interface layer 22 in the embodiment of the present application is a graphene material.
  • the graphene-based material can not only block the direct contact between the transition metal oxide in the hole injection layer 21 and the organic hole transport material in the hole transport layer 23; After the hole-transporting material enters the interface layer 22, the orientation of the organic hole-transporting material in the graphene-based material is "dumping type", thereby improving the HOMO energy level of the organic hole-transporting material.
  • the material of the interface layer 22 is selected from at least one of unmodified graphene, graphene oxide, reduced graphene oxide, and graphene quantum dots.
  • the material of the interface layer 22 is a material, such as one of unmodified graphene, graphene oxide, reduced graphene oxide, and graphene quantum dots; in some embodiments, the interface layer The materials of 22 are two materials, such as unmodified graphene and graphene oxide, reduced graphene oxide and graphene quantum dots; unmodified graphene and graphene quantum dots; in some embodiments, the interface layer 22 The materials are three or more kinds of materials, such as unmodified graphene and graphene oxide and graphene quantum dots. Wherein, the unmodified graphene is original graphene without any treatment on graphene; the reduced graphene oxide is graphene obtained by reducing graphene oxide.
  • the material of the interface layer 22 can increase the HOMO level of the organic hole transport material.
  • the material of the interface layer 22 is selected from reduced graphene oxide or graphene quantum dots. In some embodiments, the material of the interface layer 22 is selected from reduced graphene oxide and graphene quantum dots.
  • the reduced graphene oxide and the graphene quantum dots not only have good conductivity, but also have good light transmittance. As a material of the interface layer 22, since the material has a band gap, the light transmittance is good. Therefore, the quantum dot light emitting diode can emit light from the anode 1 side.
  • the conductivity of the unmodified graphene is good, the light transmittance is not quite as good as the reduced graphene oxide and the graphene quantum dots; while the graphene oxide can meet the requirements of light transmittance, it is conductive The performance is not as good as the reduced graphene oxide and the graphene quantum dots.
  • the thickness of the interface layer 22 is 1 nm to 30 nm. If the thickness of the interface layer 22 is too thick, it will cause an increase in resistance, which on the other hand reduces the light emitting performance of the quantum dot diode.
  • the material of the interface layer 22 is reduced graphene oxide, and the thickness of the interface layer 22 is 1 nm to 5 nm. Since the reduced graphene oxide is a large-sized sheet-like molecule, its planar direction generally has several hundred nanometers to several micrometers. Therefore, when the thickness of the formed interface layer 22 is large, defects such as wrinkles are inevitably generated, resulting in thin films Non-uniformity and non-density, which can easily cause device leakage and uneven light emission.
  • the material of the interface layer 22 is graphene quantum dots. Due to the small size of the graphene quantum dots in the plane direction, generally only a few tens of nanometers, it is easy to form a dense and uniform thin film. Therefore, in some embodiments, the thickness of the interface layer 22 is 2 nm to 15 nm. Improve the HOMO energy level of organic hole-transporting materials; and have a smaller resistance.
  • the material of the interface layer 22 is unmodified graphene, and the thickness of the interface layer 22 is less than or equal to 10 nm. Because the unmodified graphene has poor light transmittance, if it is too thick, it can still exert the effect of improving the HOMO level of the organic hole transport material. However, when it is used as the material of the interface layer 22, due to the poor light transmittance of the material, Not conducive to obtaining quantum dot light-emitting diodes that emit light from the anode.
  • the material of the interface layer 22 is graphene oxide.
  • Graphene oxide quantum dots have a band gap and good light transmittance.
  • the thickness of the interface layer 22 is 5 nm-10 nm. The film layer formed at this time can not only improve the HOMO level of the organic hole transport material; but also have a small resistance.
  • the quantum dot light emitting diode further includes an electronic functional layer 4 disposed between the cathode 5 and the quantum dot light emitting layer 3, and the electronic functional layer 4 includes an electron transport layer, an electron injection layer, and a hole blocking layer At least one layer.
  • the quantum dot light emitting diode includes an electron transport layer, and the electron transport layer is disposed between the cathode 5 and the quantum dot light emitting layer 3.
  • the quantum dot light emitting diode includes an electron transport layer and an electron injection layer, the electron injection layer is disposed adjacent to the cathode 5, and the electron transport layer is disposed adjacent to the quantum dot light emitting layer 3.
  • the quantum dot light emitting diode includes an electron transport layer, an electron injection layer, and a hole blocking layer, the electron injection layer is disposed adjacent to the cathode 5, and the hole blocks light emission adjacent to the quantum dot Layer 3 is provided, and the electron transport layer is provided between the electron injection layer and the hole blocking layer.
  • the quantum dot light emitting diode further includes an electron transport layer disposed between the cathode 5 and the quantum dot light emitting layer 3.
  • the material of the electron transport layer may be n-type inorganic metal oxides such as ZnO and TiO 2 ; it may also be an organic electron transport material such as Bphen, TmPyPb, TPBi, BCP, B3PYMPM, etc.; or a combination of the above organic/inorganic materials.
  • the quantum dot light-emitting diodes described in the examples of the present application can be prepared by the following method.
  • the second aspect of the embodiments of the present application provides a method for manufacturing a quantum dot light emitting diode, including the following steps:
  • An interface layer is prepared between the hole transport layer and the hole injection layer, wherein the hole injection layer is disposed adjacent to the anode, and the material of the hole injection layer contains a transition metal oxide; the hole transport The layer is disposed adjacent to the quantum dot light-emitting layer, and the material of the hole transport layer contains an organic hole transport material; the material of the interface layer is a graphene-based material.
  • the preparation method of the quantum dot light-emitting diode provided by the embodiment of the present application can be realized only by preparing the interface layer between the hole transport layer and the hole injection layer based on the preparation method of the conventional quantum dot light-emitting diode, and the method is simple Controllable.
  • a substrate with a surface layer as a hole transport layer or a hole injection layer is provided, and an interface material is deposited on the hole transport layer of the substrate to form an interface layer.
  • the material of the interface layer is selected from at least one of unmodified graphene, graphene oxide, reduced graphene oxide, and graphene quantum dots.
  • the material of the interface layer is a material, such as one of unmodified graphene, graphene oxide, reduced graphene oxide, and graphene quantum dots; in some embodiments, all The materials of the interface layer are two kinds of materials, such as unmodified graphene and graphene oxide, reduced graphene oxide and graphene quantum dots; unmodified graphene and graphene quantum dots; in some embodiments, the The materials of the interface layer are three or more materials, such as unmodified graphene, graphene oxide, and graphene quantum dots.
  • an interface material is deposited on the hole transport layer of the substrate by a solution processing method to form an interface layer.
  • the material of the interface layer is reduced graphene oxide
  • the preparation method of the interface layer is to deposit reduced oxidation on the substrate where the surface layer is a hole transport layer or a hole injection layer
  • the graphene solution is dried to obtain the interface layer.
  • the material of the interface layer is reduced graphene oxide.
  • the preparation method of the interface layer is: depositing a graphene oxide solution on a substrate whose surface layer is a hole injection layer at a temperature of Annealing treatment under the condition of 150°C ⁇ 180°C to obtain the interface layer. By annealing at a temperature of 150°C to 180°C, graphene oxide and transition metal oxide form an M-O-C bond (M refers to a transition metal atom), causing graphene oxide to be reduced.
  • M refers to a transition metal atom
  • the substrate where the surface layer is a hole transport layer or a hole injection layer includes two cases.
  • the substrate is a substrate whose surface layer is a hole injection layer.
  • the substrate includes at least an anode and a hole injection layer provided on the anode.
  • the anode may be provided on the substrate.
  • after preparing the interface layer it also includes preparing a hole transport layer on the interface layer, preparing a quantum dot light emitting layer on the hole transport layer, and preparing a cathode on the quantum dot light emitting layer.
  • the cathode is prepared on the electronic functional layer.
  • the cathode and the anode are prepared by evaporation
  • the hole injection layer may be prepared by evaporation or solution processing, and in some embodiments, other layers are prepared by solution processing.
  • the substrate is a substrate whose surface layer is a hole transport layer.
  • the substrate includes at least a cathode, a quantum dot light emitting layer provided on the cathode, and a hole transport layer prepared on the quantum dot light emitting layer.
  • it before preparing the quantum dot light emitting layer, it further includes preparing an electronic functional layer on the cathode.
  • the cathode electrode may be provided on the substrate.
  • after preparing the interface layer it further includes preparing a hole injection layer on the interface layer and preparing an anode on the hole injection layer.
  • the cathode and the anode are prepared by evaporation.
  • the hole injection layer may be prepared by evaporation or solution processing. In some embodiments, other layers are prepared by solution processing.
  • a preparation method of quantum dot light-emitting diode includes the following steps:
  • the transparent conductive thin film ITO is used as the anode, and the thickness of the anode is 50 nm;
  • PVK is deposited on the interface layer by a solution processing method, and annealed at 150° C. for 30 minutes to prepare an organic hole transport layer, the thickness of the organic hole transport layer is 20 nm;
  • a solution processing method is used to deposit CdSe/ZnS on the organic hole transport layer, and annealed at 100°C for 30 minutes to prepare a quantum dot light emitting layer, and the thickness of the quantum dot light emitting layer is 25 nm;
  • the solution processing method was used to deposit ZnO nanoparticles on the quantum dot light-emitting layer by the solution method, and annealed at 80°C for 30 minutes to prepare an electron transport layer with a thickness of 30 nm;
  • Al was vapor-deposited on the electron transport layer as a cathode, and the thickness of the cathode was 100 nm.
  • a preparation method of quantum dot light-emitting diode includes the following steps:
  • the transparent conductive thin film ITO is used as the anode, and the thickness of the anode is 50 nm;
  • a solution processing method is used to deposit V 2 O 5 nanoparticles on the anode, and annealed at 100° C. for 30 minutes to prepare a hole injection layer with a thickness of 30 nm;
  • the solution processing method is used to deposit graphene oxide on the hole injection layer, and annealed at 180°C for 60 minutes to prepare an interface layer, the thickness of the interface layer is 3 nm;
  • PVK is deposited on the interface layer by a solution processing method, and annealed at 150° C. for 30 minutes to prepare an organic hole transport layer, the thickness of the organic hole transport layer is 20 nm;
  • a solution processing method is used to deposit CdSe/ZnS on the organic hole transport layer, and annealed at 100°C for 30 minutes to prepare a quantum dot light emitting layer, and the thickness of the quantum dot light emitting layer is 25 nm;
  • the solution processing method was used to deposit ZnO nanoparticles on the quantum dot light-emitting layer by the solution method, and annealed at 80°C for 30 minutes to prepare an electron transport layer with a thickness of 30 nm;
  • Al was vapor-deposited on the electron transport layer as a cathode, and the thickness of the cathode was 100 nm.
  • a preparation method of quantum dot light-emitting diode includes the following steps:
  • the transparent conductive thin film ITO is used as the anode, and the thickness of the anode is 50 nm;
  • a solution processing method is used to deposit V 2 O 5 nanoparticles on the anode, and annealed at 100° C. for 30 minutes to prepare a hole injection layer with a thickness of 30 nm;
  • PVK is deposited on the interface layer by a solution processing method, and annealed at 150° C. for 30 minutes to prepare an organic hole transport layer, the thickness of the organic hole transport layer is 20 nm;
  • a solution processing method is used to deposit CdSe/ZnS on the organic hole transport layer, and annealed at 100°C for 30 minutes to prepare a quantum dot light emitting layer, and the thickness of the quantum dot light emitting layer is 25 nm;
  • the solution processing method was used to deposit ZnO nanoparticles on the quantum dot light-emitting layer by the solution method, and annealed at 80°C for 30 minutes to prepare an electron transport layer with a thickness of 30 nm;
  • Al was vapor-deposited on the electron transport layer as a cathode, and the thickness of the cathode was 100 nm.

Abstract

Provided is a quantum dot light-emitting diode, comprising an anode and a cathode provided oppositely, a quantum dot light-emitting layer provided between the anode and the cathode, and a hole function stack layer provided between the anode and the quantum dot light-emitting layer, the hole function stack layer comprises a hole injection layer, a hole transport layer provided on the hole injection layer, and an interface layer provided between the hole injection layer and the hole transport layer, wherein the hole injection layer is provided adjacent to the anode, and the material of the hole injection layer contains a transition metal oxide; the hole transport layer is provided adjacent to the quantum dot light-emitting layer, and the material of the hole transport layer contains organic hole transport material; and the material of the interface layer is graphene-based material.

Description

量子点发光二极管及其制备方法Quantum dot light emitting diode and preparation method thereof 技术领域Technical field
本申请属于光电显示技术领域，尤其涉及一种量子点发光二极管及其制备方法。The present application belongs to the technical field of photoelectric display, and in particular relates to a quantum dot light-emitting diode and a preparation method thereof.
背景技术Background technique
由于量子点独特的光电性质，例如发光波长随尺寸和成分连续可调、发光光谱窄、荧光效率高、稳定性好等，基于量子点的电致发光二极管(QLED)在显示领域得到广泛的关注和研究。此外，QLED显示还具有可视角大、对比度高、响应速度快、可柔性等诸多LCD所无法实现的优势，因而有望成为下一代的显示技术。Due to the unique photoelectric properties of quantum dots, such as continuously adjustable emission wavelength with size and composition, narrow emission spectrum, high fluorescence efficiency, and good stability, quantum dot-based electroluminescent diodes (QLEDs) have received widespread attention in the display field And research. In addition, QLED display also has many advantages that cannot be realized by LCD, such as large viewing angle, high contrast, fast response speed, and flexibility, so it is expected to become the next generation of display technology.
经过几十年的发展，QLED的性能取得了很大的提高，已经步入商业化的轨道，但一些瓶颈也愈发凸显，制约着QLED的发展。其中一个严重的问题就是空穴和电子不平衡，电子在量子点发光层过量，导致量子点荧光猝灭以及俄歇复合，严重制约QLED的使用寿命。而导致QLED电子空穴不平衡的根源在于：金属氧化物电子传输层（尤其是ZnO）的导带底能级与量子点的导带底能级接近，电子注入势垒很小；而有机空穴传输层的HOMO能级与量子点价带顶能级差距较大，一般>0.5eV以上；能级的不匹配导致电子更容易注入到量子点发光层。此外，金属氧化物的电子迁移率一般也大于有机空穴传输材料的空穴迁移率，更加剧了这种现象。因此，减小空穴传输层与量子点发光层之间的能级差距至关重要。After decades of development, the performance of QLED has been greatly improved, and has entered the track of commercialization, but some bottlenecks have become more prominent, restricting the development of QLED. One of the serious problems is the imbalance of holes and electrons. Excessive electrons in the quantum dot light-emitting layer lead to quantum dot fluorescence quenching and Auger recombination, which seriously restricts the service life of QLED. The root cause of the QLED electron hole imbalance is that the bottom energy level of the conduction band of the metal oxide electron transport layer (especially ZnO) is close to the bottom energy level of the conduction band of quantum dots, and the electron injection barrier is very small; The gap between the HOMO energy level of the hole transport layer and the top energy level of the quantum dot valence band is large, generally >0.5eV or more; mismatches in the energy levels result in easier injection of electrons into the quantum dot light-emitting layer. In addition, the electron mobility of metal oxides is generally greater than the hole mobility of organic hole transport materials, which exacerbates this phenomenon. Therefore, it is important to reduce the energy gap between the hole transport layer and the quantum dot light-emitting layer.
当前，过渡金属氧化物因其独有的高功函数特性而被广泛用于空穴注入材料，它能够在阳极/空穴传输层界面形成有效的欧姆接触，大大提高空穴从阳极至空穴传输层的注入效率。但是，另一方面，过渡金属原子与有机空穴传输材料之间存在强烈的C2p-M3d轨道杂化（M指金属），使得有机物的HOMO能级与过渡金属氧化物的费米能级相近，难以继续提高有机空穴传输材料的HOMO能级。因此，只有打破或减弱这种强烈的C2p-M3d轨道杂化，才能够继续提高有机空穴传输材料的HOMO能级，从而减小空穴传输层/量子点发光层之间的空穴注入势垒。Currently, transition metal oxides are widely used as hole injection materials because of their unique high work function characteristics. It can form an effective ohmic contact at the anode/hole transport layer interface, greatly improving the hole from anode to hole Transport layer injection efficiency. However, on the other hand, there is a strong C2p-M3d orbital hybridization (M refers to metal) between the transition metal atom and the organic hole transport material, making the HOMO energy level of the organic matter close to the Fermi energy level of the transition metal oxide, It is difficult to continue to increase the HOMO energy level of organic hole transport materials. Therefore, only by breaking or weakening this strong C2p-M3d orbital hybridization can we continue to increase the HOMO level of the organic hole transport material, thereby reducing the hole injection potential between the hole transport layer/quantum dot light emitting layer base.
技术问题technical problem
本申请实施例提供了一种量子点发光二极管及其制备方法，以解决现有的量子点发光二极管过渡金属原子与有机空穴传输材料之间存在强烈的C 2p-M 3d轨道杂化，难以继续提高有机空穴传输材料的HOMO能级的问题。 The embodiments of the present application provide a quantum dot light emitting diode and a preparation method thereof to solve the problem that there is a strong C 2p -M 3d orbital hybridization between the existing quantum dot light emitting diode transition metal atom and the organic hole transport material, which is difficult Continue to improve the HOMO energy level of organic hole transport materials.
技术解决方案Technical solution
本申请实施例是这样实现的，第一方面，提供了一种量子点发光二极管，包括相对设置的阳极和阴极，在所述阳极和所述阴极之间设置的量子点发光层，以及设置在所述阳极和所述量子点发光层之间的空穴功能叠层，所述空穴功能叠层包括空穴注入层、在所述空穴注入层上设置的空穴传输层以及设置在所述空穴注入层和所述空穴传输层之间的界面层，其中，所述空穴注入层邻近所述阳极设置，且所述空穴注入层的材料含有过渡金属氧化物；所述空穴传输层邻近所述量子点发光层设置，且所述空穴传输层的材料含有有机空穴传输材料；所述界面层的材料为石墨烯类材料。The embodiments of the present application are implemented in this way. In the first aspect, a quantum dot light emitting diode is provided, including an anode and a cathode disposed oppositely, a quantum dot light emitting layer disposed between the anode and the cathode, and a A hole function stack between the anode and the quantum dot light-emitting layer, the hole function stack includes a hole injection layer, a hole transport layer provided on the hole injection layer, and a An interface layer between the hole injection layer and the hole transport layer, wherein the hole injection layer is disposed adjacent to the anode, and the material of the hole injection layer contains a transition metal oxide; the void The hole transport layer is disposed adjacent to the quantum dot light-emitting layer, and the material of the hole transport layer contains an organic hole transport material; the material of the interface layer is a graphene-based material.
第二方面，提供了一种量子点发光二极管的制备方法，包括以下步骤：In a second aspect, a method for manufacturing a quantum dot light-emitting diode is provided, including the following steps:
在空穴传输层和空穴注入层之间制备界面层，其中，所述空穴注入层邻近所述阳极设置，且所述空穴注入层的材料含有过渡金属氧化物；所述空穴传输层邻近所述量子点发光层设置，且所述空穴传输层的材料含有有机空穴传输材料；所述界面层的材料为石墨烯类材料。An interface layer is prepared between the hole transport layer and the hole injection layer, wherein the hole injection layer is disposed adjacent to the anode, and the material of the hole injection layer contains a transition metal oxide; the hole transport The layer is disposed adjacent to the quantum dot light-emitting layer, and the material of the hole transport layer contains an organic hole transport material; the material of the interface layer is a graphene-based material.
有益效果Beneficial effect
本申请提供的量子点发光二极管，在所述空穴注入层和所述空穴传输层之间设置界面层，且所述界面层的材料为石墨烯类材料。具有该结构的量子点发光二极管，界面层的设置可以减弱甚至打破有机空穴传输材料分子与过渡金属氧化物之间强烈的C 2p-M 3d轨道杂化；同时，相对于有机空穴传输材料分子在过渡金属氧化物表面的分子取向为“直立型”的情况，采用石墨烯类材料作为界面层后，有机空穴传输材料分子在所述界面层的分子取向转变为“倾倒型”，从而使得分子取向角大幅减小，此时，有机空穴传输材料分子最外层主要为Π轨道，对σ(C-H)轨道有屏蔽作用，从而提高了有机空穴传输材料的HOMO能级，降低空穴传输层/量子点发光层之间的空穴注入势垒，提高空穴的数量和注入效率，促进电荷平衡，进一步提高QLED的性能。 In the quantum dot light emitting diode provided by the present application, an interface layer is provided between the hole injection layer and the hole transport layer, and the material of the interface layer is a graphene-based material. In the quantum dot light-emitting diode with this structure, the arrangement of the interface layer can weaken or even break the strong C 2p -M 3d orbital hybridization between the organic hole transport material molecule and the transition metal oxide; meanwhile, compared with the organic hole transport material When the molecular orientation of the transition metal oxide surface is "upright", after the graphene-based material is used as the interface layer, the molecular orientation of the organic hole transport material molecules at the interface layer changes to "poured type", thereby The molecular orientation angle is greatly reduced. At this time, the outermost layer of the organic hole transport material molecule is mainly the Π orbital, which has a shielding effect on the σ(CH) orbital, thereby increasing the HOMO energy level of the organic hole transport material and reducing the space. The hole injection barrier between the hole transport layer/quantum dot light emitting layer improves the number of holes and injection efficiency, promotes charge balance, and further improves the performance of QLED.
本申请提供的量子点发光二极管的制备方法，只需在常规量子点发光二极管的制备方法的基础上，在空穴传输层和空穴注入层之间制备界面层即可实现，方法简单可控。The preparation method of the quantum dot light-emitting diode provided by the present application can be realized only by preparing the interface layer between the hole transport layer and the hole injection layer on the basis of the preparation method of the conventional quantum dot light-emitting diode, and the method is simple and controllable .
附图说明BRIEF DESCRIPTION
图1是本申请实施例提供的空穴功能叠层的结构示意图；1 is a schematic structural diagram of a hole function stack provided by an embodiment of the present application;
图2是本申请实施例提供的量子点发光二极管的结构示意图；2 is a schematic structural diagram of a quantum dot light emitting diode provided by an embodiment of the present application;
图3是本申请实施例提供的量子点发光二极管的制备方法流程示意图。3 is a schematic flow chart of a method for manufacturing a quantum dot light emitting diode provided by an embodiment of the present application.
本发明的实施方式Embodiments of the invention
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。In order to make the purpose, technical solutions and advantages of the present application more clear, the following describes the present application in further detail with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present application, and are not used to limit the present application.
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。In the description of the present application, it should be understood that the terms “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. Thus, the features defined as "first" and "second" may explicitly or implicitly include one or more of the features. In the description of this application, the meaning of "plurality" is two or more, unless otherwise specifically limited.
如图1所示，本申请实施例第一方面提供一种量子点发光二极管，包括相对设置的阳极1和阴极5，在阳极1和阴极5之间设置的量子点发光层3，以及设置在阳极1和量子点发光层3之间的空穴功能叠层2，空穴功能叠层2包括空穴注入层21在空穴注入层21上设置的空穴传输层23以及设置在空穴注入层21和空穴传输层23之间的界面层22，其中，所述空穴注入层21邻近阳极1设置，且空穴注入层21的材料含有过渡金属氧化物；空穴传输层23邻近量子点发光层3设置，且空穴传输层23的材料含有有机空穴传输材料；界面层22的材料为石墨烯类材料。As shown in FIG. 1, a first aspect of an embodiment of the present application provides a quantum dot light emitting diode, including an anode 1 and a cathode 5 disposed oppositely, a quantum dot light emitting layer 3 disposed between the anode 1 and the cathode 5, and disposed at A hole function stack 2 between the anode 1 and the quantum dot light emitting layer 3, the hole function stack 2 includes a hole injection layer 21, a hole transport layer 23 provided on the hole injection layer 21, and a hole injection An interface layer 22 between the layer 21 and the hole transport layer 23, wherein the hole injection layer 21 is disposed adjacent to the anode 1, and the material of the hole injection layer 21 contains a transition metal oxide; the hole transport layer 23 is adjacent to quantum The point light emitting layer 3 is provided, and the material of the hole transport layer 23 contains an organic hole transport material; the material of the interface layer 22 is a graphene-based material.
本申请实施例提供的量子点发光二极管，在所述空穴注入层和所述空穴传输层之间设置界面层，且所述界面层的材料为石墨烯类材料。具有该结构的量子点发光二极管，界面层的设置可以减弱甚至打破有机空穴传输材料分子与过渡金属氧化物之间强烈的C 2p-M 3d轨道杂化；同时，相对于有机空穴传输材料分子在过渡金属氧化物表面的分子取向为“直立型”的情况，采用石墨烯类材料作为界面层后，有机空穴传输材料分子在所述界面层的分子取向转变为“倾倒型”，从而使得分子取向角大幅减小，此时，有机空穴传输材料分子最外层主要为Π轨道，对σ(C-H)轨道有屏蔽作用，从而提高了有机空穴传输材料的HOMO能级，降低空穴传输层/量子点发光层之间的空穴注入势垒，提高空穴的数量和注入效率，促进电荷平衡，进一步提高QLED的性能。 In the quantum dot light emitting diode provided by the embodiment of the present application, an interface layer is provided between the hole injection layer and the hole transport layer, and the material of the interface layer is a graphene-based material. In the quantum dot light-emitting diode with this structure, the arrangement of the interface layer can weaken or even break the strong C 2p -M 3d orbital hybridization between the organic hole transport material molecule and the transition metal oxide; meanwhile, compared with the organic hole transport material When the molecular orientation of the transition metal oxide surface is "upright", after the graphene-based material is used as the interface layer, the molecular orientation of the organic hole transport material molecules at the interface layer changes to "poured type", thereby The molecular orientation angle is greatly reduced. At this time, the outermost layer of the organic hole transport material molecule is mainly the Π orbital, which has a shielding effect on the σ(CH) orbital, thereby improving the HOMO energy level of the organic hole transport material and reducing The hole injection barrier between the hole transport layer/quantum dot light emitting layer improves the number of holes and injection efficiency, promotes charge balance, and further improves the performance of QLED.
具体的，本申请实施例中，所述量子点发光二极管还可以包括基板10。基板10可以选择常规的衬底材料，包括柔性基板和硬质基板，如玻璃基板。Specifically, in the embodiment of the present application, the quantum dot light emitting diode may further include a substrate 10. The substrate 10 may be selected from conventional substrate materials, including flexible substrates and hard substrates, such as glass substrates.
根据基板10设置位置的不同，所述量子点发光二极管可以分为正置型量子点发光二极管和倒置型量子点发光二极管。其中，所述正置型量子点发光二极管中，阳极1设置在基板10上；所述倒置型量子点发光二极管中，阴极5设置在基板10上。According to different positions of the substrate 10, the quantum dot light-emitting diodes can be classified into an upright type quantum dot light-emitting diode and an inverted type quantum dot light-emitting diode. Among them, in the upright type quantum dot light emitting diode, the anode 1 is provided on the substrate 10; in the upside down type quantum dot light emitting diode, the cathode 5 is provided on the substrate 10.
所述量子点发光二极管包括相对设置的阳极1和阴极5，阳极1和阴极5的材料选择及其厚度范围，可以参照常规量子点发光二极管进行设定。The quantum dot light-emitting diode includes an anode 1 and a cathode 5 disposed oppositely. The material selection and thickness range of the anode 1 and the cathode 5 can be set with reference to a conventional quantum dot light-emitting diode.
所述量子点发光二极管中，在阳极1和阴极5之间设置的量子点发光层3，量子点发光层3中至少含有量子点。在一些实施例中，所述量子点可以是II-VI族化合物半导体的单核结构，也可以是II-VI族形成的核壳量子点，具体包括但不限于CdSe、ZnCdS、CdSeS、ZnCdSeS、CdSe/ZnS、CdSeS/ZnS、CdSe/CdS、CdSe/CdS/ZnS、ZnCdS/ZnS、CdS/ZnS或ZnCdSeS/ZnS。在一些实施例中，所述量子点可以是III-V族化合物半导体的单核结构，也可以是III-V族形成的核壳量子点，具体包括但不限于GaAs、GaN、InP、InP/ZnS。在一些实施例中，所述量子点可以是I-III-VI 族化合物半导体的单核结构，也可以是I-III-VI 族形成的核壳量子点，具体包括但不限于CuInS、AgInS、CuInS/ZnS、AnInS/ZnS。在一些实施例中，所述量子点可以是IV族单质半导体，如Si、C、Graphene等。在一些实施例中，所述量子点可以是钙钛矿量子点等。In the quantum dot light emitting diode, the quantum dot light emitting layer 3 provided between the anode 1 and the cathode 5 contains at least quantum dots. In some embodiments, the quantum dot may be a single-core structure of a group II-VI compound semiconductor or a core-shell quantum dot formed by a group II-VI, specifically including but not limited to CdSe, ZnCdS, CdSeS, ZnCdSeS, CdSe/ZnS, CdSeS/ZnS, CdSe/CdS, CdSe/CdS/ZnS, ZnCdS/ZnS, CdS/ZnS or ZnCdSeS/ZnS. In some embodiments, the quantum dot may be a single-core structure of a group III-V compound semiconductor or a core-shell quantum dot formed by a group III-V, specifically including but not limited to GaAs, GaN, InP, InP/ ZnS. In some embodiments, the quantum dots may be I-III-VI The single-core structure of the group compound semiconductor may also be a core-shell quantum dot formed by the group I-III-VI, specifically including but not limited to CuInS, AgInS, CuInS/ZnS, AnInS/ZnS. In some embodiments, the quantum dots may be group IV element semiconductors, such as Si, C, Graphene, and the like. In some embodiments, the quantum dots may be perovskite quantum dots or the like.
量子点发光层3的厚度，可以参照常规的量子点发光二极管中量子点发光层的厚度进行设定。The thickness of the quantum dot light emitting layer 3 can be set with reference to the thickness of the quantum dot light emitting layer in a conventional quantum dot light emitting diode.
本申请实施例中，在阳极1和量子点发光层3之间的空穴功能叠层2，具体的，如图2所示，空穴功能叠层2包括空穴注入层21在空穴注入层21上设置的空穴传输层23以及设置在空穴注入层21和空穴传输层23之间的界面层22，其中，所述空穴注入层21邻近阳极1设置，且空穴注入层21的材料含有过渡金属氧化物。In the embodiment of the present application, the hole function stack 2 between the anode 1 and the quantum dot light-emitting layer 3, specifically, as shown in FIG. 2, the hole function stack 2 includes a hole injection layer 21 that is injected into the hole A hole transport layer 23 provided on the layer 21 and an interface layer 22 provided between the hole injection layer 21 and the hole transport layer 23, wherein the hole injection layer 21 is provided adjacent to the anode 1, and the hole injection layer The material of 21 contains transition metal oxides.
其中，空穴注入层21的材料中至少含有过渡金属氧化物，在一些实施例中，空穴注入层21的材料为过渡金属氧化物。具体的，所述过渡金属氧化物包括但不限于MoO 3、WO 3、V 2O 5、Rb 2O中的至少一种。在一些实施例中，所述过渡金属氧化物包括一种组分，如MoO 3、WO 3、V 2O 5、Rb 2O中的一种；在一些实施例中，所述过渡金属氧化物包括两种组分，如MoO 3和WO 3，MoO 3和V 2O 5、WO 3和Rb 2O、WO 3和V 2O 5；在一些实施例中，所述过渡金属氧化物包括三种组分，如MoO 3和WO 3和V 2O 5，MoO 3和V 2O 5和Rb 2O。空穴注入层21的厚度，可以参考量子点发光二极管中空穴注入层的厚度进行设定。 Wherein, the material of the hole injection layer 21 contains at least a transition metal oxide. In some embodiments, the material of the hole injection layer 21 is a transition metal oxide. Specifically, the transition metal oxide includes, but is not limited to, at least one of MoO 3 , WO 3 , V 2 O 5 , and Rb 2 O. In some embodiments, the transition metal oxide includes a component, such as one of MoO 3 , WO 3 , V 2 O 5 , and Rb 2 O; in some embodiments, the transition metal oxide Including two components, such as MoO 3 and WO 3 , MoO 3 and V 2 O 5 , WO 3 and Rb 2 O, WO 3 and V 2 O 5 ; in some embodiments, the transition metal oxide includes three Components such as MoO 3 and WO 3 and V 2 O 5 , MoO 3 and V 2 O 5 and Rb 2 O. The thickness of the hole injection layer 21 can be set with reference to the thickness of the hole injection layer in the quantum dot light emitting diode.
空穴传输层23的材料中至少含有有机空穴传输材料，在一些实施例中，空穴传输层23的材料为有机空穴传输材料。具体的，所述有机空穴传输材料为具有空穴传输能力的有机物，可以为小分子和/或聚合物，具体包括但不限于CBP、TCTA、NPB、NPD、PVK、TFB中的至少一种。在一些实施例中，所述有机空穴传输材料包括一种组分，如CBP、TCTA、NPB、NPD、PVK、TFB中的一种；在一些实施例中，所述有机空穴传输材料包括两种组分，如CBP和TCTA、CBP和NPB、TCTA和NPD、PVK和TFB；在一些实施例中，所述有机空穴传输材料包括三种组分，如CBP和TCTA和TFB、CBP和NPB和NPD、TCTA和NPD和PVK。空穴传输层23的厚度，可以参考量子点发光二极管中空穴注入层的厚度进行设定。The material of the hole transport layer 23 contains at least an organic hole transport material. In some embodiments, the material of the hole transport layer 23 is an organic hole transport material. Specifically, the organic hole-transporting material is an organic substance having a hole-transporting capability, which may be a small molecule and/or a polymer, including but not limited to at least one of CBP, TCTA, NPB, NPD, PVK, TFB . In some embodiments, the organic hole transport material includes a component, such as one of CBP, TCTA, NPB, NPD, PVK, and TFB; in some embodiments, the organic hole transport material includes Two components, such as CBP and TCTA, CBP and NPB, TCTA and NPD, PVK and TFB; in some embodiments, the organic hole transport material includes three components, such as CBP and TCTA and TFB, CBP and NPB and NPD, TCTA and NPD and PVK. The thickness of the hole transport layer 23 can be set with reference to the thickness of the hole injection layer in the quantum dot light emitting diode.
本申请实施例中，在空穴注入层21和空穴传输层23之间设置界面层22。界面层的设置，可以阻隔空穴注入层21中的过渡金属氧化物和空穴传输层23中的有机空穴传输材料之间的直接接触，从而减弱甚至打破有机空穴传输材料分子与过渡金属氧化物之间强烈的C 2p-M 3d轨道杂化。同时，相对于有机空穴传输材料分子在过渡金属氧化物表面的分子取向为“直立型”的情况，采用石墨烯类材料作为界面层后，有机空穴传输材料分子在界面层22的分子取向转变为“倾倒型”，从而使得分子取向角大幅减小，此时，有机空穴传输材料分子最外层主要为Π轨道，对σ(C-H)轨道有屏蔽作用，从而提高了有机空穴传输材料的HOMO能级。 In the embodiment of the present application, an interface layer 22 is provided between the hole injection layer 21 and the hole transport layer 23. The setting of the interface layer can block the direct contact between the transition metal oxide in the hole injection layer 21 and the organic hole transport material in the hole transport layer 23, thereby weakening or even breaking the molecules of the organic hole transport material and the transition metal Strong C 2p -M 3d orbital hybridization between oxides. At the same time, relative to the case where the molecular orientation of the organic hole transport material molecule on the transition metal oxide surface is "upright", after the graphene-based material is used as the interface layer, the molecular orientation of the organic hole transport material molecule at the interface layer 22 Transformed into "pour-over type", which greatly reduces the molecular orientation angle. At this time, the outermost layer of the organic hole transport material molecule is mainly the Π orbital, which has a shielding effect on the σ(CH) orbital, thereby improving the organic hole transport The HOMO energy level of the material.
具体的，本申请实施例中的界面层22的材料为石墨烯类材料。所述石墨烯类材料作为界面层22的材料，不仅可以阻隔空穴注入层21中的过渡金属氧化物和空穴传输层23中的有机空穴传输材料之间的直接接触；而且，有机空穴传输材料进入界面层22后，有机空穴传输材料在石墨烯类材料中的取向为“倾倒型”，从而提高了有机空穴传输材料的HOMO能级。Specifically, the material of the interface layer 22 in the embodiment of the present application is a graphene material. As the material of the interface layer 22, the graphene-based material can not only block the direct contact between the transition metal oxide in the hole injection layer 21 and the organic hole transport material in the hole transport layer 23; After the hole-transporting material enters the interface layer 22, the orientation of the organic hole-transporting material in the graphene-based material is "dumping type", thereby improving the HOMO energy level of the organic hole-transporting material.
在一些实施例中，界面层22的材料选自未改性石墨烯、氧化石墨烯、还原的氧化石墨烯、石墨烯量子点中的至少一种。在一些实施例中，界面层22的材料为一种材料，如未改性石墨烯、氧化石墨烯、还原的氧化石墨烯、石墨烯量子点中的一种；在一些实施例中，界面层22的材料为两种材料，如未改性石墨烯和氧化石墨烯、还原的氧化石墨烯和石墨烯量子点；未改性石墨烯和石墨烯量子点；在一些实施例中，界面层22的材料为三种及以上种材料，如未改性石墨烯和氧化石墨烯和石墨烯量子点。其中，所述未改性石墨烯为没有对石墨烯进行过任何处理的原始石墨烯；所述还原的氧化石墨烯为将氧化石墨烯进行还原后获得的石墨烯。上述界面层22的材料，能够提高了有机空穴传输材料的HOMO能级。In some embodiments, the material of the interface layer 22 is selected from at least one of unmodified graphene, graphene oxide, reduced graphene oxide, and graphene quantum dots. In some embodiments, the material of the interface layer 22 is a material, such as one of unmodified graphene, graphene oxide, reduced graphene oxide, and graphene quantum dots; in some embodiments, the interface layer The materials of 22 are two materials, such as unmodified graphene and graphene oxide, reduced graphene oxide and graphene quantum dots; unmodified graphene and graphene quantum dots; in some embodiments, the interface layer 22 The materials are three or more kinds of materials, such as unmodified graphene and graphene oxide and graphene quantum dots. Wherein, the unmodified graphene is original graphene without any treatment on graphene; the reduced graphene oxide is graphene obtained by reducing graphene oxide. The material of the interface layer 22 can increase the HOMO level of the organic hole transport material.
从量子点发光二极管的出光方向和材料导电性考虑，在一些实施例中，界面层22的材料选自还原的氧化石墨烯或石墨烯量子点。在一些实施例中，界面层22的材料选自还原的氧化石墨烯和石墨烯量子点。所述还原的氧化石墨烯、所述石墨烯量子点不仅具有较好的导电性，而且透光性较好，以其作为界面层22的材料，由于材料具有带隙，透光性较好，因此可以实现量子点发光二极管从阳极1一侧出光。所述未改性石墨烯导电性虽好，但透光性相当不如所述还原的氧化石墨烯、所述石墨烯量子点好；而所述氧化石墨烯虽然能够满足透光性要求，但导电性不如所述还原的氧化石墨烯、所述石墨烯量子点好。Considering the light emitting direction of the quantum dot light emitting diode and the material conductivity, in some embodiments, the material of the interface layer 22 is selected from reduced graphene oxide or graphene quantum dots. In some embodiments, the material of the interface layer 22 is selected from reduced graphene oxide and graphene quantum dots. The reduced graphene oxide and the graphene quantum dots not only have good conductivity, but also have good light transmittance. As a material of the interface layer 22, since the material has a band gap, the light transmittance is good. Therefore, the quantum dot light emitting diode can emit light from the anode 1 side. Although the conductivity of the unmodified graphene is good, the light transmittance is not quite as good as the reduced graphene oxide and the graphene quantum dots; while the graphene oxide can meet the requirements of light transmittance, it is conductive The performance is not as good as the reduced graphene oxide and the graphene quantum dots.
本申请实施例中，界面层22的厚度为1nm~30nm。若界面层22的厚度过厚，会导致电阻增加，从而从另一方面降低量子点二极管的发光性能。In the embodiment of the present application, the thickness of the interface layer 22 is 1 nm to 30 nm. If the thickness of the interface layer 22 is too thick, it will cause an increase in resistance, which on the other hand reduces the light emitting performance of the quantum dot diode.
在一些实施例中，界面层22的材料为还原的氧化石墨烯，界面层22的厚度为1nm~5nm。由于所述还原的氧化石墨烯为大尺寸片状分子，其平面方向一般具有几百纳米至数微米，因此，当形成的界面层22厚度较大时，不可避免地产生褶皱等缺陷，造成薄膜不均匀、不致密，进而容易造成器件漏电以及发光不均匀的问题。In some embodiments, the material of the interface layer 22 is reduced graphene oxide, and the thickness of the interface layer 22 is 1 nm to 5 nm. Since the reduced graphene oxide is a large-sized sheet-like molecule, its planar direction generally has several hundred nanometers to several micrometers. Therefore, when the thickness of the formed interface layer 22 is large, defects such as wrinkles are inevitably generated, resulting in thin films Non-uniformity and non-density, which can easily cause device leakage and uneven light emission.
在一些实施例中，界面层22的材料为石墨烯量子点。由于石墨烯量子点平面方向尺寸小，一般只有几十纳米，容易形成致密、均匀的薄膜，因此，在一些实施例中，界面层22的厚度为2nm~15nm，此时形成的膜层不仅能够提高有机空穴传输材料的HOMO能级；而且具有较小的电阻。In some embodiments, the material of the interface layer 22 is graphene quantum dots. Due to the small size of the graphene quantum dots in the plane direction, generally only a few tens of nanometers, it is easy to form a dense and uniform thin film. Therefore, in some embodiments, the thickness of the interface layer 22 is 2 nm to 15 nm. Improve the HOMO energy level of organic hole-transporting materials; and have a smaller resistance.
在一些实施例中，界面层22的材料为未改性石墨烯，界面层22的厚度小于等于10nm。由于未改性石墨烯透光性较差，若厚度过厚，仍然能够发挥提高有机空穴传输材料的HOMO能级的效果，但采用其作为界面层22的材料时，由于材料透光性差，不利于获得从阳极出光的量子点发光二极管。In some embodiments, the material of the interface layer 22 is unmodified graphene, and the thickness of the interface layer 22 is less than or equal to 10 nm. Because the unmodified graphene has poor light transmittance, if it is too thick, it can still exert the effect of improving the HOMO level of the organic hole transport material. However, when it is used as the material of the interface layer 22, due to the poor light transmittance of the material, Not conducive to obtaining quantum dot light-emitting diodes that emit light from the anode.
在一些实施例中，界面层22的材料为氧化石墨烯。氧化石墨烯量子点具有带隙，透光性较好。在一些实施例中，界面层22的厚度为5nm~10nm。此时形成的膜层不仅能够提高有机空穴传输材料的HOMO能级；而且具有较小的电阻。In some embodiments, the material of the interface layer 22 is graphene oxide. Graphene oxide quantum dots have a band gap and good light transmittance. In some embodiments, the thickness of the interface layer 22 is 5 nm-10 nm. The film layer formed at this time can not only improve the HOMO level of the organic hole transport material; but also have a small resistance.
本申请实施例中，所述量子点发光二极管还包括设置在阴极5和量子点发光层3之间的电子功能层4，电子功能层4包括电子传输层、电子注入层、空穴阻挡层中的至少一层。具体地，在一实施例中，所述量子点发光二极管包括电子传输层，所述电子传输层设置在所述阴极5和所述量子点发光层3之间。在一实施例中，所述量子点发光二极管包括电子传输层、电子注入层，所述电子注入层邻近所述阴极5设置，所述电子传输层邻近所述量子点发光层3设置。在另一实施例中，所述量子点发光二极管包括电子传输层、电子注入层、空穴阻挡层，所述电子注入层邻近所述阴极5设置，所述空穴阻挡邻近所述量子点发光层3设置，所述电子传输层设于所述电子注入层与所述空穴阻挡层之间。In the embodiment of the present application, the quantum dot light emitting diode further includes an electronic functional layer 4 disposed between the cathode 5 and the quantum dot light emitting layer 3, and the electronic functional layer 4 includes an electron transport layer, an electron injection layer, and a hole blocking layer At least one layer. Specifically, in an embodiment, the quantum dot light emitting diode includes an electron transport layer, and the electron transport layer is disposed between the cathode 5 and the quantum dot light emitting layer 3. In one embodiment, the quantum dot light emitting diode includes an electron transport layer and an electron injection layer, the electron injection layer is disposed adjacent to the cathode 5, and the electron transport layer is disposed adjacent to the quantum dot light emitting layer 3. In another embodiment, the quantum dot light emitting diode includes an electron transport layer, an electron injection layer, and a hole blocking layer, the electron injection layer is disposed adjacent to the cathode 5, and the hole blocks light emission adjacent to the quantum dot Layer 3 is provided, and the electron transport layer is provided between the electron injection layer and the hole blocking layer.
在一些实施例中，所述量子点发光二极管还包括设置在阴极5和量子点发光层3之间的电子传输层。电子传输层的材料可以为ZnO、TiO 2等n型无机金属氧化物；也可以为有机电子传输材料，如Bphen、TmPyPb、TPBi、BCP、B3PYMPM等；还可以上述有机/无机材料的复合。 In some embodiments, the quantum dot light emitting diode further includes an electron transport layer disposed between the cathode 5 and the quantum dot light emitting layer 3. The material of the electron transport layer may be n-type inorganic metal oxides such as ZnO and TiO 2 ; it may also be an organic electron transport material such as Bphen, TmPyPb, TPBi, BCP, B3PYMPM, etc.; or a combination of the above organic/inorganic materials.
本申请实施例所述量子点发光二极管可以通过下述方法制备获得。The quantum dot light-emitting diodes described in the examples of the present application can be prepared by the following method.
相应的，如图3所示，本申请实施例第二方面提供一种量子点发光二极管的制备方法，包括以下步骤：Correspondingly, as shown in FIG. 3, the second aspect of the embodiments of the present application provides a method for manufacturing a quantum dot light emitting diode, including the following steps:
在空穴传输层和空穴注入层之间制备界面层，其中，所述空穴注入层邻近所述阳极设置，且所述空穴注入层的材料含有过渡金属氧化物；所述空穴传输层邻近所述量子点发光层设置，且所述空穴传输层的材料含有有机空穴传输材料；所述界面层的材料为石墨烯类材料。An interface layer is prepared between the hole transport layer and the hole injection layer, wherein the hole injection layer is disposed adjacent to the anode, and the material of the hole injection layer contains a transition metal oxide; the hole transport The layer is disposed adjacent to the quantum dot light-emitting layer, and the material of the hole transport layer contains an organic hole transport material; the material of the interface layer is a graphene-based material.
本申请实施例提供的量子点发光二极管的制备方法，只需在常规量子点发光二极管的制备方法的基础上，在空穴传输层和空穴注入层之间制备界面层即可实现，方法简单可控。The preparation method of the quantum dot light-emitting diode provided by the embodiment of the present application can be realized only by preparing the interface layer between the hole transport layer and the hole injection layer based on the preparation method of the conventional quantum dot light-emitting diode, and the method is simple Controllable.
具体的，提供表层为空穴传输层或空穴注入层的基底，在所述基底的空穴传输层上沉积界面材料，形成界面层。所述界面层的材料选自未改性石墨烯、氧化石墨烯、还原的氧化石墨烯、石墨烯量子点中的至少一种。在一些实施例中，所述界面层的材料为一种材料，如未改性石墨烯、氧化石墨烯、还原的氧化石墨烯、石墨烯量子点中的一种；在一些实施例中，所述界面层的材料为两种材料，如未改性石墨烯和氧化石墨烯、还原的氧化石墨烯和石墨烯量子点；未改性石墨烯和石墨烯量子点；在一些实施例中，所述界面层的材料为三种及以上种材料，如未改性石墨烯和氧化石墨烯和石墨烯量子点。Specifically, a substrate with a surface layer as a hole transport layer or a hole injection layer is provided, and an interface material is deposited on the hole transport layer of the substrate to form an interface layer. The material of the interface layer is selected from at least one of unmodified graphene, graphene oxide, reduced graphene oxide, and graphene quantum dots. In some embodiments, the material of the interface layer is a material, such as one of unmodified graphene, graphene oxide, reduced graphene oxide, and graphene quantum dots; in some embodiments, all The materials of the interface layer are two kinds of materials, such as unmodified graphene and graphene oxide, reduced graphene oxide and graphene quantum dots; unmodified graphene and graphene quantum dots; in some embodiments, the The materials of the interface layer are three or more materials, such as unmodified graphene, graphene oxide, and graphene quantum dots.
在一些实施例中，通过溶液加工法在所述基底的空穴传输层上沉积界面材料，形成界面层。In some embodiments, an interface material is deposited on the hole transport layer of the substrate by a solution processing method to form an interface layer.
在一些实施例中，所述所述界面层的材料为还原的氧化石墨烯，所述界面层的制备方法为：在表层为空穴传输层或空穴注入层的基底上，沉积还原的氧化石墨烯溶液，干燥后得到界面层。In some embodiments, the material of the interface layer is reduced graphene oxide, and the preparation method of the interface layer is to deposit reduced oxidation on the substrate where the surface layer is a hole transport layer or a hole injection layer The graphene solution is dried to obtain the interface layer.
在一些实施例中，所述所述界面层的材料为还原的氧化石墨烯，所述界面层的制备方法为：在表层为空穴注入层的基底上，沉积氧化石墨烯溶液，在温度为150℃~180℃的条件下退火处理，得到界面层。通过在温度为150℃~180℃的条件下退火处理，使氧化石墨烯和过渡金属氧化物形成M-O-C键（M指过渡金属原子），造成氧化石墨烯被还原。In some embodiments, the material of the interface layer is reduced graphene oxide. The preparation method of the interface layer is: depositing a graphene oxide solution on a substrate whose surface layer is a hole injection layer at a temperature of Annealing treatment under the condition of 150℃~180℃ to obtain the interface layer. By annealing at a temperature of 150°C to 180°C, graphene oxide and transition metal oxide form an M-O-C bond (M refers to a transition metal atom), causing graphene oxide to be reduced.
本申请实施例中，所述表层为空穴传输层或空穴注入层的基底包括两种情形。在一种情形中，基底为表层是空穴注入层的基底。此时，所述基底至少包括阳极和设置在所述阳极上的空穴注入层。进一步的，所述阳极可以设置在基板上。在该情形中，在制备完界面层后，还包括在界面层上制备空穴传输层，在空穴传输层上制备量子点发光层，在量子点发光层上制备阴极。在一些实施例中，在量子点发光层上制备电子功能层后，再在电子功能层上制备阴极。其中，在一些实施例中，所述阴极和所述阳极通过蒸镀制备，所述空穴注入层可以采用蒸镀或溶液加工法制备，在一些实施例中，其他层通过溶液加工法制备。In the embodiments of the present application, the substrate where the surface layer is a hole transport layer or a hole injection layer includes two cases. In one case, the substrate is a substrate whose surface layer is a hole injection layer. At this time, the substrate includes at least an anode and a hole injection layer provided on the anode. Further, the anode may be provided on the substrate. In this case, after preparing the interface layer, it also includes preparing a hole transport layer on the interface layer, preparing a quantum dot light emitting layer on the hole transport layer, and preparing a cathode on the quantum dot light emitting layer. In some embodiments, after preparing the electronic functional layer on the quantum dot light emitting layer, the cathode is prepared on the electronic functional layer. Wherein, in some embodiments, the cathode and the anode are prepared by evaporation, the hole injection layer may be prepared by evaporation or solution processing, and in some embodiments, other layers are prepared by solution processing.
在另一种情形中，基底为表层是空穴传输层的基底。此时，所述基底至少包括阴极，在阴极上设置的量子点发光层，在量子点发光层上制备的空穴传输层。在一些实施例中，在制备量子点发光层之前，还包括在阴极上制备电子功能层。进一步的，所述阴极极可以设置在基板上。在该情形中，在制备完界面层后，还包括在界面层上制备空穴注入层，在空穴注入层上制备阳极。在一些实施例中，所述阴极和所述阳极通过蒸镀制备，所述空穴注入层可以采用蒸镀或溶液加工法制备，在一些实施例中，其他层通过溶液加工法制备。In another case, the substrate is a substrate whose surface layer is a hole transport layer. At this time, the substrate includes at least a cathode, a quantum dot light emitting layer provided on the cathode, and a hole transport layer prepared on the quantum dot light emitting layer. In some embodiments, before preparing the quantum dot light emitting layer, it further includes preparing an electronic functional layer on the cathode. Further, the cathode electrode may be provided on the substrate. In this case, after preparing the interface layer, it further includes preparing a hole injection layer on the interface layer and preparing an anode on the hole injection layer. In some embodiments, the cathode and the anode are prepared by evaporation. The hole injection layer may be prepared by evaporation or solution processing. In some embodiments, other layers are prepared by solution processing.
下面结合具体实施例进行说明。The following is a description with reference to specific embodiments.
实施例1Example 1
一种量子点发光二极管的制备方法，包括以下步骤：A preparation method of quantum dot light-emitting diode includes the following steps:
以透明导电薄膜ITO作为阳极，所述阳极的厚度为50nm；The transparent conductive thin film ITO is used as the anode, and the thickness of the anode is 50 nm;
采用溶液加工法在阳极上沉积WO 3纳米颗粒，100℃退火30分钟，制备空穴注入层，所述空穴注入层的厚度为30nm； Depositing WO 3 nanoparticles on the anode using a solution processing method and annealing at 100°C for 30 minutes to prepare a hole injection layer with a thickness of 30 nm;
采用溶液加工法在空穴注入层上沉积还原的氧化石墨烯，70℃退火30分钟，制备界面层，所述界面层的厚度为5nm；Depositing reduced graphene oxide on the hole injection layer by a solution processing method, annealing at 70°C for 30 minutes to prepare an interface layer, the thickness of the interface layer is 5 nm;
采用溶液加工法在界面层上沉积PVK，150℃退火30分钟，制备有机空穴传输层，所述有机空穴传输层的厚度为20nm；PVK is deposited on the interface layer by a solution processing method, and annealed at 150° C. for 30 minutes to prepare an organic hole transport layer, the thickness of the organic hole transport layer is 20 nm;
采用溶液加工法在有机空穴传输层上沉积CdSe/ZnS，100℃退火30分钟制备量子点发光层，所述量子点发光层的厚度为25nm；A solution processing method is used to deposit CdSe/ZnS on the organic hole transport layer, and annealed at 100°C for 30 minutes to prepare a quantum dot light emitting layer, and the thickness of the quantum dot light emitting layer is 25 nm;
采用溶液加工法在量子点发光层上利用溶液法沉积ZnO纳米颗粒，80℃退火30分钟，制备电子传输层，电子传输层的厚度为30nm；The solution processing method was used to deposit ZnO nanoparticles on the quantum dot light-emitting layer by the solution method, and annealed at 80°C for 30 minutes to prepare an electron transport layer with a thickness of 30 nm;
在电子传输层上蒸镀Al作为阴极，所述阴极的厚度为100nm。Al was vapor-deposited on the electron transport layer as a cathode, and the thickness of the cathode was 100 nm.
实施例2Example 2
一种量子点发光二极管的制备方法，包括以下步骤：A preparation method of quantum dot light-emitting diode includes the following steps:
以透明导电薄膜ITO作为阳极，所述阳极的厚度为50nm；The transparent conductive thin film ITO is used as the anode, and the thickness of the anode is 50 nm;
采用溶液加工法在阳极上沉积V 2O 5纳米颗粒，100℃退火30分钟，制备空穴注入层，所述空穴注入层的厚度为30nm； A solution processing method is used to deposit V 2 O 5 nanoparticles on the anode, and annealed at 100° C. for 30 minutes to prepare a hole injection layer with a thickness of 30 nm;
采用溶液加工法在空穴注入层上沉积氧化石墨烯，180℃退火60分钟，制备界面层，所述界面层的厚度为3nm；The solution processing method is used to deposit graphene oxide on the hole injection layer, and annealed at 180°C for 60 minutes to prepare an interface layer, the thickness of the interface layer is 3 nm;
采用溶液加工法在界面层上沉积PVK，150℃退火30分钟，制备有机空穴传输层，所述有机空穴传输层的厚度为20nm；PVK is deposited on the interface layer by a solution processing method, and annealed at 150° C. for 30 minutes to prepare an organic hole transport layer, the thickness of the organic hole transport layer is 20 nm;
采用溶液加工法在有机空穴传输层上沉积CdSe/ZnS，100℃退火30分钟制备量子点发光层，所述量子点发光层的厚度为25nm；A solution processing method is used to deposit CdSe/ZnS on the organic hole transport layer, and annealed at 100°C for 30 minutes to prepare a quantum dot light emitting layer, and the thickness of the quantum dot light emitting layer is 25 nm;
采用溶液加工法在量子点发光层上利用溶液法沉积ZnO纳米颗粒，80℃退火30分钟，制备电子传输层，电子传输层的厚度为30nm；The solution processing method was used to deposit ZnO nanoparticles on the quantum dot light-emitting layer by the solution method, and annealed at 80°C for 30 minutes to prepare an electron transport layer with a thickness of 30 nm;
在电子传输层上蒸镀Al作为阴极，所述阴极的厚度为100nm。Al was vapor-deposited on the electron transport layer as a cathode, and the thickness of the cathode was 100 nm.
实施例3Example 3
一种量子点发光二极管的制备方法，包括以下步骤：A preparation method of quantum dot light-emitting diode includes the following steps:
以透明导电薄膜ITO作为阳极，所述阳极的厚度为50nm；The transparent conductive thin film ITO is used as the anode, and the thickness of the anode is 50 nm;
采用溶液加工法在阳极上沉积V 2O 5纳米颗粒，100℃退火30分钟，制备空穴注入层，所述空穴注入层的厚度为30nm； A solution processing method is used to deposit V 2 O 5 nanoparticles on the anode, and annealed at 100° C. for 30 minutes to prepare a hole injection layer with a thickness of 30 nm;
采用溶液加工法在空穴注入层上沉积石墨烯量子点，100℃退火60分钟，制备界面层，所述界面层的厚度为10nm；Depositing graphene quantum dots on the hole injection layer by solution processing, annealing at 100°C for 60 minutes to prepare an interface layer, the thickness of the interface layer is 10 nm;
采用溶液加工法在界面层上沉积PVK，150℃退火30分钟，制备有机空穴传输层，所述有机空穴传输层的厚度为20nm；PVK is deposited on the interface layer by a solution processing method, and annealed at 150° C. for 30 minutes to prepare an organic hole transport layer, the thickness of the organic hole transport layer is 20 nm;
采用溶液加工法在有机空穴传输层上沉积CdSe/ZnS，100℃退火30分钟制备量子点发光层，所述量子点发光层的厚度为25nm；A solution processing method is used to deposit CdSe/ZnS on the organic hole transport layer, and annealed at 100°C for 30 minutes to prepare a quantum dot light emitting layer, and the thickness of the quantum dot light emitting layer is 25 nm;
采用溶液加工法在量子点发光层上利用溶液法沉积ZnO纳米颗粒，80℃退火30分钟，制备电子传输层，电子传输层的厚度为30nm；The solution processing method was used to deposit ZnO nanoparticles on the quantum dot light-emitting layer by the solution method, and annealed at 80°C for 30 minutes to prepare an electron transport layer with a thickness of 30 nm;
在电子传输层上蒸镀Al作为阴极，所述阴极的厚度为100nm。Al was vapor-deposited on the electron transport layer as a cathode, and the thickness of the cathode was 100 nm.
以上所述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。The above are only the preferred embodiments of this application and are not intended to limit this application. Any modification, equivalent replacement and improvement made within the spirit and principle of this application should be included in the protection of this application Within range.

Claims (16)

  1. 一种量子点发光二极管，其特征在于，包括相对设置的阳极和阴极，在所述阳极和所述阴极之间设置的量子点发光层，以及设置在所述阳极和所述量子点发光层之间的空穴功能叠层，所述空穴功能叠层包括空穴注入层、在所述空穴注入层上设置的空穴传输层以及设置在所述空穴注入层和所述空穴传输层之间的界面层，其中，所述空穴注入层邻近所述阳极设置，且所述空穴注入层的材料含有过渡金属氧化物；所述空穴传输层邻近所述量子点发光层设置，且所述空穴传输层的材料含有有机空穴传输材料；所述界面层的材料为石墨烯类材料。A quantum dot light emitting diode, characterized by comprising an anode and a cathode arranged oppositely, a quantum dot light emitting layer provided between the anode and the cathode, and one of the anode and the quantum dot light emitting layer Between the hole function stack, the hole function stack includes a hole injection layer, a hole transport layer provided on the hole injection layer, and a hole injection layer and the hole transport provided on the hole injection layer An interface layer between layers, wherein the hole injection layer is disposed adjacent to the anode, and the material of the hole injection layer contains a transition metal oxide; the hole transport layer is disposed adjacent to the quantum dot light emitting layer , And the material of the hole transport layer contains an organic hole transport material; the material of the interface layer is a graphene-based material.
  2. 如权利要求1所述的量子点发光二极管，其特征在于，所述界面层的材料选自未改性石墨烯、氧化石墨烯、还原的氧化石墨烯、石墨烯量子点中的至少一种。The quantum dot light emitting diode according to claim 1, wherein the material of the interface layer is selected from at least one of unmodified graphene, graphene oxide, reduced graphene oxide, and graphene quantum dots.
  3. 如权利要求1所述的量子点发光二极管，其特征在于，所述界面层的材料选自还原的氧化石墨烯或石墨烯量子点。The quantum dot light-emitting diode according to claim 1, wherein the material of the interface layer is selected from reduced graphene oxide or graphene quantum dots.
  4. 如权利要求1所述的量子点发光二极管，其特征在于，所述界面层的材料选自还原的氧化石墨烯和石墨烯量子点。The quantum dot light-emitting diode according to claim 1, wherein the material of the interface layer is selected from reduced graphene oxide and graphene quantum dots.
  5. 如权利要求1所述的量子点发光二极管，其特征在于，所述界面层的厚度为1nm~30nm。The quantum dot light emitting diode according to claim 1, wherein the thickness of the interface layer is 1 nm to 30 nm.
  6. 如权利要求3或4所述的量子点发光二极管，其特征在于，所述界面层的材料为还原的氧化石墨烯，界面层的厚度为1nm~5nm。The quantum dot light emitting diode according to claim 3 or 4, wherein the material of the interface layer is reduced graphene oxide, and the thickness of the interface layer is 1 nm to 5 nm.
  7. 如权利要求3所述的量子点发光二极管，其特征在于，所述界面层的材料为石墨烯量子点，界面层的厚度为2nm~15nm。The quantum dot light emitting diode according to claim 3, wherein the material of the interface layer is graphene quantum dots, and the thickness of the interface layer is 2 nm to 15 nm.
  8. 如权利要求2所述的量子点发光二极管，其特征在于，所述界面层的材料为未改性石墨烯，界面层的厚度小于等于10nm。The quantum dot light-emitting diode according to claim 2, wherein the material of the interface layer is unmodified graphene, and the thickness of the interface layer is less than or equal to 10 nm.
  9. 如权利要求2所述的量子点发光二极管，其特征在于，所述界面层的材料为氧化石墨烯，界面层的厚度为5nm~10nm。The quantum dot light emitting diode according to claim 2, wherein the material of the interface layer is graphene oxide, and the thickness of the interface layer is 5 nm to 10 nm.
  10. 如权利要求1所述的量子点发光二极管，其特征在于，所述量子点发光二极管还包括设置在所述阴极和所述量子点发光层之间的电子功能层，所述电子功能层包括电子传输层、电子注入层、空穴阻挡层中的至少一层。The quantum dot light emitting diode according to claim 1, wherein the quantum dot light emitting diode further comprises an electronic functional layer disposed between the cathode and the quantum dot light emitting layer, the electronic functional layer including electrons At least one layer of the transport layer, the electron injection layer, and the hole blocking layer.
  11. 如权利要求1所述的量子点发光二极管，其特征在于，所述过渡金属氧化物选自MoO 3、WO 3、V 2O 5、Rb 2O中的至少一种。 The quantum dot light emitting diode according to claim 1, wherein the transition metal oxide is selected from at least one of MoO 3 , WO 3 , V 2 O 5 , and Rb 2 O.
  12. 一种量子点发光二极管的制备方法，其特征在于，包括以下步骤：A preparation method of quantum dot light-emitting diode, which is characterized by comprising the following steps:
    在空穴传输层和空穴注入层之间制备界面层，其中，所述空穴注入层邻近阳极设置，且所述空穴注入层的材料含有过渡金属氧化物；所述空穴传输层邻近量子点发光层设置，且所述空穴传输层的材料含有有机空穴传输材料；所述界面层的材料为石墨烯类材料。An interface layer is prepared between the hole transport layer and the hole injection layer, wherein the hole injection layer is disposed adjacent to the anode, and the material of the hole injection layer contains a transition metal oxide; the hole transport layer is adjacent A quantum dot light emitting layer is provided, and the material of the hole transport layer contains an organic hole transport material; the material of the interface layer is a graphene-based material.
  13. 如权利要求12所述的量子点发光二极管的制备方法，其特征在于，在所述空穴传输层和所述空穴注入层之间制备界面层的方法为：在表层为空穴传输层或空穴注入层的基底上，通过溶液法沉积石墨烯类材料，制备界面层。The method for preparing a quantum dot light-emitting diode according to claim 12, wherein the method for preparing the interface layer between the hole transport layer and the hole injection layer is: the surface layer is a hole transport layer or On the substrate of the hole injection layer, a graphene-based material is deposited by a solution method to prepare an interface layer.
  14. 如权利要求12所述的量子点发光二极管的制备方法，其特征在于，所述界面层的材料选自未改性石墨烯、氧化石墨烯、还原的氧化石墨烯、石墨烯量子点中的至少一种。The method for preparing a quantum dot light-emitting diode according to claim 12, wherein the material of the interface layer is selected from at least one of unmodified graphene, graphene oxide, reduced graphene oxide, and graphene quantum dots One kind.
  15. 如权利要求14所述的量子点发光二极管的制备方法，其特征在于，所述所述界面层的材料为还原的氧化石墨烯，所述界面层的制备方法为：在表层为空穴传输层或空穴注入层的基底上，沉积还原的氧化石墨烯溶液，干燥后得到界面层。The method for preparing a quantum dot light emitting diode according to claim 14, wherein the material of the interface layer is reduced graphene oxide, and the method for preparing the interface layer is: a hole transport layer on the surface layer Or on the substrate of the hole injection layer, a reduced graphene oxide solution is deposited, and the interface layer is obtained after drying.
  16. 如权利要求14所述的量子点发光二极管的制备方法，其特征在于，所述界面层的材料为还原的氧化石墨烯，所述界面层的制备方法为：在表层为空穴注入层的基底上，沉积氧化石墨烯溶液，在温度为150℃~180℃的条件下退火处理，得到界面层。The method for preparing a quantum dot light-emitting diode according to claim 14, wherein the material of the interface layer is reduced graphene oxide, and the method for preparing the interface layer is: the surface is a substrate of a hole injection layer Above, the graphene oxide solution is deposited and annealed at a temperature of 150°C to 180°C to obtain an interface layer.
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CN111816683A (en) * 2020-07-13 2020-10-23 广东聚华印刷显示技术有限公司 Display device and method for manufacturing the same
CN114497401A (en) * 2020-11-13 2022-05-13 夏普株式会社 Light emitting device and light emitting structure
CN113066933A (en) * 2021-03-11 2021-07-02 北京京东方技术开发有限公司 Light-emitting device, preparation method thereof, display substrate and display device
CN113066933B (en) * 2021-03-11 2024-03-01 北京京东方技术开发有限公司 Light emitting device, manufacturing method thereof, display substrate and display device

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