WO2021136044A1 - Diode électroluminescente à points quantiques et son procédé de fabrication - Google Patents

Diode électroluminescente à points quantiques et son procédé de fabrication Download PDF

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WO2021136044A1
WO2021136044A1 PCT/CN2020/138768 CN2020138768W WO2021136044A1 WO 2021136044 A1 WO2021136044 A1 WO 2021136044A1 CN 2020138768 W CN2020138768 W CN 2020138768W WO 2021136044 A1 WO2021136044 A1 WO 2021136044A1
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layer
quantum dot
dot light
znmgo
zno
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PCT/CN2020/138768
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Chinese (zh)
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郭煜林
吴龙佳
张天朔
李俊杰
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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
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
    • 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
    • H10K50/166—Electron 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
    • H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
    • H10K71/421—Thermal treatment, e.g. annealing in the presence of a solvent vapour using coherent electromagnetic radiation, e.g. laser annealing
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass

Definitions

  • the present disclosure relates to the field of quantum dot light-emitting devices, in particular to a quantum dot light-emitting diode and a preparation method thereof.
  • Quantum dots are semiconductor clusters with a size of 1-10 nm. Due to the quantum size effect, they have photoelectronic properties with adjustable band gaps and can be used in light-emitting diodes, solar cells, bioluminescent labels and other fields. People adjust the size of quantum dots to achieve the required specific wavelength of light emission. According to the elements of quantum dots, quantum dots can be divided into group II-VI quantum dots (such as CdSe, CdS, CdTe, ZnSe, ZnS, etc.), group III-V Quantum dots (such as GaAs, InAs, InP, etc.), carbon quantum dots and silicon quantum dots. At present, CdSe QDs are more researched, and their emission wavelength tuning range can be from blue light to red light.
  • group II-VI quantum dots such as CdSe, CdS, CdTe, ZnSe, ZnS, etc.
  • group III-V Quantum dots such as GaAs, InAs, InP, etc.
  • inorganic electroluminescent devices electrons and holes are injected from the cathode and anode respectively, and then recombine in the light-emitting layer to form excitons to emit light.
  • the conduction band electrons in wide-bandgap semiconductors can be accelerated under high electric fields to obtain high enough energy to hit QDs to make them emit light.
  • semiconductor quantum dot material has important commercial application value.
  • ZnO is a direct bandgap n-type semiconductor material, with a wide band gap of 3.37eV and a low work function of 3.7eV, and has the advantages of good stability, high transparency, safety and non-toxicity, making ZnO a suitable electronic Transmission layer material.
  • ZnO has many potential advantages. Its exciton binding energy is as high as 60meV, which is much higher than other wide-gap semiconductor materials (GaN is 25meV), and it is 2.3 times the room temperature thermal energy (26meV), so the excitons of ZnO can be at room temperature. Stable existence.
  • ZnO has a hexagonal wurtzite structure, showing strong spontaneous polarization; in the ZnO-based heterostructure, the strain of the material will lead to extremely strong piezoelectric polarization, leading to a polarization effect in the ZnO-based heterostructure .
  • the polarization electric field generated by the polarization induces a high concentration of interface polarization charges on the ZnO heterojunction surface, thereby regulating the energy band of the material, and then affecting the performance of related structural devices.
  • QLED devices widely adopt a mixed structure of organic and inorganic carrier transport layers, which are composed of an anode, an organic hole transport layer, a light-emitting layer, an inorganic electron transport layer, and a cathode.
  • This device structure often uses p-type organic semiconductors, such as PVK, Poly-TPD, TFB, etc., as the hole transport layer material, and n-type inorganic semiconductor ZnO as the electron transport layer material.
  • the hole mobility of these organic semiconductor materials is less than that of ZnO. Therefore, the electron injection and transport efficiency in QLED devices is much greater than the hole injection and transport efficiency, resulting in an imbalance of electron and hole injection and limiting the improvement of device efficiency. .
  • the purpose of the present disclosure is to provide a quantum dot light-emitting diode and a manufacturing method thereof, aiming to solve the problem that the existing method of improving the electron transmission efficiency requires the introduction of new materials.
  • a method for preparing a quantum dot light-emitting diode which comprises the steps:
  • the electron transport layer including a stacked ZnO layer and a ZnMgO layer, and the ZnO layer is arranged close to the quantum dot light-emitting layer;
  • a cathode is formed on the electron transport layer to obtain a quantum dot light-emitting diode.
  • a quantum dot light emitting diode comprising: an anode, a cathode, a quantum dot light emitting layer arranged between the anode and the cathode, and an electron transport layer arranged between the cathode and the quantum dot light emitting layer, wherein the electron
  • the transmission layer includes a laminated ZnO layer and a ZnMgO layer, and the ZnO layer is arranged close to the quantum dot light-emitting layer side.
  • the present disclosure introduces an interface inside the electron transport layer by setting the ZnO layer/ZnMgO layer double layer as the electron transport layer, and uses the newly added interface to effectively block the excess electrons from reaching the QD interface, thereby reducing the exciton quenching caused by the charging of the QD. And efficiency roll-off.
  • the method does not need to introduce new materials, nor does it involve contact with other functional layers. It just adds an interface to the existing ZnO electron transport layer to control the injection of electrons and achieve a balance between it and hole injection.
  • ZnMgO Mg-doped ZnO
  • ZnMgO can adjust the forbidden band width of the electron transport layer, adjust the electron injection barrier, reduce the electron injection efficiency, and balance the electron-hole injection to promote electron-hole in the quantum dot The purpose of effective radiation recombination in the light-emitting layer, thereby improving the efficiency of the device.
  • ZnMgO has a wide band gap, so it can also play a role in blocking holes in the device, enabling the device to achieve better performance.
  • the preparation of the electron transport layer is simple, which is suitable for large-area and large-scale preparation.
  • FIG. 1 is a schematic structural diagram of a quantum dot light-emitting diode provided in an embodiment of the disclosure.
  • FIG. 2 is a schematic flow chart of a method for manufacturing a quantum dot light-emitting diode provided in an embodiment of the 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, but not used to limit the present disclosure.
  • the embodiment of the present disclosure provides a method for manufacturing a quantum dot light-emitting diode, which includes the following steps:
  • the electron transport layer including a stacked ZnO layer and a ZnMgO layer, and the ZnO layer is arranged close to the quantum dot light-emitting layer;
  • a cathode is formed on the electron transport layer to obtain a quantum dot light-emitting diode.
  • the electron transport layer is composed of a stacked ZnO layer and a ZnMgO (a small amount of Mg doped ZnO) layer.
  • a ZnO layer/ZnMgO layer as the electron transport layer, the inside of the electron transport layer Introduce an interface, use the new interface to effectively block the excess electrons from reaching the QD interface, and reduce the exciton quenching and efficiency roll-off caused by the charging of the QD.
  • the existing single-layer ZnO electron transport layer is configured as a ZnO layer/ZnMgO layer double layer as the electron transport layer to increase the electron transport barrier and delay the electron injection.
  • ZnMgO is a small amount of Mg-doped ZnO, the main material in the ZnMgO layer is still ZnO, and Mg and Zn are approximately the same quality, so this method does not introduce new materials (such as no need to introduce heterogeneous Material), it does not involve contact with other functional layers, but an interface is added to the existing ZnO electron transport layer to control the injection of electrons and achieve a balance with hole injection.
  • ZnMgO can adjust the forbidden band width of the electron transport layer, adjust the electron injection barrier, reduce the electron injection efficiency, and balance the electron-hole injection to promote effective electron-hole radiation in the quantum dot light-emitting layer The purpose of recombination, thereby improving the efficiency of the device.
  • ZnMgO has a wide band gap, so it can also play a role in blocking holes in the device, enabling the device to achieve better performance.
  • the preparation of the electron transport layer is simple, which is suitable for large-area and large-scale preparation.
  • the quantum dot light-emitting diode has many forms, and the quantum dot light-emitting diode is divided into a positive structure and an inverted structure.
  • This embodiment will mainly use a quantum dot light-emitting diode with a positive structure as shown in FIG. 1 As an example, the above preparation method is introduced in detail. In one embodiment, as shown in FIG. 1
  • the quantum dot light emitting diode includes a substrate 1, an anode 2, a hole transport layer 3, a quantum dot light emitting layer 4, an electron transport layer 5 and Cathode 6; wherein, the electron transport layer 5 includes a stacked ZnO layer and a ZnMgO layer, and the ZnO layer is located close to the quantum dot light-emitting layer 4 side.
  • the manufacturing method of the quantum dot light-emitting diode, as shown in FIG. 2, includes the steps:
  • the electron transport layer including a stacked ZnO layer and a ZnMgO layer, and the ZnO layer is disposed close to a side of the quantum dot light-emitting layer;
  • step S40 specifically includes:
  • the method for preparing ZnO nanoparticles includes the steps of mixing zinc salt and alkali, and reacting to obtain ZnO nanoparticles.
  • the method for preparing ZnO nanoparticles specifically includes the steps of: adding zinc salt to an organic solvent to form a zinc salt solution; adding lye to the zinc salt solution and stirring for 1-4 hours, A clear and transparent solution is obtained, and ZnO nanoparticles are obtained after purification (such as precipitation with acetone and centrifugation).
  • concentration of the zinc salt solution is 0.1-1M.
  • the zinc salt solution is mixed with the lye.
  • the pH of the lye is 12-14.
  • the zinc salt is a soluble inorganic zinc salt or a soluble organic zinc salt.
  • the zinc salt includes zinc acetate, zinc nitrate, zinc chloride, zinc sulfate, and zinc acetate dihydrate, etc., which are not limited to one or more of these.
  • the lye is prepared by dispersing an alkali in a solvent, and the concentration of the lye is 0.1-1M.
  • the base includes potassium hydroxide, sodium hydroxide, and tetramethylammonium hydroxide, etc., which are not limited to one or more of these.
  • the solvent includes DMF, DMSO, etc., which are not limited to one or more of them.
  • the method for preparing ZnMgO nanoparticles includes the steps of mixing zinc salt, magnesium salt and alkali, and reacting to obtain ZnMgO nanoparticles.
  • the method for preparing ZnMgO nanoparticles specifically includes the steps of: adding zinc salt and magnesium salt to an organic solvent to form a salt solution; adding lye to the salt solution and stirring for 1-4 hours , To obtain a clear and transparent solution, after purification (such as precipitation with acetone, centrifugation) to obtain ZnMgO nanoparticles. Further, the total concentration of the salt solution is 0.1-1M. Further, the pH of the lye is 12-14.
  • the mass ratio of the zinc salt to the magnesium salt is (10-20):1.
  • the molar ratio of the Zn element in the zinc salt to the OH - in the alkali is 1: (1.5-3.0).
  • the zinc salt is a soluble inorganic zinc salt or a soluble organic zinc salt.
  • the zinc salt includes zinc acetate, zinc nitrate, zinc chloride, zinc sulfate, and zinc acetate dihydrate, etc., which are not limited to one or more of these.
  • the magnesium salt is a soluble inorganic magnesium salt or a soluble organic magnesium salt.
  • the magnesium salt includes magnesium acetate, magnesium nitrate, magnesium chloride, magnesium sulfate, and magnesium acetate dihydrate, etc., which are not limited to one or more of these.
  • the lye is prepared by dispersing an alkali in a solvent, and the concentration of the alkali in the lye is 0.1-1M.
  • the base includes potassium hydroxide, sodium hydroxide, and tetramethylammonium hydroxide, etc., which are not limited to one or more of these.
  • the solvent includes DMF, DMSO, etc., which are not limited to one or more of them.
  • the method of covering the ZnO nanoparticle solution may be spin coating, spraying, printing, etc., but is not limited thereto.
  • the spin coating speed may be 3000-5000 rpm/min
  • the spin coating time may be 0.5-1.5 min.
  • the thickness of the ZnO layer is controlled by adjusting the concentration of the ZnO nanoparticle solution, the spin coating speed and the spin coating time, and then annealed to form a film.
  • the annealing temperature may be 60-120°C.
  • the method of covering the ZnMgO nanoparticle solution may be spin coating, spray coating, printing, etc., but is not limited thereto.
  • the spin coating speed may be 3000-5000 rpm/min
  • the spin coating time may be 0.5-1.5 min.
  • the thickness of the ZnMgO layer is controlled by adjusting the concentration of the ZnMgO nanoparticle solution, the spin coating speed and the spin coating time, and then annealed to form a film.
  • the annealing temperature may be 60-120°C.
  • the anode in order to obtain a high-quality hole transport layer, the anode needs to undergo a pretreatment process.
  • the pretreatment process specifically includes: cleaning the anode with a cleaning agent to initially remove the stains on the anode surface, followed by ultrasonic cleaning in deionized water, acetone, absolute ethanol, and deionized water for 20 minutes to remove the stains on the surface. Impurities are finally blown dry with high-purity nitrogen to obtain the anode.
  • the step of forming a hole transport layer on the anode includes: placing the substrate on a homogenizer and spin-coating the prepared solution of the hole transport material to form a film; by adjusting the concentration of the solution, The film thickness is controlled by spin coating speed and spin coating time, and then thermally annealed at an appropriate temperature to obtain the hole transport layer.
  • the step of preparing a quantum dot light-emitting layer on the hole transport layer includes: placing the substrate on which the hole transport layer has been prepared on a homogenizer, and preparing a solution of a certain concentration of light-emitting substance The film is formed by spin coating, the thickness of the quantum dot light-emitting layer is controlled by adjusting the concentration of the solution, the spin-coating speed, and the spin-coating time, and finally the quantum dot light-emitting layer is dried at an appropriate temperature to obtain the quantum dot light-emitting layer.
  • the obtained quantum dot light emitting diode is packaged.
  • the packaging process can adopt common machine packaging or manual packaging.
  • the oxygen content and water content in the environment of the packaging process are both lower than 0.1 ppm to ensure the stability of the device.
  • the preparation method of each layer can be a chemical method or a physical method
  • the chemical method includes but not limited to chemical vapor deposition method, continuous ion layer adsorption and reaction method, anodic oxidation method, electrolytic deposition method, co-precipitation method.
  • One or more; physical methods include, but are not limited to, solution methods (such as spin coating, printing, blade coating, dipping, dipping, dipping, spraying, roller coating, casting, 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, element One or more of layer deposition method, pulsed laser deposition method, etc.).
  • solution methods such as spin coating, printing, blade coating, dipping, dipping, dipping, spraying, roller coating, casting, 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, element One or more of layer deposition method, pulsed laser deposition method,
  • the embodiments of the present disclosure provide a quantum dot light emitting diode, which includes an anode, a cathode, a quantum dot light emitting layer arranged between the anode and the cathode, and an electron transport layer arranged between the cathode and the quantum dot light emitting layer,
  • the electron transport layer material includes a laminated ZnO layer and a ZnMgO layer, and the ZnO layer is arranged on a side close to the quantum dot light-emitting layer.
  • the electron transport layer is a ZnO layer and a ZnMgO layer that are stacked.
  • the quantum dot light emitting diode includes a substrate 1, an anode 2, a hole transport layer 3, a quantum dot light emitting layer 4, an electron transport layer 5 and Cathode 6; wherein, the material of the electron transport layer 5 is a laminated ZnO layer and a ZnMgO layer, and the ZnO layer is located close to the quantum dot light-emitting layer 4 side.
  • the electron transport layer is composed of two layers of laminated ZnO layer and ZnMgO layer.
  • ZnO layer/ZnMgO layer By setting the ZnO layer/ZnMgO layer as the electron transport layer, an interface is introduced inside the electron transport layer, and the new interface is used to effectively block excess Electrons reach the QD interface, reducing the exciton quenching and efficiency roll-off caused by the charging of the QD.
  • the interface barrier can be used to control the injection of electrons to achieve a balance with the injection of holes. This method does not need to introduce new materials, nor does it involve contact with other functional layers. It just adds an interface to the existing ZnO electron transport layer to control the transport of electrons.
  • ZnMgO Mg-doped ZnO
  • ZnMgO can adjust the forbidden band width of the electron transport layer, adjust the electron injection barrier, reduce the electron injection efficiency, and balance the electron-hole injection to promote electron-hole in the quantum dot The purpose of effective radiation recombination in the light-emitting layer, thereby improving the efficiency of the device.
  • ZnMgO has a wide band gap, so it can also play a role in blocking holes in the device, enabling the device to achieve better performance.
  • the thickness of the ZnO layer is 20-50 nm.
  • the thickness of the ZnMgO layer is 20-50 nm.
  • the thickness of the electron transport layer is 20 nm-60 nm. If the thickness of the electron transport layer is too thin, the carrier transport performance cannot be guaranteed, resulting in electrons failing to reach the quantum dot light-emitting layer, which causes hole-electron recombination in the transport layer, thereby causing quenching; If the thickness of the layer is too thick, the light transmittance of the film layer will decrease, and the carrier passability of the device will decrease, resulting in a decrease in the overall conductivity of the device.
  • the substrate may be a substrate made of rigid material, such as glass, or it may be a substrate made of flexible material, such as one of PET or PI.
  • the anode may be selected from one of indium-doped tin oxide (ITO), fluorine-doped tin oxide (FTO), antimony-doped tin oxide (ATO), and aluminum-doped zinc oxide (AZO). kind or more.
  • ITO indium-doped tin oxide
  • FTO fluorine-doped tin oxide
  • ATO antimony-doped tin oxide
  • AZO aluminum-doped zinc oxide
  • the material of the hole transport layer can be selected from materials with good hole transport properties, for example, can include but not limited to TFB, PVK, Poly-TPD, TCTA, PEDOT: PSS, CBP, NiO, MoO One or more of 3 grades.
  • the material of the quantum dot light-emitting layer may be oil-soluble quantum dots, and the oil-soluble quantum dots include one or more of binary phase, ternary phase, quaternary phase quantum dots, etc.; wherein Binary phase quantum dots include one or more of CdS, CdSe, CdTe, InP, AgS, PbS, PbSe, HgS, etc., and ternary phase quantum dots include ZnCdS, CuInS, ZnCdSe, ZnSeS, ZnCdTe, PbSeS, etc.
  • One or more, quaternary phase quantum dots include one or more of ZnCdS/ZnSe, CuInS/ZnS, ZnCdSe/ZnS, CuInSeS, ZnCdTe/ZnS, PbSeS/ZnS, etc.
  • the material of the quantum dot light-emitting layer may be any one of the common red, green, and blue quantum dots or other yellow light.
  • the quantum dots may contain cadmium or not contain cadmium.
  • the quantum dot light-emitting layer of the material has the characteristics of wide excitation spectrum and continuous distribution, and high emission spectrum stability. In this embodiment, the thickness of the quantum dot light-emitting layer is about 20 nm to 60 nm.
  • the cathode can be selected from one of aluminum (Al) electrodes, silver (Ag) electrodes, gold (Au) electrodes, etc., and can also be selected from nano aluminum wires, nano silver wires, and nano gold wires. One of them.
  • the above-mentioned materials have relatively low resistance, which enables smooth injection of carriers.
  • the thickness of the cathode is about 15 nm-30 nm.
  • the quantum dot light emitting diode of the present disclosure may also include one or more layers of the following functional layers: a hole injection layer arranged between the hole transport layer and the anode, and a hole injection layer arranged between the electron transport layer and the cathode. Electron injection layer.
  • This embodiment uses zinc chloride, magnesium chloride, and sodium hydroxide (NaOH) as examples for detailed introduction.
  • Zinc chloride was added to DMF to form a solution with a total concentration of 0.5M, 0.6M NaOH ethanol solution was added dropwise at room temperature, and stirring was continued for 1.5 hours to obtain a clear and transparent solution. Precipitated with acetone, collected after centrifugation, and prepared ZnO nanoparticles. Dissolve the ZnO nanoparticles with ethanol for use.
  • Zinc chloride and magnesium chloride were added to DMF to form a solution with a total concentration of 0.5M, 0.6M NaOH ethanol solution was added dropwise at room temperature, and stirring was continued for 1.5 hours to obtain a clear and transparent solution.
  • This embodiment takes zinc nitrate hexahydrate, magnesium chloride, and potassium hydroxide (KOH) as examples for detailed introduction.
  • Zinc nitrate was added to DMF to form a solution with a total concentration of 0.5M, 0.6M KOH ethanol solution was added dropwise at room temperature, and stirring was continued for 1.5 hours to obtain a clear and transparent solution.
  • This embodiment uses zinc acetate dihydrate, magnesium acetate dihydrate, and tetramethylammonium hydroxide as examples for detailed introduction.
  • Zinc acetate was added to DMF to form a solution with a total concentration of 0.5M, 0.6M tetramethylammonium hydroxide ethanol solution was added dropwise at room temperature, and stirring was continued for 1.5h to obtain a clear and transparent solution.
  • Zinc acetate and magnesium acetate were added to DMF to form a solution with a total concentration of 0.5M, 0.6M KOH ethanol solution was added dropwise at room temperature, and stirring was continued for 1.5 hours to obtain a clear and transparent solution.
  • a quantum dot light-emitting diode includes a laminated structure of an anode and a cathode disposed oppositely, a quantum dot light-emitting layer disposed between the anode and the cathode, and a quantum dot light-emitting layer disposed between the cathode and the quantum dot light-emitting layer
  • the electron transport layer is provided on the hole transport layer between the anode and the quantum dot light-emitting layer, and the anode is provided on the substrate.
  • the material of the substrate is a glass sheet
  • the material of the anode is an ITO substrate
  • the hole transport layer is a material TFB
  • the electron transport layer is a ZnO layer/ZnMgO layer
  • the material of the cathode is Al.
  • the manufacturing method of the quantum dot light-emitting diode includes the following steps:
  • a cathode is prepared on the ZnMgO layer.
  • a quantum dot light-emitting diode comprising a laminated structure of an anode and a cathode arranged oppositely, a quantum dot light-emitting layer arranged between the anode and the cathode, and a quantum dot light-emitting layer arranged between the cathode and the quantum dot light-emitting layer
  • the electron transport layer is provided on the hole transport layer between the anode and the quantum dot light-emitting layer, and the anode is provided on the substrate.
  • the material of the substrate is a glass sheet
  • the material of the anode is an ITO substrate
  • the material of the hole transport layer is TFB
  • the electron transport layer is a ZnO layer/ZnMgO layer
  • the material of the cathode is Al.
  • the manufacturing method of the quantum dot light-emitting diode includes the following steps:
  • a cathode is prepared on the ZnMgO layer.
  • a quantum dot light-emitting diode comprising a laminated structure of an anode and a cathode arranged oppositely, a quantum dot light-emitting layer arranged between the anode and the cathode, and a quantum dot light-emitting layer arranged between the cathode and the quantum dot light-emitting layer
  • the electron transport layer is provided on the hole transport layer between the anode and the quantum dot light-emitting layer, and the anode is provided on the substrate.
  • the material of the substrate is a glass sheet
  • the material of the anode is an ITO substrate
  • the material of the hole transport layer is TFB
  • the electron transport layer is a ZnO layer/ZnMgO layer
  • the material of the cathode is Al.
  • the manufacturing method of the quantum dot light-emitting diode includes the following steps:
  • a cathode is prepared on the ZnMgO layer.
  • a quantum dot light-emitting diode comprising a laminated structure of an anode and a cathode arranged oppositely, a quantum dot light-emitting layer arranged between the anode and the cathode, and a quantum dot light-emitting layer arranged between the cathode and the quantum dot light-emitting layer
  • the electron transport layer is provided on the hole transport layer between the anode and the quantum dot light-emitting layer, and the cathode is provided on the substrate.
  • the material of the substrate is a glass sheet
  • the material of the cathode is an ITO substrate
  • the material of the hole transport layer is TFB
  • the electron transport layer is a ZnO layer/ZnMgO layer
  • the material of the anode is Al.
  • the manufacturing method of the quantum dot light-emitting diode includes the following steps:
  • a quantum dot light-emitting layer is prepared on the ZnO layer, and a hole transport layer is prepared on the quantum dot light-emitting layer;
  • An anode is prepared on the hole transport layer.
  • a quantum dot light-emitting diode comprising a laminated structure of an anode and a cathode arranged oppositely, a quantum dot light-emitting layer arranged between the anode and the cathode, and a quantum dot light-emitting layer arranged between the cathode and the quantum dot light-emitting layer
  • the electron transport layer is provided on the hole transport layer between the anode and the quantum dot light-emitting layer, and the cathode is provided on the substrate.
  • the material of the substrate is a glass sheet
  • the material of the cathode is an ITO substrate
  • the material of the hole transport layer is TFB
  • the electron transport layer is a ZnO layer/ZnMgO layer
  • the material of the anode is Al.
  • the manufacturing method of the quantum dot light-emitting diode includes the following steps:
  • a quantum dot light-emitting layer is prepared on the ZnO layer, and a hole transport layer is prepared on the quantum dot light-emitting layer;
  • An anode is prepared on the hole transport layer.
  • a quantum dot light-emitting diode comprising a laminated structure of an anode and a cathode arranged oppositely, a quantum dot light-emitting layer arranged between the anode and the cathode, and a quantum dot light-emitting layer arranged between the cathode and the quantum dot light-emitting layer
  • the electron transport layer is provided on the hole transport layer between the anode and the quantum dot light-emitting layer, and the cathode is provided on the substrate.
  • the material of the substrate is a glass sheet
  • the material of the cathode is an ITO substrate
  • the material of the hole transport layer is TFB
  • the electron transport layer is a ZnO layer/ZnMgO layer
  • the material of the anode is Al.
  • the manufacturing method of the quantum dot light-emitting diode includes the following steps:
  • a quantum dot light-emitting layer is prepared on the ZnO layer, and a hole transport layer is prepared on the quantum dot light-emitting layer;
  • An anode is prepared on the hole transport layer.
  • a quantum dot light-emitting diode comprising a laminated structure of an anode and a cathode arranged oppositely, a quantum dot light-emitting layer arranged between the anode and the cathode, and a quantum dot light-emitting layer arranged between the cathode and the quantum dot light-emitting layer
  • the electron transport layer is provided on the hole transport layer between the anode and the quantum dot light-emitting layer, and the anode is provided on the substrate.
  • the material of the substrate is a glass sheet
  • the material of the anode is an ITO substrate
  • the material of the hole transport layer is TFB
  • the material of the electron transport layer is a commercial ZnO material (purchased from sigma)
  • the material of the cathode is Al.
  • a quantum dot light-emitting diode comprising a laminated structure of an anode and a cathode arranged oppositely, a quantum dot light-emitting layer arranged between the anode and the cathode, and a quantum dot light-emitting layer arranged between the cathode and the quantum dot light-emitting layer
  • the electron transport layer is provided on the hole transport layer between the anode and the quantum dot light-emitting layer, and the anode is provided on the substrate.
  • the material of the substrate is a glass sheet
  • the material of the anode is an ITO substrate
  • the material of the hole transport layer is TFB
  • the material of the electron transport layer is the ZnMgO material synthesized in the embodiment
  • the material of the cathode is Al.
  • the electron transport films prepared in Examples 1-3, the electron transport films in Comparative Examples 1-2, the quantum dot light-emitting diodes prepared in Examples 4-9 and Comparative Examples 1-2 were tested for performance, and the test indicators and The test method is as follows:
  • Electron mobility test the current density (J)-voltage (V) of the quantum dot light-emitting diode, draw a curve relationship diagram, fit the space charge limited current (SCLC) area in the relationship diagram, and then according to Child,s
  • the law formula calculates the electron mobility:
  • J represents the current density in mAcm -2 ;
  • ⁇ r represents the relative permittivity,
  • ⁇ 0 represents the vacuum permittivity;
  • ⁇ e represents the electron mobility in cm 2 V -1 s -1 ;
  • V represents the driving voltage,
  • the unit is V;
  • d represents the thickness of the film, and the unit is m.
  • the electron mobility test is a single-layer film structure device, namely: cathode/electron transport film/anode.
  • the initial potential and external quantum efficiency test are for the QLED device, namely: anode/hole transport film/quantum dot/electron transport film/cathode, or cathode/electron transport film/quantum dot/hole transport film/anode.
  • the external quantum efficiency of the quantum dot light-emitting diode (the material of the electron transport layer is ZnO/ZnMgO double-layer electron transport film) provided by Examples 4-9 of the present disclosure is significantly higher than that of the quantum dots of the single-layer electron transport layer in Comparative Example 1-2
  • the external quantum efficiency of the light-emitting diode indicates that the quantum dot light-emitting diode obtained in the embodiment has better luminous efficiency.
  • the present disclosure provides a quantum dot light-emitting diode and a manufacturing method thereof.
  • the present disclosure adopts the ZnO layer/ZnMgO layer double layer as the electron transport layer, introduces an interface inside the electron transport layer, and uses the new interface to effectively block excess electrons from reaching the QD interface, delay the electron injection rate, and reduce the excitation caused by the charging of the QD. Sub-quenching and efficiency roll-off.
  • the interface barrier can be used to control the injection of electrons to achieve a balance with the injection of holes.
  • the method does not need to introduce new materials, nor does it involve contact with other functional layers, but only adds an interface to the existing ZnO electron transport layer to control the transport of electrons.
  • ZnMgO Mg-doped ZnO
  • ZnMgO can adjust the forbidden band width of the electron transport layer, adjust the electron injection barrier, reduce the electron injection efficiency, and balance the electron-hole injection to promote electron-hole in the quantum dot
  • ZnMgO has a wide band gap, so it can also play a role in blocking holes in the device, enabling the device to achieve better performance.
  • the preparation of the electron transport layer is simple, which is suitable for large-area and large-scale preparation.

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

L'invention concerne une diode électroluminescente à points quantiques et son procédé de fabrication. Le procédé de fabrication de la diode électroluminescente à points quantiques comprend les étapes consistant à : fournir une anode (2) ; former une couche électroluminescente à points quantiques (4) sur l'anode (2) ; former une couche de transport d'électrons (5) sur la couche électroluminescente à points quantiques (4), la couche de transport d'électrons (5) comprenant une couche de ZnO et une couche de ZnMgO qui sont disposées de manière empilée, et la couche de ZnO étant disposée sur un côté proche de la couche électroluminescente à points quantiques (4) ; et former une cathode (6) sur la couche de transport d'électrons (5), de manière à obtenir une diode électroluminescente à points quantiques. Sans l'introduction d'autres couches de matériau hétérogène, l'utilisation de barrières d'interface peut commander l'injection d'électrons, de manière à équilibrer l'injection d'électrons et de trous. Le ZnMgO peut ajuster la largeur de bande interdite de la couche de transport d'électrons (5), régler les barrières d'injection pour les électrons, réduire l'efficacité d'injection d'électrons, et peut équilibrer l'injection d'électrons et de trous, de manière à obtenir l'objectif de favoriser la recombinaison radiative efficace d'électrons et de trous dans la couche électroluminescente à points quantiques (4), ce qui permet d'améliorer l'efficacité du dispositif.
PCT/CN2020/138768 2019-12-30 2020-12-24 Diode électroluminescente à points quantiques et son procédé de fabrication WO2021136044A1 (fr)

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