WO2020134161A1 - 一种量子点发光二极管及其制备方法 - Google Patents

一种量子点发光二极管及其制备方法 Download PDF

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WO2020134161A1
WO2020134161A1 PCT/CN2019/104010 CN2019104010W WO2020134161A1 WO 2020134161 A1 WO2020134161 A1 WO 2020134161A1 CN 2019104010 W CN2019104010 W CN 2019104010W WO 2020134161 A1 WO2020134161 A1 WO 2020134161A1
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layer
quantum dot
dot light
electron blocking
functional
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聂志文
杨一行
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TCL Technology Group Co Ltd
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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
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/18—Carrier blocking layers
    • H10K50/181—Electron blocking layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/85—Arrangements for extracting light from the devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/40—Interrelation of parameters between multiple constituent active layers or sublayers, e.g. HOMO values in adjacent layers

Definitions

  • the present disclosure relates to the field of quantum dots, in particular to a quantum dot light-emitting diode and a preparation method thereof.
  • the quantum dot light-emitting diode is a typical sandwich structure, which is composed of electrodes, functional layers, and light-emitting layers. Under the excitation of the applied voltage, the carriers enter the quantum dots from the functional layers through the electrodes at both ends to recombine to form excitons. The recombined excitons release photons in the form of radiation transitions, thereby emitting light. Because colloidal quantum dots have the characteristics of high luminous efficiency, high color purity, wide color gamut, and good stability, QLED not only inherits these excellent properties of quantum dots, but also has self-luminous, wide viewing angle, flexible, etc. Features, showing great commercial application prospects, have become an important research direction in the field of new generation of new and lighting display.
  • the quantum dot itself is processed and prepared by the solution method, it is very suitable for configuration as an ink, and then printing, inkjet and other methods are used to achieve large-scale and large-area preparation.
  • QLED devices have developed rapidly and achieved remarkable results.
  • the alloying of the quantum dot and the growth of the thick shell layer have greatly promoted the performance of QLED devices.
  • semiconductor quantum dots generally have a deep HOMO energy level, and there is a large potential barrier for charge transport in each functional layer, resulting in an imbalance between electron and hole injection during device operation.
  • a high carrier injection barrier will increase the operating voltage of the device; on the other hand, unbalanced charge injection will greatly reduce the recombination probability of carriers in the light-emitting layer, and easily lead to non-radiative transitions of excitons , Thereby affecting the luminous efficiency and life of the device.
  • the purpose of the present disclosure is to provide a quantum dot light emitting diode and a preparation method thereof, aiming to solve the recombination probability of carriers in the light emitting layer caused by the imbalance of carrier injection in the existing QLED device The problem of reducing the luminous efficiency and life of the device is reduced.
  • a quantum dot light-emitting diode includes a cathode, an anode, and a quantum dot light-emitting layer disposed between the cathode and the anode, wherein a functional layer is provided between the anode and the quantum dot light-emitting layer, and the functional layer includes n layer stacks
  • a functional structural unit is provided, the functional structural unit is composed of a hole transport layer and an electron blocking material layer that are stacked, the hole transport layer in the functional structural unit is disposed near the anode, and the electron blocking in the functional structural unit
  • the material layer is disposed near the quantum dot light-emitting layer, n is an integer greater than or equal to 2, and in the two adjacent functional functional units of the n-layer functional structural unit, the electron blocking material layer material near the quantum dot light-emitting layer
  • the HOMO energy level is greater than that of the electron blocking material layer material near the anode.
  • a preparation method of quantum dot light-emitting diode which includes the following steps:
  • a functional layer is prepared on the substrate.
  • the functional layer includes n layers of stacked functional structural units.
  • the functional structural unit is composed of a stacked hole transport layer and an electron blocking material layer.
  • the hole transport layer is disposed near the anode
  • the electron blocking material layer in the functional structural unit is disposed near the quantum dot light emitting layer
  • the n is an integer greater than or equal to 2
  • two adjacent layers in the n-layer functional structural unit In the functional structural unit, the HOMO energy level of the electron blocking material layer material near the quantum dot light emitting layer is greater than the HOMO energy level of the electron blocking material layer material near the anode.
  • the quantum dot light-emitting diode provided by the present disclosure can improve the transmission rate of holes from the quantum dot light-emitting layer through the arrangement of the functional layer, thereby balancing the injection rate of electrons and holes, so as to improve the carrier in the quantum dot Recombination efficiency in the layer, thereby improving the luminous efficiency, stability and service life of quantum dot light-emitting diodes.
  • FIG. 1 is a schematic structural diagram of a preferred embodiment of a quantum dot light emitting diode of the present disclosure.
  • FIG. 2 is a schematic diagram of the energy band structure of the quantum dot light emitting diode of the present disclosure.
  • FIG. 3 is a flowchart of a preferred embodiment of a method for manufacturing a quantum dot light emitting diode of the present disclosure.
  • the present disclosure provides a quantum dot light emitting diode and a preparation method thereof.
  • the present disclosure will be described in further detail below. It should be understood that the specific embodiments described herein are only used to explain the present disclosure and are not intended to limit the present disclosure.
  • the quantum dot light emitting diodes are divided into a positive structure and an inverse structure.
  • the positive structure quantum dot light emitting diodes include a substrate stacked from bottom to top , Anode, quantum dot light-emitting layer, electron transport layer and cathode.
  • the substrate may include a substrate, an anode stacked on the surface of the substrate, and a hole injection layer stacked on the anode; in yet another embodiment of the present disclosure, the The substrate may include a substrate, an anode stacked on the surface of the substrate, a hole injection layer stacked on the surface of the anode, and a hole transport layer stacked on the surface of the hole injection layer.
  • the inverted-type quantum dot light-emitting diode may include a substrate, a cathode, a quantum dot light-emitting layer, and an anode layered from bottom to top.
  • the substrate may include a substrate, a cathode stacked on the surface of the substrate, and an electron injection layer stacked on the surface of the cathode; in yet another embodiment of the present disclosure, the The substrate may include a substrate, a cathode stacked on the surface of the substrate, an electron injection layer stacked on the surface of the cathode, and an electron transport layer stacked on the surface of the electron injection layer; in still another embodiment of the present disclosure, the The substrate may include a substrate, a cathode stacked on the surface of the substrate, an electron injection layer stacked on the surface of the cathode, an electron transport layer stacked on the surface of the electron injection layer, and a hole blocking layer stacked on the surface of the electron transport layer.
  • the positive-type quantum dot light-emitting diode shown in FIG. 1 will be mainly used as an example for introduction.
  • the positive-type quantum dot light-emitting diode includes a substrate 10, an anode 20, a functional layer, a quantum dot light-emitting layer 40, an electron transport layer 50, and a cathode 60 stacked from bottom to top.
  • the functional layer includes n layers of stacked functional structural units.
  • the functional structural unit is composed of a stacked hole transport layer 31 and an electron blocking material layer 32.
  • the hole transport layer 31 in the functional structural unit is close to the anode 20 Setting, the electron blocking material layer 32 in the functional structural unit is disposed close to the quantum dot light emitting layer 40, the n is an integer greater than or equal to 2, and two adjacent functional structural units in the n-layer functional structural unit
  • the HOMO energy level of the material of the electron blocking material layer 32 near the quantum dot light emitting layer 40 is greater than the HOMO energy level of the material of the electron blocking material layer 32 near the anode 20.
  • the quantum dot light emitting diode can effectively balance the injection rate of electrons and holes through the arrangement of the functional layer, thereby improving the recombination efficiency of carriers in the quantum dot light emitting layer, and thereby improving the luminous efficiency of the quantum dot light emitting diode. Stability and service life.
  • the mechanism for achieving the above effect is as follows:
  • the functional layer in the quantum dot light-emitting diode described in this embodiment includes n layers of stacked functional structural units, and the functional structural units are stacked Composed of a hole transport layer and an electron blocking material layer, the hole transport layer in the functional structural unit is disposed near the anode, the electron blocking material layer in the functional structural unit is disposed near the quantum dot light emitting layer, and n is greater than Equal to an integer, and in the adjacent two functional structural units of the n-layer functional structural unit, the HOMO energy level of the electron blocking material layer material near the quantum dot light emitting layer is greater than the HOMO energy of the electron blocking material layer material near the anode level.
  • the HOMO energy level of the electron blocking material layer gradually increases, and the maximum HOMO energy level of the electron blocking material layer is less than the quantum dot light emission Layer HOMO energy level, this HOMO energy level increases in a stepped electron blocking material layer is very helpful to accelerate the hole transport performance, thereby balancing the injection rate of electrons and holes, in order to improve the carrier in the quantum dot layer
  • the composite efficiency of the LED can further improve the luminous efficiency, stability and service life of the quantum dot light-emitting diode.
  • the number of layers of the electron blocking material layer and the hole transport layer is the same, and the number of layers of the electron blocking material layer and the hole transport layer is 2-10 layers. Preferably, the number of layers of the electron blocking material layer and the hole transport layer are 2-5 layers.
  • the thickness of each electron blocking material layer is 2-5 nm.
  • the electron blocking material layer has a HOMO energy level of -5.0 to -8.0 eV.
  • the electron blocking material layer material near the quantum dot light emitting layer has a HOMO energy level greater than that of the electron blocking material layer material near the anode HOMO energy level, the HOMO energy level difference between adjacent electron blocking material layers is -0.1 ⁇ -0.5eV.
  • the electron blocking material layer whose HOMO energy level is increased stepwise can effectively accelerate the hole transport rate, so that the hole enters the quantum dot light-emitting layer and the electron enters the quantum dot light-emitting layer to achieve a balance State, increasing the recombination probability of electrons and holes.
  • the electron blocking material layer material is selected from one or more of PVK, Poly-TPD, NPB, TCTA, TAPC, CBP, TFB, and DNA, but is not limited thereto.
  • the material of the electron blocking material layer is selected from one or more of compound doped PVK, Poly-TPD, NPB, TCTA, TAPC, CBP, TFB, and DNA, and the compound is selected from One of Li-TFSI, NiO, CuSCN, MoO 3 , CuO, V 2 O 5 or CuS, but is not limited thereto.
  • the electron blocking layer material is selected from one of PVK, Poly-TPD, NPB, TCTA, TAPC, CBP, TFB, and DNA and Li-TFSI, NiO, CuSCN, MoO 3 , CuO, V A mixed material composed of 2 O 5 and CuS.
  • the purpose of selecting a mixed material compound doped electron blocking material is mainly to adjust the LUMO energy level of the electron blocking material layer material, to achieve a stepped barrier between level energy levels, and thereby to adjust the electron and hole transport rate, Improve the recombination efficiency of excitons.
  • the material of the electron blocking material layer is selected from PVK:Li-TFSI, PVK:NiO, PVK:CuSCN, PVK:MoO 3 , PVK:CuO, PVK:V 2 O 5 , PVK:CuS, Poly-TPD, Poly-TPD: Li-TFSI, Poly-TPD: -NiO, Poly-TPD: CuSCN, Poly-TPD: MoO 3 , Poly-TPD: CuO, Poly-TPD: V 2 O 5 , Poly-TPD: CuS, NPB , NPB: Li-TFSI, NPB-TPD: -NiO, NPB-TPD: CuSCN, NPB: MoO 3 , NPB: CuO, NPB: V 2 O 5 , NPB: CuS, TCTA, TCTA: Li-TFSI, TCTA- TPD:-NiO, TCTA-TPD:CuSCN, TCTA:MoO 3 , TC
  • the functional layer includes at least one functional structural unit, wherein the LUMO energy level in the electron blocking material layer in the functional structural unit is greater than the LUMO energy level of the hole transport layer.
  • the LUMO energy level of the hole transport layer is -2.0 to -3.0 eV.
  • the hole transport layer material is selected from TFB, PVK, Poly-TBP, Poly-TPD, NPB, TCTA, TAPC, CBP, PEODT: PSS, MoO 3 , WoO 3 , NiO, CuO, V One or more of 2 O 5 and CuS, but not limited to this.
  • the thickness of each hole transport layer is 10-40 nm.
  • the quantum dot light-emitting layer material is selected from one or more of group II-VI compounds, group III-V compounds, and group I-III-VI compounds, but is not limited thereto.
  • the group II-VI compound is selected from CdSe, CdS, CdTe, ZnSe, ZnS, CdTe, ZnTe, CdZnS, CdZnSe, CdZnTe, ZnSeS, ZnSeTe, ZnTeS, CdSeS, CdSeTe, CdTeS; CdZnSeS, CdZnSeTe and CdZnSTe
  • the group III-V compound is selected from one or more of InP, InAs, GaP, GaAs, GaSb, AlN, AlP, InAsP, InNP, InNSb, GaAlNP, and InAlNP
  • the I -Group III-VI compounds are selected from one or more of InP, In
  • the thickness of the quantum dot light emitting layer is 30-120 nm.
  • the anode material is selected from one or more of Li, Ca, Ba, LiF, CsN 3 , Cs 2 CO 3 , CsF, Ag, Mo, Al, Cu, and Au, but is not limited to this.
  • the thickness of the anode is 20-150 nm.
  • the electron transport layer material is selected from one or more of ZnO, TiO 2, Alq 3 , SnO, ZrO, AlZnO, ZnSnO, BCP, TAZ, PBD, TPBI, Bphen, and CsCO 3 , But it is not limited to this.
  • the thickness of the electron transport layer is 10-120 nm. In some embodiments, the thickness of the electron transport layer is 30-120 nm.
  • the cathode material is selected from one of ITO, FTO, or ZTO. In some embodiments, the thickness of the cathode is 60-130 nm.
  • the quantum dot light emitting diode of the present disclosure may further include one or more of the following functional layers: a hole injection layer provided between the anode and the hole transport layer, and a hole injection layer provided between the cathode and the functional layer Electron injection layer.
  • Embodiments of the present disclosure also provide a method for manufacturing a quantum dot light emitting diode, as shown in FIG. 3, including the steps of:
  • the functional layer includes n layers of stacked functional structural units.
  • the functional structural unit is composed of a stacked hole transport layer and an electron blocking material layer.
  • the functional structural unit The hole transport layer in is arranged near the anode, the electron blocking material layer in the functional structural unit is arranged near the quantum dot light emitting layer, the n is an integer greater than or equal to 2, and the adjacent in the n-layer functional structural unit In the two-layer functional structural unit, the HOMO energy level of the electron blocking material layer material near the quantum dot light emitting layer is greater than the HOMO energy level of the electron blocking material layer material near the anode.
  • the quantum dot light emitting diode is divided into an upright structure and an inverted structure.
  • the upright structure includes an anode, a cathode, and a quantum dot light-emitting layer disposed between the anode and the cathode.
  • the anode of the upright structure is disposed on the substrate, and hole transport can also be provided between the anode and the quantum dot light-emitting layer.
  • the hole functional layer such as a layer, a hole injection layer, and an electron blocking layer may be provided with an electron functional layer such as an electron transport layer, an electron injection layer, and a hole blocking layer between the cathode and the quantum dot light emitting layer.
  • the inverted structure includes an anode, a cathode, and a quantum dot light-emitting layer disposed between the anode and the cathode.
  • the cathode of the inverted structure is disposed on the substrate.
  • a hole transport layer can also be provided between the anode and the quantum dot light-emitting layer.
  • a hole functional layer such as a hole injection layer and an electron blocking layer may be provided with an electron functional layer such as an electron transport layer, an electron injection layer and a hole blocking layer between the cathode and the quantum dot light emitting layer.
  • the bottom electrode provided on the substrate is an anode.
  • the substrate may include a substrate and a bottom electrode stacked on the surface of the substrate;
  • the substrate may include a substrate, a bottom electrode stacked on the surface of the substrate, and a hole injection layer stacked on the surface of the bottom electrode.
  • the bottom electrode provided on the substrate is the cathode.
  • the substrate may be the bottom electrode provided on the substrate; in still other embodiments of the present disclosure, the The substrate may include a substrate, a bottom electrode stacked on the surface of the substrate, an electron injection layer stacked on the surface of the bottom electrode, and a quantum dot light emitting layer stacked on the surface of the electron injection layer.
  • the substrate may include a substrate, a bottom electrode stacked on the surface of the substrate, an electron transport layer stacked on the surface of the electron injection layer, and quantum dots stacked on the surface of the electron transport layer Light emitting layer; in still other embodiments of the present disclosure, the substrate may include a substrate, a bottom electrode stacked on the surface of the substrate, an electron injection layer stacked on the surface of the bottom electrode, and a layer stacked on the surface of the electron injection layer An electron transport layer and a quantum dot light emitting layer stacked on the surface of the electron transport layer; in still other embodiments of the present disclosure, the substrate may include a substrate, a bottom electrode stacked on the surface of the substrate, and a bottom electrode stacked on the surface An electron injection layer on the surface, an electron transport layer stacked on the surface of the electron injection layer, a hole blocking layer stacked on the surface of the electron transport layer, and a quantum dot light emitting layer stacked on the surface of the electron blocking layer; In an embodiment, the substrate
  • the substrate is a substrate.
  • the substrate may include a base and an anode stacked on the surface of the base; in still other embodiments of the present disclosure, the substrate may It includes a substrate, an anode stacked on the surface of the substrate, and a hole injection layer stacked on the surface of the anode.
  • each layer preparation method may be a chemical method or a physical method, wherein the chemical method includes but is not limited to one of chemical vapor deposition method, continuous ion layer adsorption and reaction method, anodizing method, electrolytic deposition method, and co-precipitation method One or more; physical methods include but are not limited to solution methods (such as spin coating method, printing method, blade coating method, dipping and pulling method, dipping method, spraying method, roll coating method, casting method, slit coating method) Or strip coating method, etc.), evaporation method (such as thermal evaporation method, electron beam evaporation method, magnetron sputtering method or multi-arc ion coating method, etc.), deposition method (such as physical vapor deposition method, atomic layer One or more of deposition method, pulsed laser deposition method, etc.).
  • solution methods such as spin coating method, printing method, blade coating method, dipping and pulling method, dipping method, spraying method, roll coating method, casting method, slit coating method
  • a quantum dot light-emitting diode includes a substrate, an anode, a hole injection layer, a functional layer, a quantum dot light-emitting layer, an electron transport layer, and a cathode, which are arranged in layers from bottom to top.
  • the functional layer includes 5 layers arranged alternately A hole transport layer and a 5-layer electron transport layer.
  • the bottom layer of the functional layer is a hole transport layer and is located near the anode.
  • the top layer of the functional layer is an electron blocking material layer and is located near the quantum dot light-emitting layer.
  • the materials of the electron blocking material layer are PVK, PVK doped with 1.5wt.% Li-TFSI, PVK doped with 3wt.% Li-TFSI, and 4.5wt.% Li-TFSI PVK and 6wt.% Li-TFSI PVK;
  • the anode is ITO with a thickness of 100nm;
  • the hole injection layer material is PEDOT:PSS with a thickness of 40nm;
  • the hole transport layer material is TFB with each layer empty
  • the thickness of the hole transport layer is 10 nm;
  • the material of the quantum dot light emitting layer is InP/ZnS with a thickness of 100 nm;
  • the thickness of each electron blocking material layer is 4 nm;
  • the material of the electron transport layer is ZnO with a thickness of 100nm;
  • the cathode is Al and the thickness is 50nm.
  • a quantum dot light-emitting diode includes a substrate, an anode, a hole injection layer, a functional layer, a quantum dot light-emitting layer, an electron transport layer, and a cathode, which are arranged in layers from bottom to top.
  • the functional layer includes 5 layers arranged alternately A hole transport layer and a 5-layer electron transport layer.
  • the bottom layer of the functional layer is a hole transport layer and is located near the anode.
  • the top layer of the functional layer is an electron blocking material layer and is located near the quantum dot light-emitting layer.
  • the material of the electron blocking material layer is TFB, TFB doped with 1.5 wt.% Li-TFSI, TFB doped with 3 wt.% Li-TFSI, and 4.5 wt.% Li-TFSI.
  • the anode is ITO with a thickness of 100nm;
  • the hole injection layer material is PEDOT:PSS with a thickness of 40nm;
  • the hole transport layer material is PVK, each layer is empty
  • the thickness of the hole transport layer is 15 nm;
  • the material of the quantum dot light emitting layer is InP/ZnS with a thickness of 40 nm;
  • the thickness of each electron blocking material layer is 4 nm;
  • the material of the electron transport layer is SnO with a thickness of 100 nm;
  • the cathode is Al and the thickness is 50 nm.
  • a quantum dot light-emitting diode includes a substrate, an anode, a hole injection layer, a functional layer, a quantum dot light-emitting layer, an electron transport layer, and a cathode, which are arranged in layers from bottom to top.
  • the functional layer includes 5 layers arranged alternately A hole transport layer and a 5-layer electron transport layer.
  • the bottom layer of the functional layer is a hole transport layer and is located near the anode.
  • the top layer of the functional layer is an electron blocking material layer and is located near the quantum dot light-emitting layer.
  • the materials of the electron blocking material layer are TCTA, TCTA doped with 1.5wt.% MoO 3 , TCTA doped with 3wt.% MoO 3 , TCTA with 4.5wt.% MoO 3 , and 6wt .TCA of %MoO 3 ;
  • the anode is ITO with a thickness of 100 nm;
  • the hole injection layer material is PEDOT:PSS with a thickness of 40 nm;
  • the hole transport layer material is Poly-TBP with hole transport per layer
  • the thickness of the layer is 8 nm;
  • the material of the quantum dot light-emitting layer is InP/ZnS with a thickness of 80 nm;
  • the thickness of each electron blocking material layer is 4 nm;
  • the material of the electron transport layer is TiO with a thickness of 100 nm;
  • the cathode is Al and the thickness is 50 nm.
  • a quantum dot light-emitting diode includes a substrate, an anode, a hole injection layer, a functional layer, a quantum dot light-emitting layer, an electron transport layer, and a cathode, which are arranged in layers from bottom to top.
  • the functional layer includes 5 layers arranged alternately A hole transport layer and a 5-layer electron transport layer.
  • the bottom layer of the functional layer is a hole transport layer and is located near the anode.
  • the top layer of the functional layer is an electron blocking material layer and is located near the quantum dot light-emitting layer.
  • the materials of the electron blocking material layer are PVK, PVK doped with 1.5wt.% Li-TFSI, PVK doped with 3wt.% Li-TFSI, and 4.5wt.% Li-TFSI PVK and PVK of 6wt.% Li-TFSI;
  • the anode is ITO with a thickness of 100nm;
  • the hole injection layer material is PEDOT:PSS with a thickness of 40nm;
  • the hole transport layer material is Poly-TPD, each The thickness of the hole transport layer is 10 nm;
  • the material of the quantum dot light-emitting layer is CdZnS/CdZnSe/ZnS with a thickness of 120 nm;
  • the thickness of each electron blocking material layer is 4 nm;
  • the material of the electron transport layer is AlZnO , The thickness is 100nm;
  • the cathode is Al, the thickness is 50nm.
  • a quantum dot light-emitting diode includes a substrate, an anode, a hole injection layer, a functional layer, a quantum dot light-emitting layer, an electron transport layer, and a cathode, which are arranged in layers from bottom to top.
  • the functional layer includes 5 layers arranged alternately A hole transport layer and a 5-layer electron transport layer.
  • the bottom layer of the functional layer is a hole transport layer and is located near the anode.
  • the top layer of the functional layer is an electron blocking material layer and is located near the quantum dot light-emitting layer.
  • the material of the electron blocking material layer is TFB, TFB doped with 1.5 wt.% Li-TFSI, TFB doped with 3 wt.% Li-TFSI, and 4.5 wt.% Li-TFSI.
  • the anode is ITO with a thickness of 100nm;
  • the hole injection layer material is PEDOT:PSS with a thickness of 40nm;
  • the hole transport layer material is TCTA, each layer is empty
  • the thickness of the hole transport layer is 20 nm;
  • the material of the quantum dot light-emitting layer is CdZnS/CdZnSe/ZnS with a thickness of 30 nm;
  • the thickness of each electron blocking material layer is 4 nm;
  • the material of the electron transport layer is TPBI with a thickness Is 100 nm;
  • the cathode is Al and the thickness is 50 nm.
  • a quantum dot light-emitting diode includes a substrate, an anode, a hole injection layer, a functional layer, a quantum dot light-emitting layer, an electron transport layer, and a cathode, which are arranged in layers from bottom to top.
  • the functional layer includes 5 layers arranged alternately A hole transport layer and a 5-layer electron transport layer.
  • the bottom layer of the functional layer is a hole transport layer and is located near the anode.
  • the top layer of the functional layer is an electron blocking material layer and is located near the quantum dot light-emitting layer.
  • the materials of the electron blocking material layer are TCTA, TCTA doped with 1.5wt.% MoO 3 , TCTA doped with 3wt.% MoO 3 , TCTA with 4.5wt.% MoO 3 , and 6wt .TCA of %MoO 3 ;
  • the anode is ITO with a thickness of 100 nm;
  • the hole injection layer material is PEDOT:PSS with a thickness of 40 nm;
  • the hole transport layer material is TFB, each hole transport layer has a The thickness is 10 nm;
  • the material of the quantum dot light emitting layer is CdZnS/CdZnSe/ZnS, and the thickness is 110 nm;
  • the thickness of each electron blocking material layer is 4 nm;
  • the material of the electron transport layer is ZnO, and the thickness is 100 nm ;
  • the cathode is Al with a thickness of 50 nm.
  • the quantum dot light emitting diode provided by the present disclosure includes a cathode, an anode, and a quantum dot light emitting layer disposed between the cathode and the anode.
  • a functional layer is provided between the anode and the quantum dot light emitting layer.
  • n layers of stacked functional structural units which are composed of a hole transport layer and an electron blocking material layer that are stacked, the hole transport layer in the functional structural unit is arranged near the anode, and the functional structural unit
  • the electron blocking material layer in is arranged close to the quantum dot light emitting layer, n is an integer greater than or equal to 2, and in the adjacent two functional structural units of the n layer functional structural unit, the electron blocking near the quantum dot light emitting layer
  • the HOMO energy level of the material layer material is greater than the HOMO energy level of the electron blocking material layer material near the anode.
  • the quantum dot light-emitting diode of the present disclosure can increase the transmission rate of holes from the quantum dot light-emitting layer through the arrangement of the functional layer, thereby balancing the injection rate of electrons and holes to improve the recombination efficiency of carriers in the quantum dot layer , Thereby improving the luminous efficiency, stability and service life of quantum dot light-emitting diodes.

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Abstract

公开一种量子点发光二极管及其制备方法，所述量子点发光二极管包括设置在阳极和量子点发光层之间的功能层，所述功能层包括n层层叠设置的功能结构单元，所述功能结构单元由层叠设置的空穴传输层和电子阻挡材料层组成，所述功能结构单元中的空穴传输层靠近阳极设置，所述功能结构单元中的电子阻挡材料层靠近量子点发光层设置，所述n为大于等于2的整数，且所述n层功能结构单元中的相邻两层功能结构单元中，靠近量子点发光层的电子阻挡材料层材料的HOMO能级大于靠近阳极的电子阻挡材料层材料的HOMO能级。本公开通过所述功能层的设置能够提升空穴传输至量子点发光层的传输速率，从而平衡电子和空穴的注入速率，以提高载流子在量子点层中的复合效率，进而提高量子点发光二极管的发光效率、稳定性和使用寿命。

Description

一种量子点发光二极管及其制备方法 技术领域
本公开涉及量子点领域，尤其涉及一种量子点发光二极管及其制备方法。
背景技术
量子点发光二极管(QLED)为典型的三明治结构，由电极，功能层，发光层等构成。在外加电压的激发下，载流子通过两端电极由各功能层进入到量子点进行复合形成激子，复合后的激子通过辐射跃迁的形式释放光子，从而发光。由于胶体量子点自身具有发光效率高、色纯度高、色域广、稳定性好等特性，QLED不仅承袭了量子点的这些优异的性能，而且QLED还具有自发光、可视角广、可弯曲等特点，表现出极大的商业应用前景，成为新一代新型与照明显示领域的重要研究方向。同时，由于量子点本身是采用溶液法加工制备，非常适合配置成油墨，然后采用印刷、喷墨等方式实现大规模、大面积化制备。目前，经过二十多年的研究与发展，QLED器件得到了迅速发展，并取得了显著的成果。特别是近年来由对功能层的调控转至对量子点自身的调控，对量子点进行合金化和厚壳层的生长极大的推动了QLED器件性能的提升。
现阶段，对于QLED器件而言，如何同步提升器件效率、寿命和稳定性，仍然是一个极具挑战性的难题。通常，半导体量子点普遍具有很深的HOMO能级，电荷在各功能层传输时存在较大的势垒，导致器件在工作时电子和空穴注入不平衡。一方面，高的载流子注入势垒会增加器件的工作电压；另一方面，不平衡的电荷注入会使得载流子在发光层内的复合几率大大降低，容易引发激子的非辐射跃迁，从而影响了器件的发光效率和寿命。
因此，现有技术还有待于改进和发展。
发明内容
鉴于上述现有技术的不足，本公开的目的在于提供一种量子点发光二极管及其制备方法，旨在解决现有QLED器件中载流子注入不平衡导致载流子在发光层内的复合几率降低，影响了器件的发光效率和寿命的问题。
本公开的技术方案如下：
一种量子点发光二极管，包括阴极、阳极以及设置在阴极和阳极之间的量子点发光层，其中，所述阳极和量子点发光层之间设置有功能层，所述功能层包括n层层叠设置的功能结构单元，所述功能结构单元由层叠设置的空穴传输层和电子阻挡材料层组成，所述功能结构单元中的空穴传输层靠近阳极设置，所述功能结构单元中的电子阻挡材料层靠近量子点发光层设置，所述n为大于等于2的整数，且所述n层功能结构单元中的相邻两层功能结构单元中，靠近量子点发光层的电子阻挡材料层材料的HOMO能级大于靠近阳极的电子阻挡材料层材料的HOMO能级。
一种量子点发光二极管的制备方法，其中，包括如下步骤：
提供基板；
在所述基板上制备功能层，所述功能层包括n层层叠设置的功能结构单元，所述功能结构单元由层叠设置的空穴传输层和电子阻挡材料层组成，所述功能结构单元中的空穴传输层靠近阳极设置，所述功能结构单元中的电子阻挡材料层靠近量子点发光层设置，所述n为大于等于2的整数，且所述n层功能结构单元中的相邻两层功能结构单元中，靠近量子点发光层的电子阻挡材料层材料的HOMO能级大于靠近阳极的电子阻挡材料层材料的HOMO能级。
有益效果：本公开提供的量子点发光二极管通过所述功能层的设置能够提升空穴传输至量子点发光层的传输速率，从而平衡电子和空穴的注入速率，以提高载流子在量子点层中的复合效率，进而提高量子点发光二极管的发光效率、稳定性和使用寿命。
附图说明
图1为本公开一种量子点发光二极管较佳实施例的结构示意图。
图2为本公开量子点发光二极管的能带结构示意图。
图3为本公开一种量子点发光二极管的制备方法较佳实施例的流程图。
具体实施方式
本公开提供一种量子点发光二极管及其制备方法，为使本公开的目的、技术方案及效果更加清楚、明确，以下对本公开进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本公开，并不用于限定本公开。
量子点发光二极管有多种形式，且所述量子点发光二极管分为正型结构和反型结构，在一些实施方式中，所述正型结构的量子点发光二极管包括从下至上层叠设置的基板、阳极、量子点发光层、电子传输层以及阴极。在本公开的又一实施方式中，所述基板可以包括衬底、层叠设置在衬底表面的阳极和层叠设置在阳极的空穴注入层；在本公开的又一种实施方式中，所述基板可以包括衬底、层叠设置在衬底表面的阳极、层叠设置在阳极表面的空穴注入层和层叠设置在空穴注入层表面的空穴传输层。
在一些实施方式中，所述反型结构的量子点发光二极管可包括从下往上层叠设置的基板、阴极、量子点发光层以及阳极。在本公开的一种实施方式中，所述基板可以包括衬底、层叠设置在衬底表面的阴极和层叠设置在阴极表面的电子注入层；在本公开的又一种实施方式中，所述基板可以包括衬底、层叠设置在衬底表面的阴极、层叠设置在阴极表面的电子注入层和层叠设置在电子注入层表面的电子传输层；在本公开的还一种实施方式中，所述基板可以包括衬底、层叠设置在衬底表面的阴极、层叠设置在阴极表面的电子注入层、层叠设置在电子注入层表面的电子传输层和层叠设置在电子传输层表面的空穴阻挡层。
本公开的具体实施方式中将主要以如图1所示的正型结构的量子点发光二极管为例进行介绍。具体的，如图1所示，所述正型结构的量子点发光二极管包括从下至上层叠设置的基板10、阳极20、功能层、量子点发光层40、电子传输层50以及阴极60，所述功能层包括n层层叠设置的功能结构单元，所述功能结构单元由层叠设置的空穴传输层31和电子阻挡材料层32组成，所述功能结构单元中的空穴传输层31靠近阳极20设置，所述功能结构单元中的电子阻挡材料层32靠近量子点发光层40设置，所述n为大于等于2的整数，且所述n层功能结构单元中的相邻两层功能结构单元中，靠近量子点发光层40的电子阻挡材料层32材料的HOMO能级大于靠近阳极20的电子阻挡材料层32材料的HOMO能级。
本实施例量子点发光二极管通过所述功能层的设置能够有效平衡电子和空穴的注入速率，从而提高载流子在量子点发光层中的复合效率，进而提高量子点 发光二极管的发光效率、稳定性和使用寿命。实现上述效果的机理具体如下：
对于量子点发光二极管而言，空穴从阳极传输至量子点发光层的过程中，空穴在各传输层的HOMO能级越深，空穴传输时的势垒越大，空穴隧穿过该传输层时所需要的能量越高，导致空穴传输速率越慢；本实施例所述量子点发光二极管中的功能层包括n层层叠设置的功能结构单元，所述功能结构单元由层叠设置的空穴传输层和电子阻挡材料层组成，所述功能结构单元中的空穴传输层靠近阳极设置，所述功能结构单元中的电子阻挡材料层靠近量子点发光层设置，所述n为大于等于的整数，且所述n层功能结构单元中的相邻两层功能结构单元中，靠近量子点发光层的电子阻挡材料层材料的HOMO能级大于靠近阳极的电子阻挡材料层材料的HOMO能级。如图2所示，空穴从阳极传输至量子点发光层的过程中，所述电子阻挡材料层的HOMO能级逐渐增大，且电子阻挡材料层的最大HOMO能级小于所述量子点发光层HOMO能级，这种HOMO能级呈阶梯式增大的电子阻挡材料层非常有利于加快空穴的传输性能，从而平衡电子和空穴的注入速率，以提高载流子在量子点层中的复合效率，进而提高量子点发光二极管的发光效率、稳定性和使用寿命。
在一些实施方式中，所述电子阻挡材料层和空穴传输层的层数相同，且所述电子阻挡材料层和空穴传输层的层数均为2-10层。优选的，所述电子阻挡材料层和空穴传输层的层数均为2-5层。
在一些实施方式中，所述每层电子阻挡材料层的厚度为2-5nm。
在一些实施方式中，所述电子阻挡材料层的HOMO能级为-5.0～-8.0eV。在一些具体的实施方式中，所述n层功能结构单元中的相邻两层功能结构单元中，靠近量子点发光层的电子阻挡材料层材料的HOMO能级大于靠近阳极的电子阻挡材料层材料的HOMO能级，相邻电子阻挡材料层的HOMO能级差为-0.1～-0.5eV。本实施方式中，HOMO能级呈阶梯式增大的电子阻挡材料层能够有效地加快空穴的传输速率，使得空穴进入到量子点发光层和电子进入到量子点发光层能达到一种平衡态，增加电子和空穴的复合几率。
在一些实施方式中，电子阻挡材料层材料选自PVK、Poly-TPD、NPB、TCTA、TAPC、CBP、TFB和DNA中的一种或多种，但不限于此。
在一些实施方式中，所述电子阻挡材料层的材料选自化合物掺杂的PVK、 Poly-TPD、NPB、TCTA、TAPC、CBP、TFB和DNA中的一种或多种，所述化合物选自Li-TFSI、NiO、CuSCN、MoO 3、CuO、V 2O 5或CuS中的一种，但不限于此。在一些实施方式中，所述电子阻挡层材料选自PVK、Poly-TPD、NPB、TCTA、TAPC、CBP、TFB和DNA中的一种与Li-TFSI，NiO、CuSCN、MoO 3、CuO、V 2O 5和CuS中的一种组成的混合材料。选择混合材料化合物掺杂的电子阻挡材料的目的，主要是为了调整电子阻挡层电子阻挡材料层材料的LUMO能级，实现阶能级间的阶梯势垒，从而调整电子和空穴的传输速率，提高激子的复合效率。作为举例，所述电子阻挡材料层材料选自PVK:Li-TFSI，PVK:NiO、PVK:CuSCN、PVK:MoO 3、PVK:CuO、PVK:V 2O 5、PVK:CuS、Poly-TPD、Poly-TPD:Li-TFSI，Poly-TPD:-NiO，Poly-TPD:CuSCN，Poly-TPD:MoO 3、Poly-TPD:CuO、Poly-TPD:V 2O 5、Poly-TPD:CuS、NPB、NPB:Li-TFSI，NPB-TPD:-NiO，NPB-TPD:CuSCN，NPB:MoO 3、NPB:CuO、NPB:V 2O 5、NPB:CuS、TCTA、TCTA:Li-TFSI，TCTA-TPD:-NiO，TCTA-TPD:CuSCN、TCTA:MoO 3、TCTA:CuO、TCTA:V 2O 5、TCTA:CuS、TAPC、TAPC:Li-TFSI、TAPC-TPD:-NiO，TAPC-TPD:CuSCN，TAPC:MoO 3、TAPC:CuO、TAPC:V 2O 5、TAPC:CuS、CBP、CBP:Li-TFSI，CBP-TPD:-NiO、CBP-TPD:CuSCN、CBP:MoO 3、CBP:CuO、CBP:V 2O 5、CBP:CuS、TFB、TFB:Li-TFSI、TFB-TPD:-NiO、TFB-TPD:CuSCN、TFB:MoO 3、TFB:CuO、TFB:V 2O 5和TFB:CuS中的一种或多种，但不限于此。
在一些实施方式中，所述功能层中至少包括1层功能结构单元，其中，所述功能结构单元中的电子阻挡材料层中的LUMO能级大于所述空穴传输层的LUMO能级。本实施方式中，当电子阻挡材料层的LUMO能级高于空穴传输层的LUMO能级时，可以更好的将电子束缚在量子点发光层中，从而加大电子和空穴的复合几率，大大提高量子点的发光效率。在一种具体的实施方式中，所述空穴传输层的LUMO能级为-2.0～-3.0eV。
在一些实施方式中，所述空穴传输层材料选自TFB、PVK、Poly-TBP、Poly-TPD、NPB、TCTA、TAPC、CBP、PEODT：PSS、MoO 3、WoO 3、NiO、CuO、V 2O 5、CuS中的一种或多种，但不限于此。在一些实施方式中，所述每层空穴传输层的厚度为10-40nm。
在一些实施方式中，所述量子点发光层材料选自II-VI族化合物、III-V族化合物和I-III-VI族化合物中的一种或多种，但不限于此。作为举例，所述II-VI 族化合物选自CdSe、CdS、CdTe、ZnSe、ZnS、CdTe、ZnTe、CdZnS、CdZnSe、CdZnTe、ZnSeS、ZnSeTe、ZnTeS、CdSeS、CdSeTe、CdTeS；CdZnSeS、CdZnSeTe和CdZnSTe中的一种或多种；所述III-V族化合物选自InP、InAs、GaP、GaAs、GaSb、AlN、AlP、InAsP、InNP、InNSb、GaAlNP和InAlNP中的一种或多种；所述I-III-VI族化合物选自CuInS 2、CuInSe 2和AgInS 2中的一种或多种。
在一些实施方式中，所述量子点发光层的厚度为30-120nm。
在一些实施方式中，所述阳极材料选自Li、Ca、Ba、LiF、CsN 3、Cs 2CO 3、CsF、Ag、Mo、Al、Cu和Au中的一种或多种，但不限于此。在一些实施方式中，所述阳极的厚度为20-150nm。
在一些实施方式中，所述电子传输层材料选自ZnO、TiO 2、Alq 3、SnO、ZrO、AlZnO、ZnSnO、BCP、TAZ、PBD、TPBI、Bphen和CsCO 3中的一种或多种，但不限于此。在一些实施方式中，所述电子传输层的厚度为10-120nm。在一些实施方式中，所述电子传输层的厚度为30-120nm。
在一些实施方式中，所述阴极材料选自ITO、FTO或ZTO中的一种。在一些实施方式中，所述阴极的厚度为60-130nm。
需要说明的是，本公开量子点发光二极管还可包含以下功能层中的一层或多层：设置于阳极和空穴传输层之间的空穴注入层，设置于阴极和功能层之间的电子注入层。
本公开的实施方式还提供一种量子点发光二极管的制备方法，如图3所示，包括步骤：
S10、提供基板；
S20、在所述基板上制备功能层，所述功能层包括n层层叠设置的功能结构单元，所述功能结构单元由层叠设置的空穴传输层和电子阻挡材料层组成，所述功能结构单元中的空穴传输层靠近阳极设置，所述功能结构单元中的电子阻挡材料层靠近量子点发光层设置，所述n为大于等于2的整数，且所述n层功能结构单元中的相邻两层功能结构单元中，靠近量子点发光层的电子阻挡材料层材料的HOMO能级大于靠近阳极的电子阻挡材料层材料的HOMO能级。
具体的，量子点发光二极管分正置结构和倒置结构。正置结构包括层叠设置的阳极、阴极和设置在阳极和阴极之间的量子点发光层，正置结构的阳极设置在 衬底上，在阳极和量子点发光层之间还可以设置空穴传输层、空穴注入层和电子阻挡层等空穴功能层，在阴极和量子点发光层之间还可以设置电子传输层、电子注入层和空穴阻挡层等电子功能层。倒置结构包括层叠设置的阳极、阴极和设置在阳极和阴极之间的量子点发光层，倒置结构的阴极设置在衬底上，在阳极和量子点发光层之间还可以设置空穴传输层、空穴注入层和电子阻挡层等空穴功能层，在阴极和量子点发光层之间还可以设置电子传输层、电子注入层和空穴阻挡层等电子功能层。
对于正置结构而言，设置在衬底上的底电极为阳极，在本公开的一些实施方式中，所述基板可以包括衬底、层叠设置在衬底表面的底电极；在本公开的另一些实施方式中，所述基板可以包括衬底、层叠设置在衬底表面的底电极、层叠设置在底电极表面的空穴注入层。
对于倒置结构而言，设置在衬底上的底电极为阴极，在本公开的一些实施方式中，所述基板可以为衬底上设置的底电极；在本公开的又一些实施方式中，所述基板可以包括衬底、层叠设置在衬底表面的底电极、层叠设置在底电极表面的电子注入层、层叠设置在电子注入层表面的量子点发光层。在本公开的又一些实施方式中，所述基板可以包括衬底、层叠设置在衬底表面的底电极、层叠设置在电子注入层表面的电子传输层、层叠设置在电子传输层表面的量子点发光层；在本公开的又一些实施方式中，所述基板可以包括衬底、层叠设置在衬底表面的底电极、层叠设置在底电极表面的电子注入层、层叠设置在电子注入层表面的电子传输层和层叠设置在电子传输层表面的量子点发光层；在本公开的又一些实施方式中，所述基板可以包括衬底、层叠设置在衬底表面的底电极、层叠设置在底电极表面的电子注入层、层叠设置在电子注入层表面的电子传输层、层叠设置在电子传输层表面的空穴阻挡层和层叠设置在电子阻挡层表面的量子点发光层；在本公开的又一些实施方式中，所述基板可以包括衬底、层叠设置在衬底表面的底电极、层叠设置在底电极表面的电子注入层、层叠设置在电子注入层表面的电子传输层、层叠设置在电子传输层表面的空穴阻挡层、层叠设置在空穴阻挡层表面的量子点发光层和层叠设置在量子点发光层表面的电子阻挡层。
在一些实施方式中，所述基板为基板，在本公开的一些实施方式中，所述基板可以包括基底、层叠设置在基底表面的阳极；在本公开的又一些实施方式中， 所述基板可以包括基底、层叠设置在基底表面的阳极、层叠设置在阳极表面的空穴注入层。
本公开中，各层制备方法可以是化学法或物理法，其中化学法包括但不限于化学气相沉积法、连续离子层吸附与反应法、阳极氧化法、电解沉积法、共沉淀法中的一种或多种；物理法包括但不限于溶液法(如旋涂法、印刷法、刮涂法、浸渍提拉法、浸泡法、喷涂法、滚涂法、浇铸法、狭缝式涂布法或条状涂布法等)、蒸镀法(如热蒸镀法、电子束蒸镀法、磁控溅射法或多弧离子镀膜法等)、沉积法(如物理气相沉积法、原子层沉积法、脉冲激光沉积法等)中的一种或多种。
下面通过实施例对本公开进行详细说明。
实施例1
一种量子点发光二极管，从下至上依次包括层叠设置的衬底、阳极、空穴注入层、功能层、量子点发光层、电子传输层和阴极，所述功能层包括交替层叠设置的5层空穴传输层和5层电子传输层，所述功能层的最底层为空穴传输层且靠近阳极设置，所述功能层的最顶层为电子阻挡材料层且靠近量子点发光层设置，沿阳极至阴极的方向，所述电子阻挡材料层的材料依次为PVK、掺杂有1.5wt.％Li-TFSI的PVK、掺杂有3wt.％Li-TFSI的PVK、4.5wt.％Li-TFSI的PVK以及6wt.％Li-TFSI的PVK；所述阳极为ITO，厚度为100nm；所述空穴注入层材料为PEDOT:PSS，厚度为40nm；所述空穴传输层材料为TFB，每层空穴传输层的厚度为10nm；所述量子点发光层的材料为InP/ZnS，厚度为100nm；所述每层电子阻挡材料层的厚度为4nm；所述电子传输层的材料为ZnO，厚度为100nm；所述阴极为Al，厚度为50nm。
实施例2
一种量子点发光二极管，从下至上依次包括层叠设置的衬底、阳极、空穴注入层、功能层、量子点发光层、电子传输层和阴极，所述功能层包括交替层叠设置的5层空穴传输层和5层电子传输层，所述功能层的最底层为空穴传输层且靠近阳极设置，所述功能层的最顶层为电子阻挡材料层且靠近量子点发光层设置，沿阳极至阴极的方向，所述电子阻挡材料层的材料依次为TFB、掺杂有1.5wt.％Li-TFSI的TFB、掺杂有3wt.％Li-TFSI的TFB、4.5wt.％Li-TFSI的TFB以及6wt.％Li-TFSI的TFB；所述阳极为ITO，厚度为100nm；所述空穴注入层材 料为PEDOT:PSS，厚度为40nm；所述空穴传输层材料为PVK，每层空穴传输层厚度为15nm；所述量子点发光层的材料为InP/ZnS，厚度为40nm；所述每层电子阻挡材料层的厚度为4nm；所述电子传输层材料为SnO，厚度为100nm；所述阴极为Al，厚度为50nm。
实施例3
一种量子点发光二极管，从下至上依次包括层叠设置的衬底、阳极、空穴注入层、功能层、量子点发光层、电子传输层和阴极，所述功能层包括交替层叠设置的5层空穴传输层和5层电子传输层，所述功能层的最底层为空穴传输层且靠近阳极设置，所述功能层的最顶层为电子阻挡材料层且靠近量子点发光层设置，沿阳极至阴极的方向，所述电子阻挡材料层的材料依次为TCTA、掺杂有1.5wt.％MoO 3的TCTA、掺杂有3wt.％MoO 3的TCTA、4.5wt.％MoO 3的TCTA以及6wt.％MoO 3的TCTA；所述阳极为ITO，厚度为100nm；所述空穴注入层材料为PEDOT:PSS，厚度为40nm；所述空穴传输层材料为Poly-TBP，每层空穴传输层的厚度为8nm；所述量子点发光层的材料为InP/ZnS，厚度为80nm；所述每层电子阻挡材料层的厚度为4nm；所述电子传输层材料为TiO，厚度为100nm；所述阴极为Al，厚度为50nm。
实施例4
一种量子点发光二极管，从下至上依次包括层叠设置的衬底、阳极、空穴注入层、功能层、量子点发光层、电子传输层和阴极，所述功能层包括交替层叠设置的5层空穴传输层和5层电子传输层，所述功能层的最底层为空穴传输层且靠近阳极设置，所述功能层的最顶层为电子阻挡材料层且靠近量子点发光层设置，沿阳极至阴极的方向，所述电子阻挡材料层的材料依次为PVK、掺杂有1.5wt.％Li-TFSI的PVK、掺杂有3wt.％Li-TFSI的PVK、4.5wt.％Li-TFSI的PVK以及6wt.％Li-TFSI的PVK；所述阳极为ITO，厚度为100nm；所述空穴注入层材料为PEDOT:PSS，厚度为40nm；所述空穴传输层材料为Poly-TPD，每层空穴传输层的厚度为10nm；所述量子点发光层的材料为CdZnS/CdZnSe/ZnS，厚度为120nm；所述每层电子阻挡材料层的厚度为4nm；所述电子传输层材料为AlZnO，厚度为100nm；所述阴极为Al，厚度为50nm。
实施例5
一种量子点发光二极管，从下至上依次包括层叠设置的衬底、阳极、空穴注入层、功能层、量子点发光层、电子传输层和阴极，所述功能层包括交替层叠设置的5层空穴传输层和5层电子传输层，所述功能层的最底层为空穴传输层且靠近阳极设置，所述功能层的最顶层为电子阻挡材料层且靠近量子点发光层设置，沿阳极至阴极的方向，所述电子阻挡材料层的材料依次为TFB、掺杂有1.5wt.％Li-TFSI的TFB、掺杂有3wt.％Li-TFSI的TFB、4.5wt.％Li-TFSI的TFB以及6wt.％Li-TFSI的TFB；所述阳极为ITO，厚度为100nm；所述空穴注入层材料为PEDOT:PSS，厚度为40nm；所述空穴传输层材料为TCTA，每层空穴传输层厚度为20nm；所述量子点发光层的材料为CdZnS/CdZnSe/ZnS，厚度为30nm；所述每层电子阻挡材料层的厚度为4nm；所述电子传输层的材料为TPBI，厚度为100nm；所述阴极为Al，厚度为50nm。
实施例6
一种量子点发光二极管，从下至上依次包括层叠设置的衬底、阳极、空穴注入层、功能层、量子点发光层、电子传输层和阴极，所述功能层包括交替层叠设置的5层空穴传输层和5层电子传输层，所述功能层的最底层为空穴传输层且靠近阳极设置，所述功能层的最顶层为电子阻挡材料层且靠近量子点发光层设置，沿阳极至阴极的方向，所述电子阻挡材料层的材料依次为TCTA、掺杂有1.5wt.％MoO 3的TCTA、掺杂有3wt.％MoO 3的TCTA、4.5wt.％MoO 3的TCTA以及6wt.％MoO 3的TCTA；所述阳极为ITO，厚度为100nm；所述空穴注入层材料为PEDOT:PSS，厚度为40nm；所述空穴传输层材料为TFB，每层空穴传输层的厚度为10nm；所述量子点发光层的材料为CdZnS/CdZnSe/ZnS，且厚度为110nm；所述每层电子阻挡材料层的厚度为4nm；所述电子传输层的材料为ZnO，厚度为100nm；所述阴极为Al，厚度为50nm。
综上所述，本公开提供的量子点发光二极管包括阴极、阳极以及设置在阴极和阳极之间的量子点发光层，所述阳极和量子点发光层之间设置有功能层，所述功能层包括n层层叠设置的功能结构单元，所述功能结构单元由层叠设置的空穴传输层和电子阻挡材料层组成，所述功能结构单元中的空穴传输层靠近阳极设置，所述功能结构单元中的电子阻挡材料层靠近量子点发光层设置，所述n为大于等于2的整数，且所述n层功能结构单元中的相邻两层功能结构单元中，靠近量子 点发光层的电子阻挡材料层材料的HOMO能级大于靠近阳极的电子阻挡材料层材料的HOMO能级。本公开量子点发光二极管通过所述功能层的设置能够提升空穴传输至量子点发光层的传输速率，从而平衡电子和空穴的注入速率，以提高载流子在量子点层中的复合效率，进而提高量子点发光二极管的发光效率、稳定性和使用寿命。
应当理解的是，本公开的应用不限于上述的举例，对本领域普通技术人员来说，可以根据上述说明加以改进或变换，所有这些改进和变换都应属于本公开所附权利要求的保护范围。

Claims (15)

  1. 一种量子点发光二极管，包括阴极、阳极以及设置在阴极和阳极之间的量子点发光层，其特征在于，所述阳极和量子点发光层之间设置有功能层，所述功能层包括n层层叠设置的功能结构单元，所述功能结构单元由层叠设置的空穴传输层和电子阻挡材料层组成，所述功能结构单元中的空穴传输层靠近阳极设置，所述功能结构单元中的电子阻挡材料层靠近量子点发光层设置，所述n为大于等于2的整数，且所述n层功能结构单元中的相邻两层功能结构单元中，靠近量子点发光层的电子阻挡材料层材料的HOMO能级大于靠近阳极的电子阻挡材料层材料的HOMO能级。
  2. 根据权利要求1所述的量子点发光二极管，其特征在于，所述电子阻挡材料层的材料选自PVK、Poly-TPD、NPB、TCTA、TAPC、CBP、TFB和DNA中的一种或多种。
  3. 根据权利要求1所述的量子点发光二极管，其特征在于，所述电子阻挡材料层的材料选自化合物掺杂的PVK、Poly-TPD、NPB、TCTA、TAPC、CBP、TFB和DNA中的一种或多种，所述化合物选自Li-TFSI、NiO、CuSCN、MoO 3、CuO、V 2O 5或CuS中的一种。
  4. 根据权利要求1所述的量子点发光二极管，其特征在于，所述空穴传输层材料选自TFB、PVK、Poly-TBP、Poly-TPD、NPB、TCTA、TAPC、CBP、PEODT：PSS、MoO 3、WoO 3、NiO、CuO、V 2O 5、CuS中的一种或多种。
  5. 根据权利要求1所述的量子点发光二极管，其特征在于，所述电子阻挡材料层的HOMO能级为-5.0～-8.0eV。
  6. 根据权利要求1所述的量子点发光二极管，其特征在于，2≤n≤10。
  7. 根据权利要求1所述的量子点发光二极管，其特征在于，2≤n≤5。
  8. 根据权利要求1所述的量子点发光二极管，其特征在于，相邻电子阻挡材料层的HOMO能级差为-0.1～-0.5eV。
  9. 根据权利要求1所述的量子点发光二极管，其特征在于，所述功能层中至少包括1层功能结构单元，其中，所述功能结构单元中的电子阻挡材料层中的LUMO能级大于所述空穴传输层的LUMO能级。
  10. 根据权利要求9所述的量子点发光二极管，其特征在于，所述空穴传输层的LUMO能级为-2.0～-3.0eV。
  11. 根据权利要求1所述的量子点发光二极管，其特征在于，所述每层电子阻挡材料层的厚度为2-5nm。
  12. 根据权利要求1所述的量子点发光二极管，其特征在于，所述每层空穴传输层的厚度为10-100nm。
  13. 根据权利要求1所述的量子点发光二极管，其特征在于，所述量子点发光层材料选自II-VI族化合物、III-V族化合物和I-III-VI族化合物中的一种或多种。
  14. 根据权利要求1所述的量子点发光二极管，其特征在于，所述阴极和量子点发光层之间还设置有电子传输层，所述电子传输层材料选自ZnO、TiO 2、Alq 3、SnO、ZrO、AlZnO、ZnSnO、BCP、TAZ、PBD、TPBI、Bphen和CsCO 3中的一种或多种。
  15. 一种量子点发光二极管的制备方法，其特征在于，包括如下步骤：
    提供基板；
    在所述基板上制备功能层，所述功能层包括n层层叠设置的功能结构单元，所述功能结构单元由层叠设置的空穴传输层和电子阻挡材料层组成，所述功能结构单元中的空穴传输层靠近阳极设置，所述功能结构单元中的电子阻挡材料层靠近量子点发光层设置，所述n为大于等于2的整数，且所述n层功能结构单元中的相邻两层功能结构单元中，靠近量子点发光层的电子阻挡材料层材料的HOMO能级大于靠近阳极的电子阻挡材料层材料的HOMO能级。
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