WO2023070737A1 - 电致发光器件及其制备方法 - Google Patents

电致发光器件及其制备方法 Download PDF

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WO2023070737A1
WO2023070737A1 PCT/CN2021/129294 CN2021129294W WO2023070737A1 WO 2023070737 A1 WO2023070737 A1 WO 2023070737A1 CN 2021129294 W CN2021129294 W CN 2021129294W WO 2023070737 A1 WO2023070737 A1 WO 2023070737A1
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quantum dot
transport material
layer
hole
electron
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PCT/CN2021/129294
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English (en)
French (fr)
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龚金辉
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惠州华星光电显示有限公司
Tcl华星光电技术有限公司
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Priority to US17/621,201 priority Critical patent/US20240032318A1/en
Publication of WO2023070737A1 publication Critical patent/WO2023070737A1/zh

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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
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • 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
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting layers

Definitions

  • the invention relates to the field of display technology, in particular to an electroluminescence device and a preparation method thereof.
  • Quantum dot light-emitting materials have excellent photoelectric properties such as adjustable emission wavelength, high quantum efficiency, and high color purity. Therefore, quantum dot light-emitting diodes (QLED, Quantum Dot Light Emitting Diodes) have broad application prospects in the field of optoelectronic displays.
  • QLED Quantum Dot Light Emitting Diodes
  • the insulation of the organic long-chain ligands on the surface of quantum dots will cause a series of problems, as follows:
  • the ligands on the surface of quantum dots will hinder the transport of carriers in the quantum dot light-emitting film layer, increasing the injection barrier of the device Carriers accumulate at the interface between the electronic functional layer and the quantum dot luminescent film layer and at the interface between the hole functional layer and the quantum dot luminescent film layer, and are quenched to reduce the luminous efficiency.
  • the methods commonly used to improve the conductivity of quantum dots in the prior art include the ligand washing method and the conductive complex method, and there are certain problems: in the ligand washing method, it is difficult to control the amount of retained ligands, and too much ligand retention leads to inefficiency. Not good, too few ligands are retained, and the stability of quantum dots is poor; in the conductive complex method, there are few suitable complexes, and the synthesis process is complicated.
  • the conductivity of the existing quantum dot luminescent film layer needs to be improved.
  • An embodiment of the present invention provides an electroluminescent device to solve the problem that in the existing electroluminescent device, the carriers are at the interface between the electronic functional layer and the quantum dot light-emitting film layer and at the interface between the hole functional layer and the quantum dot light-emitting film layer. Accumulation, quenching occurs, leading to the technical problem of QLED luminous efficiency reduction.
  • An embodiment of the present invention provides an electroluminescent device, comprising: an anode, a hole functional layer, a quantum dot light-emitting layer, an electronic functional layer, and a cathode that are sequentially stacked; wherein, the quantum dot light-emitting layer is doped with a A carrier transport material, the carrier transport material includes at least one of a hole transport material and an electron transport material; the quantum dot luminescent layer includes a quantum dot luminescent material, the carrier transport material and the quantum dot light emitting layer The mass ratio of the point luminescence material is 0.1%-2%.
  • the carrier transport material includes a hole transport material and an electron transport material, and the doping mass ratio of the hole transport material to the electron transport material is 0.1-10.
  • the carrier transport material includes a hole transport material and an electron transport material
  • the quantum dot luminescent layer includes a quantum dot luminescent material
  • the quantum dot luminescent material the hole transport A p-i-n heterojunction is formed between the material and the electron transport material.
  • the quantum dot luminescent layer includes a quantum dot luminescent material, and the band formed by the conduction band/valence band of the carrier transport material and the conduction band/valence band of the quantum dot luminescent material The order is 0.1-0.5eV.
  • the hole functional layer includes a hole injection layer
  • the electron functional layer includes an electron injection layer
  • the hole injection layer is in direct contact with one side surface of the quantum dot light-emitting layer.
  • the electron injection layer is in direct contact with the other surface of the quantum dot light-emitting layer.
  • the hole functional layer includes a stacked hole injection layer and a hole transport layer
  • the electron functional layer includes a stacked electron transport layer and an electron injection layer
  • the hole The transport layer is in direct contact with one surface of the quantum dot luminescent layer
  • the electron transport layer is in direct contact with the other surface of the quantum dot luminescent layer.
  • the carrier transport material includes at least one of CBP, TFB, Poly-TBD, PFO, TPBi, Bphen, and B3PYMPM.
  • the hole transport material includes at least one of CBP, TFB, Poly-TBD, and PFO
  • the electron transport material includes at least one of TPBi, Bphen, and B3PYMPM.
  • the embodiment of the present invention also provides another electroluminescent device, including:
  • An anode, a hole functional layer, a quantum dot light-emitting layer, an electronic functional layer and a cathode are stacked in sequence.
  • the quantum dot light-emitting layer is doped with a carrier transport material.
  • the quantum dot luminescent layer includes a quantum dot luminescent material, and the mass ratio of the carrier transport material to the quantum dot luminescent material is 0.1%-2%.
  • the carrier transport material includes at least one of a hole transport material and an electron transport material.
  • the carrier transport material includes a hole transport material and an electron transport material, and the doping mass ratio of the hole transport material to the electron transport material is 0.1-10.
  • the carrier transport material includes a hole transport material and an electron transport material
  • the quantum dot luminescent layer includes a quantum dot luminescent material
  • the quantum dot luminescent material and the carrier The transport material forms a p-i-n heterojunction.
  • the quantum dot luminescent layer includes a quantum dot luminescent material, and the band formed by the conduction band/valence band of the carrier transport material and the conduction band/valence band of the quantum dot luminescent material The order is 0.1-0.5eV.
  • the hole functional layer includes a hole injection layer
  • the electron functional layer includes an electron injection layer
  • the hole injection layer is in direct contact with one side surface of the quantum dot light-emitting layer.
  • the electron injection layer is in direct contact with the other surface of the quantum dot light-emitting layer.
  • the hole functional layer includes a stacked hole injection layer and a hole transport layer
  • the electron functional layer includes a stacked electron transport layer and an electron injection layer
  • the hole The transport layer is in direct contact with one surface of the quantum dot luminescent layer
  • the electron transport layer is in direct contact with the other surface of the quantum dot luminescent layer.
  • the carrier transport material includes at least one of CBP, TFB, Poly-TBD, PFO, TPBi, Bphen, and B3PYMPM.
  • the carrier transport material includes a hole transport material
  • the hole transport material includes at least one of CBP, TFB, Poly-TBD, and PFO.
  • the carrier transport material includes an electron transport material
  • the electron transport material includes at least one of TPBi, Bphen, and B3PYMPM.
  • the embodiment of the present invention also provides the preparation method of the electroluminescent device in the above embodiment, including:
  • An embodiment of the present invention provides an electroluminescent device and a preparation method thereof.
  • the electroluminescent device includes an anode, a hole functional layer, a quantum dot light-emitting layer, an electronic functional layer, and a cathode that are sequentially stacked.
  • the quantum dot light-emitting layer is doped with Doped with carrier transport materials, on the one hand, carrier transport materials can improve the conductivity of quantum dot luminescent materials, and promote the injection and transport of carriers; on the other hand, p-type and n-type transport materials are mixed with quantum dot luminescent materials The formation of tiny p-i-n heterojunctions can increase the recombination probability of carriers and improve the luminous quantum efficiency of electroluminescent devices.
  • Fig. 1 is a schematic diagram of the film stack structure of the electroluminescent device provided by the embodiment of the present invention
  • Fig. 2 is a schematic flowchart of a method for preparing an electroluminescent device provided by an embodiment of the present invention.
  • the present invention is aimed at the existing electroluminescent devices, because the carriers will accumulate and quench at the interface between the electronic functional layer and the quantum dot light emitting layer, and at the interface between the hole functional layer and the quantum dot light emitting layer, resulting in electroluminescent devices Due to the technical problem of low luminous efficiency, this embodiment is proposed to overcome this defect.
  • an embodiment of the present invention provides an electroluminescent device 100, which includes an anode 20 stacked on one side, a hole functional layer 30, a quantum dot light-emitting layer 40, and an electronic functional layer 50 and cathode 60 .
  • the electroluminescent device 100 can be a top emitting device or a bottom emitting device, the anode 20 is arranged on a substrate 10, the hole functional layer 30 is arranged on the anode 20, the quantum dots
  • the light emitting layer 40 is disposed on the hole function layer 30 , the electron function layer 50 is disposed on the quantum dot light emitting layer 40 , and the cathode 60 is disposed on the electron function layer 50 .
  • the substrate 10 may be a glass substrate
  • the anode 20 may be a transparent ITO (Indium tin oxide, indium tin oxide) electrode
  • the cathode 60 may be an aluminum electrode.
  • the insulation of the organic long-chain ligands on the surface of the quantum dot luminescent layer 40 will cause carriers (holes, electrons) to pass through the interface between the quantum dot luminescent layer 40 and the hole functional layer 30, and Quenching is accumulated at the interface between the quantum dot light-emitting layer 40 and the electronic functional layer 50 .
  • the quantum dot light-emitting layer 40 is doped with a carrier transport material, which can change the conductivity of the quantum dot light-emitting layer 40, but will not change the light-emitting characteristics of the quantum dot light-emitting layer 40, and can increase the diffusion of carriers.
  • the number of channels promotes the diffusion of carriers in the quantum dot light-emitting layer 40, and effectively reduces the accumulation of carriers at the above-mentioned interface and causes quenching.
  • the "doping" mentioned in the embodiment of the present invention refers to mixing another material into a certain film material, and the mixed material will not change the crystal structure of the original film material, so the doping in the embodiment of the present invention The carrier transport material will not enter into the crystal structure of the quantum dot light emitting material in the quantum dot light emitting layer 40 .
  • the carrier transport material includes at least one of a hole transport material and an electron transport material.
  • the carrier transport material includes both a hole transport material and an electron transport material, and the The hole transport material may be a P-type organic transport material, and the electron transport material may be an N-type organic transport material.
  • the P-type organic transport material is conducive to the transport of holes, and the N-type organic transport material is conducive to the transport of electrons.
  • the holes are transported to the quantum dot luminescent material or hole transport material in the quantum dot light-emitting layer 40 through the hole functional layer 30, and the electrons are transported through the quantum dot light-emitting layer 40.
  • the electronic functional layer 50 is transported to the quantum dot luminescent material or the electron transport material in the quantum dot luminescent layer 40 , which increases the number of diffusion channels for carriers in the quantum dot luminescent layer 40 .
  • the quantum dot luminescent layer 40 since the contact area between the carrier transport material and the quantum dot luminescent material is increased, the gap between the quantum dot luminescent material and the hole transport material and the electron transport material Forming p-i-n heterojunctions, numerous tiny p-i-n heterojunctions can effectively increase the recombination probability of holes and electrons in the quantum dot light-emitting layer 40, thereby improving the quantum dot efficiency of the electroluminescent device.
  • the mass ratio of the carrier transport material to the quantum dot luminescent material is 0.1%-2%, within this range, the luminous efficiency of the quantum dot can be effectively improved. Doping the carrier transport material cannot be too much, otherwise the quantum dot light-emitting layer 40 which itself is a semiconductor will be changed into a conductive film layer, causing the electroluminescent device to fail to emit light.
  • the carrier transport material includes both a hole transport material and an electron transport material
  • the doping mass ratio of the hole transport material to the electron transport material is 0.1-10, which can effectively improve the Injection and transport of electrons in the quantum dot light-emitting layer 40 .
  • the selection of the carrier transport material mainly satisfies the transport ability of the carriers and can effectively transport the carriers; on the other hand, it can
  • the band order formed by the conduction band/valence band of the material is selected, and the band order formed by the conduction band/valence band of the carrier transport material and the conduction band/valence band of the quantum dot light-emitting material is 0.1-0.5eV , contribute to the recombination of holes and electrons in the quantum dot light-emitting layer 40 .
  • the carrier transport material includes CBP (4,4'-di(9-carbazole) biphenyl), TFB (poly(9,9-dioctylfluorene-CO-N-(4-butylphenyl )diphenylamine)), Poly-TBD, PFO (poly(9,9-dioctylfluorene-2,7-diyl)), TPBi(1,3,5-tris(1-phenyl-1H-benzene imidazol-2-yl)benzene), Bphen (4,7-diphenyl-1,10-phenanthroline), B3PYMPM (4,6-bis(3,5-bis(3-pyridin)ylphenyl )-2-methylpyrimidine) at least one.
  • CBP 4,4'-di(9-carbazole) biphenyl
  • TFB poly(9,9-dioctylfluorene-CO-N-(4-but
  • CBP, TFB, Poly-TBD, and PFO can be used as hole transport materials
  • TPBi, Bphen, and B3PYMPM can be used as electron transport materials
  • the quantum dot light-emitting layer 40 is doped with hole transport material and electron transport material at the same time
  • the doped hole transport material may be CBP
  • the doped electron transport material may be TPBi.
  • the hole functional layer 30 includes a hole injection layer
  • the electron function layer 50 includes an electron injection layer
  • the hole injection layer is connected to one side surface of the quantum dot light-emitting layer 40 In direct contact, the electron injection layer is in direct contact with the surface on the other side of the quantum dot light-emitting layer 40 .
  • the hole injection layer may be a PEDOT:PSS material
  • the electron injection layer may be a ZnO material
  • the hole functional layer 30 further includes a hole transport layer
  • the electron functional layer 50 further includes an electron transport layer, so as to improve the carrier transport ability before reaching the quantum dot light-emitting layer 40 .
  • the hole functional layer 30 includes a stacked hole injection layer and a hole transport layer
  • the electron functional layer 50 includes a stacked electron transport layer and an electron injection layer
  • the hole transport layer and the hole transport layer One surface of the quantum dot luminescent layer 40 is in direct contact with, and the electron transport layer is in direct contact with the other surface of the quantum dot luminescent layer 40 .
  • an embodiment of the present invention also provides a method for preparing the electroluminescent device 100 in the above embodiment, including S10, dispersing the carrier transport material in the first organic solvent, and mixing uniformly until the first organic solvent is formed. solution; S20, dissolving the quantum dot luminescent material in a second organic solvent, and mixing uniformly to form a second solution; S30, mixing the first solution and the second solution to form a mixed solution; S40, mixing the The mixed solution is coated on a substrate 10 prepared with an anode 20 and a hole functional layer 30 to form a quantum dot light-emitting layer 40 ;
  • the carrier transport material can be selected from CBP and TPBi materials, and CBP and TPBi are simultaneously dispersed in the first organic solvent, and subjected to ultrasonic vibration to fully dissolve and mix the carrier transport material uniformly.
  • the first organic solvent may be a non-polar solvent, and the first organic solvent includes at least one of hexane, heptane, octane, nonane, decane, and cyclohexane.
  • the mass fraction of the carrier transport material in the first solution is 0.1%-5%, within this range, the carrier transport material has better solubility.
  • the material selection of the second organic solvent is consistent with that of the first organic solvent, which is beneficial to increase the mixing uniformity of the first solution and the second solution.
  • first solution and the second solution When mixing the first solution and the second solution, ultrasonic vibration is also used to fully diffuse the solute in the solution, and then the mixed solution is filtered with a 0.45um PET filter membrane to remove large particles.
  • the first solution and the second solution are mixed in different proportions. When mixing, it is necessary to ensure that the mass ratio of the carrier transport material and the quantum dot luminescent material in the two solutions is 0.1%-2%.
  • the mixed solution is sequentially spin-coated or evaporated, and then subjected to processes such as baking to form the quantum dot light-emitting layer 40.
  • the first solvent and The second solvent will volatilize during the process of forming the quantum dot light emitting layer 40 and will not affect the luminous efficiency of the quantum dot light emitting layer 40 .
  • an electronic functional layer 50 and a cathode 60 are sequentially prepared on the quantum dot luminescent layer 40, the electronic functional layer 50 includes an electron injection layer, and in other embodiments, the electronic functional layer 50 may further include a An electron transport layer on the electron injection layer.
  • the embodiment of the present invention provides an electroluminescent device and a manufacturing method thereof, including an anode 20, a hole functional layer 30, a quantum dot light-emitting layer 40, an electronic functional layer 50, and a cathode 60 that are sequentially stacked.
  • the light-emitting layer 40 is doped with a carrier transport material.
  • the carrier transport material can improve the conductivity of the quantum dot light-emitting material, and promote the injection and transport of carriers.
  • the p-type and n-type transport materials and Quantum dot light-emitting materials are mixed to form tiny p-i-n heterojunctions, which can increase the recombination probability of carriers and improve the luminous quantum efficiency of electroluminescent devices.

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Abstract

公开一种电致发光器件及其制备方法，电致发光器件包括依次叠层设置的阳极、空穴功能层、量子点发光层、电子功能层以及阴极，量子点发光层中掺杂有载流子传输材料；一方面在量子点发光层中掺杂的载流子传输材料可改善量子点发光材料的导电性，促进载流子的注入和传输，另一方面也能提高载流子的复合几率。

Description

电致发光器件及其制备方法 技术领域
本发明涉及显示技术领域，尤其涉及一种电致发光器件及其制备方法。
背景技术
量子点发光材料具有发光波长可调、量子效率高、色纯度高等优异的光电性能，因而，量子点发光二极管(QLED，Quantum Dot Light Emitting Diodes)在光电显示领域具有广阔的应用前景。然而由于量子点表面的有机长链配体的绝缘性会导致一系列的问题，具体如下：量子点表面的配体会阻碍载流子在量子点发光膜层中的运输，增加器件的注入势垒；载流子在电子功能层与量子点发光膜层界面以及在空穴功能层与量子点发光膜层界面积累，发生猝灭，降低发光效率。
现有技术中常用于提高量子点导电性的方法包括洗配体法和导电配合物法均存在一定的问题：洗配体法中，难以控制保留配体的数量，配体保留过多导致效果不佳，保留配体过少，量子点稳定性差；导电配合物法中，合适的配合物较少，合成工艺复杂。
综上，现有的量子点发光膜层的导电性有待于提高。
技术问题
本发明实施例提供一种电致发光器件，以解决现有的电致发光器件中，载流子在电子功能层与量子点发光膜层界面以及在空穴功能层与量子点发光膜层界面积累，发生猝灭，导致QLED发光效率降低的技术问题。
技术解决方案
为解决上述问题，本发明提供的技术方案如下：
本发明实施例提供一种电致发光器件，包括：依次叠层设置的阳极、空穴功能层、量子点发光层、电子功能层以及阴极；其中，所述量子点发光层中掺杂有载流子传输材料，所述载流子传输材料包括空穴传输材料和电子传输材料中的至少一种；所述量子点发光层包括量子点发光材料，所述载流子传输材料与所述量子点发光材料的质量比为0.1％～2％。
在本发明的一些实施例中，所述载流子传输材料包括空穴传输材料和电子传输材料，所述空穴传输材料和所述电子传输材料的掺杂质量比值为0.1～10。
在本发明的一些实施例中，所述载流子传输材料包括空穴传输材料和电子传输材料，所述量子点发光层包括量子点发光材料，所述量子点发光材料、所述空穴传输材料和所述电子传输材料之间形成p-i-n异质结。
在本发明的一些实施例中，所述量子点发光层包括量子点发光材料，所述载流子传输材料的导带/价带与所述量子点发光材料的导带/价带形成的带阶为0.1～0.5eV。
在本发明的一些实施例中，所述空穴功能层包括空穴注入层，所述电子功能层包括电子注入层，所述空穴注入层与所述量子点发光层的一侧表面直接接触，所述电子注入层与所述量子点发光层的另一侧表面直接接触。
在本发明的一些实施例中，所述空穴功能层包括叠层的空穴注入层、空穴传输层，所述电子功能层包括叠层的电子传输层和电子注入层，所述空穴传输层与所述量子点发光层的一侧表面直接接触，所述电子传输层与所述量子点发光层的另一侧表面直接接触。
在本发明的一些实施例中，所述载流子传输材料包括CBP、TFB、Poly-TBD、PFO、TPBi、Bphen、B3PYMPM中的至少一种。
在本发明的一些实施例中，所述空穴传输材料包括CBP、TFB、Poly-TBD、PFO中的至少一种，所述电子传输材料包括TPBi、Bphen、B3PYMPM中的至少一种。
本发明实施例还提供另一种电致发光器件，包括：
依次叠层设置的阳极、空穴功能层、量子点发光层、电子功能层以及阴极其中，所述量子点发光层中掺杂有载流子传输材料。
在本发明的一些实施例中，所述量子点发光层包括量子点发光材料，所述载流子传输材料与所述量子点发光材料的质量比为0.1％～2％。
在本发明的一些实施例中，所述载流子传输材料包括空穴传输材料和电子传输材料中的至少一种。
在本发明的一些实施例中，所述载流子传输材料包括空穴传输材料和电子传输材料，所述空穴传输材料和所述电子传输材料的掺杂质量比值为0.1～10。
在本发明的一些实施例中，所述载流子传输材料包括空穴传输材料和电子传输材料，所述量子点发光层包括量子点发光材料，所述量子点发光材料与所述载流子传输材料形成p-i-n异质结。
在本发明的一些实施例中，所述量子点发光层包括量子点发光材料，所述载流子传输材料的导带/价带与所述量子点发光材料的导带/价带形成的带阶为0.1～0.5eV。
在本发明的一些实施例中，所述空穴功能层包括空穴注入层，所述电子功能层包括电子注入层，所述空穴注入层与所述量子点发光层的一侧表面直接接触，所述电子注入层与所述量子点发光层的另一侧表面直接接触。
在本发明的一些实施例中，所述空穴功能层包括叠层的空穴注入层、空穴传输层，所述电子功能层包括叠层的电子传输层和电子注入层，所述空穴传输层与所述量子点发光层的一侧表面直接接触，所述电子传输层与所述量子点发光层的另一侧表面直接接触。
在本发明的一些实施例中，所述载流子传输材料包括CBP、TFB、Poly-TBD、PFO、TPBi、Bphen、B3PYMPM中的至少一种。
在本发明的一些实施例中，所述载流子传输材料包括空穴传输材料，所述空穴传输材料包括CBP、TFB、Poly-TBD、PFO中的至少一种。
在本发明的一些实施例中，所述载流子传输材料包括电子传输材料，所述电子传输材料包括TPBi、Bphen、B3PYMPM中的至少一种。本发明实施例还提供上述实施例中的电致发光器件的制备方法，包括：
S10，将载流子传输材料分散于第一有机溶剂中，混合均匀至形成第一溶液；
S20，将量子点发光材料溶于第二有机溶剂中，混合均匀至形成第二溶液；
S30，将所述第一溶液和所述第二溶液混合，形成混合溶液；
S40，将所述混合溶液涂布于一制备有阳极和空穴功能层的基板上，形成量子点发光层；
S50，在所述量子点发光层上依次制备电子功能层和阴极。
有益效果
本发明实施例提供一种电致发光器件及其制备方法，电致发光器件包括依次叠层设置的阳极、空穴功能层、量子点发光层、电子功能层以及阴极，量子点发光层中掺杂有载流子传输材料，一方面载流子传输材料可改善量子点发光材料的导电性，促进载流子的注入和传输，另一方面p型、n型传输材料与量子点发光材料混合形成微小p-i-n型异质结，能够提高载流子的复合几率，提高电致发光器件的发光量子效率。
附图说明
图1为本发明实施例提供的电致发光器件的膜层叠构示意图；
图2为本发明实施例提供的电致发光器件的制备方法的流程示意图。
本发明的实施方式
下面将结合本申请实施例中的附图，对本申请实施例中的技术方案进行清楚、完整地描述。显然，所描述的实施例仅仅是本申请一部分实施例，而不是全部的实施例。基于本申请中的实施例，本领域技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本申请保护的范围。
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。为了简化本申请的公开，下文中对特定例子的部件和设置进行描述。当然，它们仅仅为示例，并且目的不在于限制本申请。本申请提供了的各种特定的工艺和材料的例子，但是本领域普通技术人员可以意识到其他工艺的应用和/或其他材料的使用。
本发明针对现有的电致发光器件，由于载流子在电子功能层与量子点发光层界面、以及在空穴功能层与量子点发光层界面会积累，发生猝灭，导致电致发光器件发光效率低的技术问题，提出本实施例以克服该缺陷。
请参阅图1，本发明实施例提供一种电致发光器件100，所述电致发光器件100包括一侧层叠设置的阳极20、空穴功能层30、量子点发光层40、电子功能层50以及阴极60。所述电致发光器件100可为顶发光器件，也可为底发光器件，所述阳极20设置于一基板10上，所述空穴功能层30设置于所述阳极20上，所述量子点发光层40设置于所述空穴功能层30上，所述电子功能层50设置于所述量 子点发光层40上，所述阴极60设置于所述电子功能层50上。
在本发明的实施例中，所述基板10可为玻璃基板，所述阳极20可为透明的ITO(Indium tin oxide,氧化铟锡)电极，所述阴极60可为铝电极。
由于现有技术中，量子点发光层40表面的有机长链配体的绝缘性会导致载流子(空穴、电子)在量子点发光层40与空穴功能层30之间的界面、以及在量子点发光层40与电子功能层50之间的界面积累，发生猝灭。本发明实施例在量子点发光层40中掺杂载流子传输材料，可改变量子点发光层40的导电性能，但不会改变量子点发光层40的发光特性，可增加载流子的扩散通道数，促进载流子在量子点发光层40中的扩散，有效减少载流子在上述界面积累而发生猝灭。本发明实施例提及的“掺杂”指的是在某种膜层材料中混入另外一种材料，混入的材料不会改变原来的膜层材料的晶体结构，因此本发明实施例掺杂的载流子传输材料不会进入到量子点发光层40的量子点发光材料的晶体结构中去。
所述载流子传输材料包括空穴传输材料和电子传输材料中的至少一种，在本发明的实施例中，所述载流子传输材料同时包括空穴传输材料和电子传输材料，所述空穴传输材料可为P型有机传输材料，所述电子传输材料可为N型有机传输材料。P型有机传输材料有利于运输空穴，N型有机传输材料有利于运输电子，空穴经空穴功能层30运输至量子点发光层40中的量子点发光材料或空穴传输材料，电子经电子功能层50运输至量子点发光层40中的量子点发光材料或电子传输材料，增加了载流子在量子点发光层40中的扩散通道数量。
在所述量子点发光层40中，由于增加了载流子传输材料与所述量子点发光材料的接触面积，所述量子点发光材料与所述空穴传输材料以及所述电子传输材料之间形成p-i-n异质结，无数微小的p-i-n异质结可有效提高空穴、电子在量子点发光层40中的复合几率，从而达到提高电致发光器件的量子点效率。
具体地，所述载流子传输材料与所述量子点发光材料的质量比为0.1％～2％，在此范围内，可有效改善量子点发光效率。掺杂载流子传输材料不能过多，否则会将本身为半导体的量子点发光层40变为导电膜层，导致电致发光器件无法发光。
进一步地，所述载流子传输材料同时包括空穴传输材料和电子传输材料时，所述空穴传输材料和所述电子传输材料的掺杂质量比值为0.1～10，可有效 改善空穴、电子在量子点发光层40中的注入与传输。
一方面，所述载流子传输材料的选取主要是满足载流子的传输能力，能够有效地运输载流子；另一方面可根据载流子传输材料的导带/价带与量子点发光材料的导带/价带形成的带阶大小来选取，所述载流子传输材料的导带/价带与所述量子点发光材料的导带/价带形成的带阶为0.1～0.5eV，有助于空穴、电子在量子点发光层40中的复合。
所述载流子传输材料包括CBP(4,4'-二(9-咔唑)联苯)、TFB(聚(9,9-二辛基芴-CO-N-(4-丁基苯基)二苯胺))、Poly-TBD、PFO(聚(9,9-二辛基芴-2,7-二基))、TPBi(1,3,5-三(1-苯基-1H-苯并咪唑-2-基)苯)、Bphen(4,7-二苯基-1,10-菲啰啉)、B3PYMPM(4,6-双(3,5-二(3-吡啶)基苯基)-2-甲基嘧啶)中的至少一种。其中，CBP、TFB、Poly-TBD、PFO可作为空穴传输材料，TPBi、Bphen、B3PYMPM可为电子传输材料。在本发明实施例中，在所述量子点发光层40中同时掺杂有空穴传输材料和电子传输材料，掺杂的空穴传输材料可为CBP，掺杂的电子传输材料可为TPBi。
在本发明的实施例中，所述空穴功能层30包括空穴注入层，所述电子功能层50包括电子注入层，所述空穴注入层与所述量子点发光层40的一侧表面直接接触，所述电子注入层与所述量子点发光层40的另一侧表面直接接触。
在本发明的实施例中，所述空穴注入层可为PEDOT:PSS材料，所述电子注入层可为ZnO材料。
在其他实施例中，所述空穴功能层30还包括空穴传输层，所述电子功能层50还包括电子传输层，以提高载流子在到达量子点发光层40之前的运输能力。具体地，所述空穴功能层30包括叠层的空穴注入层、空穴传输层，所述电子功能层50包括叠层的电子传输层和电子注入层，所述空穴传输层与所述量子点发光层40的一侧表面直接接触，所述电子传输层与所述量子点发光层40的另一侧表面直接接触。
请参阅图2，本发明实施例还提供一种上述实施例中的电致发光器件100的制备方法，包括S10，将载流子传输材料分散于第一有机溶剂中，混合均匀至形成第一溶液；S20，将量子点发光材料溶于第二有机溶剂中，混合均匀至形成第二溶液；S30，将所述第一溶液和所述第二溶液混合，形成混合溶液； S40，将所述混合溶液涂布于一制备有阳极20和空穴功能层30的基板10上，形成量子点发光层40；S50，在所述量子点发光层40上依次制备电子功能层50和阴极60。
具体地，所述载流子传输材料可选取CBP和TPBi材料，将CBP和TPBi同时分散于所述第一有机溶剂中，经过超声振荡以使得载流子传输材料充分溶解、混合均匀。
其中，所述第一有机溶剂可为非极性溶剂，所述第一有机溶剂包括己烷、庚烷、辛烷、壬烷、癸烷、环己烷中的至少一种。所述载流子传输材料占所述第一溶液的质量分数为0.1％～5％，在此范围内，所述载流子传输材料具有较好的溶解度。
在本发明的实施例中，所述第二有机溶剂与第一有机溶剂的材料选择保持一致，有利于增大第一溶液和第二溶液混合的均匀性。
将第一溶液和第二溶液混合时，同样用超声振荡，使溶液中的溶质充分扩散，之后利用0.45um的PET滤膜过滤混合溶液，以去除大颗粒。所述第一溶液和第二溶液按不同比例混合，混合时，需保证两种溶液中的载流子传输材料与量子点发光材料的质量配比为0.1％～2％即可。
在制备有阳极20、空穴注入层(和空穴传输层)的基板10上依次旋涂或蒸镀混合溶液，再经过烘烤等工艺，形成量子点发光层40，所述第一溶剂和所述第二溶剂会在形成量子点发光层40的过程中挥发掉，不会对量子点发光层40的发光效率造成影响。
之后，在所述量子点发光层40上依次制备电子功能层50和阴极60，所述电子功能层50包括电子注入层，在其他实施例中，所述电子功能层50还可进一步包括形成在所述电子注入层上的电子传输层。
综上，本发明实施例提供一种电致发光器件及其制备方法，包括依次叠层设置的阳极20、空穴功能层30、量子点发光层40、电子功能层50以及阴极60，量子点发光层40中掺杂有载流子传输材料，一方面载流子传输材料可改善量子点发光材料的导电性，促进载流子的注入和传输，另一方面p型、n型传输材料与量子点发光材料混合形成微小p-i-n型异质结，能够提高载流子的复合几率，提高电致发光器件的发光量子效率。
在上述实施例中，对各个实施例的描述都各有侧重，某个实施例中没有详述的部分，可以参见其他实施例的相关描述。
以上对本发明实施例所提供的一种电致发光器件及其制备方法进行了详细介绍，本文中应用了具体个例对本发明的原理及实施方式进行了阐述，以上实施例的说明只是用于帮助理解本发明的技术方案及其核心思想；本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例的技术方案的范围。

Claims (20)

  1. 一种电致发光器件，其中，包括：
    依次叠层设置的阳极、空穴功能层、量子点发光层、电子功能层以及阴极；其中，
    所述量子点发光层中掺杂有载流子传输材料，所述载流子传输材料包括空穴传输材料和电子传输材料中的至少一种；
    所述量子点发光层包括量子点发光材料，所述载流子传输材料与所述量子点发光材料的质量比为0.1％～2％。
  2. 根据权利要求1所述的电致发光器件，其中，所述载流子传输材料包括空穴传输材料和电子传输材料，所述空穴传输材料和所述电子传输材料的掺杂质量比值为0.1～10。
  3. 根据权利要求2所述的电致发光器件，其中，所述载流子传输材料包括空穴传输材料和电子传输材料，所述量子点发光层包括量子点发光材料，所述量子点发光材料、所述空穴传输材料和所述电子传输材料之间形成p-i-n异质结。
  4. 根据权利要求2所述的电致发光器件，其中，所述量子点发光层包括量子点发光材料，所述载流子传输材料的导带/价带与所述量子点发光材料的导带/价带形成的带阶为0.1～0.5eV。
  5. 根据权利要求1所述的电致发光器件，其中，所述空穴功能层包括空穴注入层，所述电子功能层包括电子注入层，所述空穴注入层与所述量子点发光层的一侧表面直接接触，所述电子注入层与所述量子点发光层的另一侧表面直接接触。
  6. 根据权利要求1所述的电致发光器件，其中，所述空穴功能层包括叠层的空穴注入层、空穴传输层，所述电子功能层包括叠层的电子传输层和电子注入层，所述空穴传输层与所述量子点发光层的一侧表面直接接触，所述电子传输层与所述量子点发光层的另一侧表面直接接触。
  7. 根据权利要求1所述的电致发光器件，其中，所述载流子传输材料包括CBP、TFB、Poly-TBD、PFO、TPBi、Bphen、B3PYMPM中的至少一种。
  8. 根据权利要求7所述的电致发光器件，其中，所述空穴传输材料包括 CBP、TFB、Poly-TBD、PFO中的至少一种，所述电子传输材料包括TPBi、Bphen、B3PYMPM中的至少一种。
  9. 一种电致发光器件，其中，包括：
    依次叠层设置的阳极、空穴功能层、量子点发光层、电子功能层以及阴极；其中，
    所述量子点发光层中掺杂有载流子传输材料。
  10. 根据权利要求9所述的电致发光器件，其中，所述量子点发光层包括量子点发光材料，所述载流子传输材料与所述量子点发光材料的质量比为0.1％～2％。
  11. 根据权利要求9所述的电致发光器件，其中，所述载流子传输材料包括空穴传输材料和电子传输材料中的至少一种。
  12. 根据权利要求11所述的电致发光器件，其中，所述载流子传输材料包括空穴传输材料和电子传输材料，所述空穴传输材料和所述电子传输材料的掺杂质量比值为0.1～10。
  13. 根据权利要求11所述的电致发光器件，其中，所述载流子传输材料包括空穴传输材料和电子传输材料，所述量子点发光层包括量子点发光材料，所述量子点发光材料、所述空穴传输材料和所述电子传输材料之间形成p-i-n异质结。
  14. 根据权利要求11所述的电致发光器件，其中，所述量子点发光层包括量子点发光材料，所述载流子传输材料的导带/价带与所述量子点发光材料的导带/价带形成的带阶为0.1～0.5eV。
  15. 根据权利要求9所述的电致发光器件，其中，所述空穴功能层包括空穴注入层，所述电子功能层包括电子注入层，所述空穴注入层与所述量子点发光层的一侧表面直接接触，所述电子注入层与所述量子点发光层的另一侧表面直接接触。
  16. 根据权利要求9所述的电致发光器件，其中，所述空穴功能层包括叠层的空穴注入层、空穴传输层，所述电子功能层包括叠层的电子传输层和电子注入层，所述空穴传输层与所述量子点发光层的一侧表面直接接触，所述电子传输层与所述量子点发光层的另一侧表面直接接触。
  17. 根据权利要求9所述的电致发光器件，其中，所述载流子传输材料包括CBP、TFB、Poly-TBD、PFO、TPBi、Bphen、B3PYMPM中的至少一种。
  18. 根据权利要求17所述的电致发光器件，其中，所述载流子传输材料包括空穴传输材料，所述空穴传输材料包括CBP、TFB、Poly-TBD、PFO中的至少一种。
  19. 根据权利要求17所述的电致发光器件，其中，所述载流子传输材料包括电子传输材料，所述电子传输材料包括TPBi、Bphen、B3PYMPM中的至少一种。
  20. 一种电致发光器件的制备方法，其中，包括：
    S10，将载流子传输材料分散于第一有机溶剂中，混合均匀至形成第一溶液；
    S20，将量子点发光材料溶于第二有机溶剂中，混合均匀至形成第二溶液；
    S30，将所述第一溶液和所述第二溶液混合，形成混合溶液；
    S40，将所述混合溶液涂布于一制备有阳极和空穴功能层的基板上，形成量子点发光层；
    S50，在所述量子点发光层上依次制备电子功能层和阴极。
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