WO2022143569A1 - Quantum dot light-emitting diode and preparation method therefor - Google Patents
Quantum dot light-emitting diode and preparation method therefor Download PDFInfo
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- WO2022143569A1 WO2022143569A1 PCT/CN2021/141801 CN2021141801W WO2022143569A1 WO 2022143569 A1 WO2022143569 A1 WO 2022143569A1 CN 2021141801 W CN2021141801 W CN 2021141801W WO 2022143569 A1 WO2022143569 A1 WO 2022143569A1
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- quantum dot
- dot light
- emitting diode
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- emitting layer
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Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
-
- 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
Definitions
- the present application relates to the field of display technology, and in particular, to a quantum dot light-emitting diode and a preparation method thereof.
- Quantum Dot Light Emitting Diode Light Emitting Diodes is an electroluminescent device based on quantum dots (QDs) technology, with self-luminescence, no backlight module, wide viewing angle, high contrast, full curing, suitable for flexible panels, temperature characteristics
- QDs quantum dots
- QLED devices borrow and utilize organic light-emitting diodes (Organic Light-Emitting Diodes) Diode, OLED) device structure, but due to the difference in material composition, the aging phenomenon and aging mechanism of the two are very different.
- QLED devices have various efficiencies (current, power or external quantum efficiency) that decay or increase over time, that is, "negative aging effect” or "positive aging effect”.
- the mechanism of the aging effect is still unclear.
- Many studies have concluded that the changes in device efficiency are mainly caused by factors such as the degradation of the hole functional layer, the accumulation of interface charges, the suppression of surface defect states in the electronic functional layer, or the change of charge mobility.
- the difference in the matching between the materials of different light-emitting color quantum dots and other functional layer materials will also cause different device aging mechanisms.
- the aging effect of red QLED devices is more caused by the degradation of the organic hole functional layer, while blue QLED devices
- the aging effect is more due to the mismatch between the conduction-band maximum (CBM) of the quantum dot light-emitting layer and the electronic functional layer, which leads to the accumulation of electrons in the electronic functional layer.
- CBM conduction-band maximum
- Some researchers have proposed a method and structure for improving the positive aging effect and stability of quantum dot diodes, which revealed that the curable resin-encapsulated QLED device containing active materials such as saturated/unsaturated carboxylic acids has a significant positive aging effect. , and the heat treatment of the packaged device can further improve the efficiency and accelerate the forward aging process (the positive aging effect is generally completed in about 4 to 8 days, and the efficiency tends to be stable).
- This technology is achieved by incorporating active materials into a curable encapsulation resin, or by exposing the QLED device to an environment containing the active material, or by cleaning the QLED stack with a solution containing the active material to introduce the active material into the QLED device.
- This technology has the most significant positive aging effect on green QLED devices, and the efficiency can be improved by 175% (the efficiency improvement ratio is the percentage of the difference between the maximum device efficiency and the first-day test efficiency and the first-day test efficiency ratio), but blue and red
- the efficiency improvement ratio is the percentage of the difference between the maximum device efficiency and the first-day test efficiency and the first-day test efficiency ratio
- One of the objectives of the embodiments of the present application is to provide a quantum dot light-emitting diode and a method for preparing the same.
- a quantum dot light-emitting diode comprising an anode and a cathode disposed opposite to each other, a quantum dot light-emitting layer disposed between the anode and the cathode, and a quantum dot light-emitting layer disposed between the quantum dot light-emitting layer and the cathode.
- the active material is selected from the group consisting of acrylic acid, benzoic acid, methacrylic acid, 3-butenoic acid, crotonic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, hydroxyethyl methacrylate, methyl methacrylate At least one of methyl methacrylate, butyl acrylate, trimethylol glycerate and N-vinylpyrrolidone.
- the active material accounts for 0.0001% to 1% of the total weight of the quantum dot light-emitting layer.
- the quantum dot light-emitting layer consists of quantum dots and the active material.
- the quantum dots are selected from the group consisting of II-VI compounds, III-V compounds, II-V compounds, III-VI compounds, IV-VI compounds, I-III-VI compounds, One or more of II-IV-VI compounds or IV elements.
- the quantum dots are one or more of CdSe/ZnSe, CdSe/CdS, CdSe/CdS/ZnS, ZnCdSeS, ZnCdSeS/ZnS, ZnCdS/ZnS, ZnSe/ZnS.
- the quantum dot light emitting diode further includes a hole functional layer disposed between the anode and the quantum dot light emitting layer.
- the first method for preparing a quantum dot light-emitting diode comprises the following steps:
- the prefabricated device is placed in an atmosphere containing a gaseous active material, and a quantum dot light-emitting layer is prepared on the prefabricated device; wherein the gaseous active material is selected from organic hydrocarbons whose at least one hydrogen atom is substituted by a carboxyl group, a carbon-containing At least one of carbon double bond or carbon-carbon triple bond or organic ester of benzene ring and unsaturated ketone.
- the gaseous active material is selected from organic hydrocarbons whose at least one hydrogen atom is substituted by a carboxyl group, a carbon-containing At least one of carbon double bond or carbon-carbon triple bond or organic ester of benzene ring and unsaturated ketone.
- the atmospheric environment is a mixed gaseous environment formed by the gaseous active material and at least one of oxygen, nitrogen, argon, and carbon dioxide.
- the active material is selected from the group consisting of acrylic acid, benzoic acid, methacrylic acid, 3-butenoic acid, crotonic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, hydroxyethyl methacrylate, methyl methacrylate At least one of methyl methacrylate, butyl acrylate, trimethylol glycerate and N-vinylpyrrolidone.
- the gaseous active material accounts for 0.1% to 50% of the total volume of gas in the atmosphere.
- the temperature of the gaseous environment is 25-150° C., and the total pressure is -0.1-4 MPa.
- the preparation method of the second quantum dot light-emitting diode comprises the following steps:
- a mixed solution of quantum dots and active materials is configured, wherein the active materials are selected from organic hydrocarbons with at least one hydrogen atom substituted by carboxyl groups, organic esters containing carbon-carbon double bonds or carbon-carbon triple bonds or benzene rings, and unsaturated ketones at least one of;
- a prefabricated device on which a quantum dot light-emitting layer is to be prepared is provided, and the mixed solution is deposited on the prefabricated device to prepare a quantum dot light-emitting layer.
- the active material accounts for 0.0001% to 1% of the total weight of the quantum dots and the active material.
- the method further includes: drying at a temperature not higher than 150° C. to prepare the quantum dot light-emitting layer.
- the active material is selected from the group consisting of acrylic acid, benzoic acid, methacrylic acid, 3-butenoic acid, crotonic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, hydroxyethyl methacrylate, methyl methacrylate At least one of methyl methacrylate, butyl acrylate, trimethylol glycerate and N-vinylpyrrolidone.
- the quantum dots are selected from the group consisting of II-VI compounds, III-V compounds, II-V compounds, III-VI compounds, IV-VI compounds, I-III-VI compounds, One or more of II-IV-VI compounds or IV elements.
- the quantum dots are one or more of CdSe/ZnSe, CdSe/CdS, CdSe/CdS/ZnS, ZnCdSeS, ZnCdSeS/ZnS, ZnCdS/ZnS, ZnSe/ZnS.
- the beneficial effect of the quantum dot light-emitting diode is that the quantum dot light-emitting layer contains an active material, and the active material is selected from organic hydrocarbons in which at least one hydrogen atom is substituted by a carboxyl group, a carbon-carbon double bond or a carbon-carbon triple bond. Or at least one of organic esters of benzene rings and unsaturated ketones.
- the carboxylic acid, delocalized ⁇ bond and/or H + contained in the active material can passivate the quantum dot material and the adjacent electronic functional material thin film by means of coordination and/or H + reaction etc.
- the cluster-distributed defect states can effectively suppress the quenching of surface excitons and increase the probability of exciton radiation recombination.
- the active material after the active material is introduced into the interface of the electronic functional layer adjacent to the quantum dot light-emitting layer through interface contact or infiltration, it contains carboxylic acid.
- delocalized ⁇ bonds and/or H + play a role in modifying the interface of the electronic functional layer/quantum dot light-emitting layer, regulating the electron injection barrier between the quantum dot light-emitting layer and the electronic functional layer, and blocking or promoting electron injection, which is beneficial to Charge injection balance.
- the blue and red quantum dot light-emitting diodes thus provided have the highest forward aging effect efficiencies of 87.6% and 117%, respectively, after 6 days, which significantly improves the positive aging effect of the device.
- the beneficial effect of the method for preparing a quantum dot light-emitting diode provided by the embodiments of the present application is that the quantum dot light-emitting diode is obtained by introducing an active material into the quantum dot light-emitting layer by a gas phase method or a mild solution processing method.
- the active material can modify/passivate the quantum dots and the interface surface defects of the electronic functional layer adjacent to the quantum dot light-emitting layer, suppress the quenching of surface excitons, reduce the charge accumulation of the electronic functional layer, increase the exciton radiation recombination probability, and
- the electron injection potential barrier between the quantum dot light-emitting layer and the electronic functional layer can block or promote electron injection, which is beneficial to the balance of charge injection, thereby significantly improving the positive aging effect of the device.
- the gas phase method or the solution processing method has simple process technology and low equipment requirements, which can effectively reduce the preparation cost.
- FIG. 1 is a schematic structural diagram of a quantum dot light-emitting diode provided by an embodiment of the present application
- FIG. 2 is a schematic structural diagram of a quantum dot light-emitting diode containing a hole function provided by an embodiment of the present application;
- FIG. 3 is a schematic structural diagram of a positive structure quantum dot light-emitting diode provided by an embodiment of the present application.
- FIG. 4 is a schematic structural diagram of another positive structure quantum dot light-emitting diode provided by an embodiment of the present application.
- FIG. 5 is a schematic structural diagram of a quantum dot light-emitting diode with an inversion structure provided by an embodiment of the present application
- FIG. 6 is a schematic structural diagram of another inversion structure quantum dot light-emitting diode provided by an embodiment of the present application.
- FIG. 7 is a flow chart of the first preparation process of the quantum dot light-emitting diode provided by the embodiment of the present application.
- FIG. 8 is a flow chart of the second preparation process of the quantum dot light-emitting diode provided by the embodiment of the present application.
- FIG. 9 is a schematic structural diagram of the quantum dot light-emitting diode provided in Embodiment 1 of the present application.
- the term "and/or" describes the association relationship of associated objects, indicating that there can be three kinds of relationships.
- a and/or B can represent three cases where A exists alone, A and B exist simultaneously, and B exists alone. where A and B can be singular or plural.
- the character "/" generally indicates that the associated objects are an "or" relationship.
- At least one means one or more
- plural items means two or more.
- At least one item(s) below” or similar expressions refer to any combination of these items, including any combination of single item(s) or plural items(s).
- at least one (one) of a, b, or c or “at least one (one) of a, b, and c” can mean: a, b, c, a-b ( That is, a and b), a-c, b-c, or a-b-c, where a, b, and c can be single or multiple respectively.
- a first aspect of the embodiment of the present application provides a quantum dot light-emitting diode, comprising an anode 10 and a cathode 50 arranged opposite to each other, and a quantum dot light-emitting layer 30 arranged between the anode 10 and the cathode 50 , and the electronic functional layer 40 arranged between the quantum dot light-emitting layer and the cathode; wherein, the quantum dot light-emitting layer 30 contains active materials, and the active materials are selected from organic hydrocarbons with at least one hydrogen atom substituted by carboxyl groups, and carbon-carbon double bonds. Or at least one of carbon-carbon triple bond or organic ester of benzene ring and unsaturated ketone.
- the quantum dot light-emitting layer 30 contains an active material, and the active material is selected from organic hydrocarbons with at least one hydrogen atom substituted by a carboxyl group, a carbon-carbon double bond or a carbon-carbon triple bond, or a benzene ring. At least one of organic esters and unsaturated ketones.
- the carboxylic acid, delocalized ⁇ bond and/or H + contained in the active material passivate the quantum dot material and the adjacent electronic functional material film by means of coordination and/or H + reaction, showing discrete, nano-scale cluster distribution on the thin film
- the defect state can effectively suppress the quenching of surface excitons and increase the probability of exciton radiation recombination; at the same time, after the active material is introduced into the interface of the electronic functional layer adjacent to the quantum dot light-emitting layer through interface contact or infiltration, it contains carboxylic acid, ionic
- the domain ⁇ bond and/or H + play a role in modifying the interface of the electronic functional layer/quantum dot light-emitting layer, regulating the electron injection barrier between the quantum dot light-emitting layer and the electronic functional layer, blocking or promoting electron injection, which is beneficial to charge injection balance.
- the efficiency of the positive aging effect is increased by up to 20%.
- the quantum dot light-emitting layer 30 is a functional layer that generates light, and at least includes a light-emitting material—quantum dots.
- the quantum dot light-emitting layer 30 in addition to quantum dots, also contains an active material for improving the positive aging effect.
- the quantum dot light-emitting layer 30 consists of quantum dots and the active material.
- the active material is selected from at least one of organic hydrocarbons with at least one hydrogen atom substituted by carboxyl groups, organic esters containing carbon-carbon double bonds or carbon-carbon triple bonds or benzene rings, and unsaturated ketones.
- organic hydrocarbons in which at least one hydrogen atom is substituted by a carboxyl group refers to saturated/or unsaturated organic carboxylic acids, and the organic carboxylic acids do not contain carboxylic acids, carbon-carbon double bonds, carbon-carbon triple bonds, and aromatic rings. other reactive functional groups.
- organic hydrocarbons having at least one hydrogen atom replaced by a carboxyl group include: acetic acid, propionic acid, butyric acid, isobutyric acid, acrylic acid, benzoic acid, methacrylic acid, 3-butenoic acid, crotonic acid, but not Limited to this; organic esters containing carbon-carbon double bonds or carbon-carbon triple bonds or benzene rings include: hydroxyethyl methacrylate, methyl methacrylate, butyl acrylate, trimethylol acrylate, but not limited thereto; unsaturated ketones include, but are not limited to, N-vinylpyrrolidone.
- the active material is selected from the group consisting of acrylic acid, benzoic acid, methacrylic acid, 3-butenoic acid, crotonic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, hydroxyethyl methacrylate, methacrylic acid At least one of methyl ester, butyl acrylate, trimethylol glycerate and N-vinylpyrrolidone. Since these active materials have carboxylic acids, delocalized ⁇ bonds and/or H + , passivated quantum dot materials and adjacent electronic functional material films exhibit discrete, nano-scale cluster distributions through coordination and/or H + reactions, etc.
- the active material can effectively suppress the quenching of surface excitons and increase the probability of exciton radiation recombination; at the same time, after the active material is introduced into the interface of the electronic functional layer 40 adjacent to the quantum dot light-emitting layer 30 through interface contact or infiltration, it contains carboxylic acid. , delocalized ⁇ bonds and/or H + play a role in modifying the interface of the electronic functional layer 40/quantum dot light-emitting layer 30, regulating the electron injection barrier between the quantum dot light-emitting layer 30 and the electronic functional layer 40, and realizing blocking or promoting electrons injection, which is beneficial to the balance of charge injection, thereby significantly improving the positive aging effect of the device.
- the active material accounts for 0.0001% to 1% of the total weight of the quantum dot light-emitting layer 30 .
- the carboxyl group, H + and other substances contained in the active material will cause the quenching of quantum dot light emission to a certain extent, but when the content of the active material in the quantum dot light-emitting layer 30 is within the above range, the active material can significantly improve the quantum dot light-emitting diode. It is the positive aging effect of blue quantum dot light-emitting diodes and red quantum dot light-emitting diodes, and the luminescence effect of quantum dots is controlled in a small range, so that the luminous efficiency can still be stronger than that of quantum dot light-emitting diodes without active materials.
- the active material may account for 0.0001%, 0.0005%, 0.001%, 0.005%, 0.01%, 0.05%, 0.1%, 0.5%, 1% of the total weight of the quantum dot light-emitting layer.
- the quantum dot light emitting diode further includes a hole functional layer 20 disposed between the anode 10 and the quantum dot light emitting layer 30 .
- the hole functional layer 20 includes at least one of a hole transport layer, a hole injection layer, and an electron blocking layer.
- the quantum dot light-emitting diode may further include a substrate, and the anode 10 or the cathode 50 is disposed on the substrate.
- the quantum dot light emitting diodes provided in the embodiments of the present application are classified into positive structure quantum dot light emitting diodes and inverse structure quantum dot light emitting diodes.
- the positive-type quantum dot light-emitting diode includes an anode 10 and a cathode 50 disposed opposite to each other, a quantum dot light-emitting layer 30 disposed between the anode 10 and the cathode 50, and a cathode disposed on the cathode.
- An electron functional layer 40 such as an electron transport layer and an electron injection layer between the quantum dot light-emitting layer 30 and the quantum dot light-emitting layer 30 , and the anode 10 is arranged on the substrate 100 .
- the quantum dot light emitting diode includes a substrate 100 , an anode 10 disposed on the surface of the substrate 100 , and a hole injection layer 21 disposed on the surface of the anode 10 .
- the quantum dot light-emitting diode of the inversion structure includes a stacked structure of an anode 10 and a cathode 50 arranged oppositely, and a quantum dot light-emitting layer 30 arranged between the anode 10 and the cathode 50, and an electron injection layer 40 such as an electron transport layer and an electron injection layer disposed between the cathode 50 and the quantum dot light-emitting layer 30 , and the cathode is disposed on the substrate 100 .
- a hole functional layer 20 such as a hole transport layer, a hole injection layer, and an electron blocking layer can be provided between the anode 10 and the quantum dot light-emitting layer 30 .
- the quantum dot light emitting diodes include a substrate 100 , a cathode 50 disposed on the surface of the substrate 100 , an electron transport layer 41 disposed on the surface of the cathode 50 , The quantum dot light-emitting layer 30 provided on the surface of the electron transport layer 41, the hole transport layer 22 provided on the surface of the quantum dot light-emitting layer 30, the hole injection layer 21 provided on the surface of the hole transport layer 22, and the hole injection layer 21 Anode 10 on the surface.
- the substrate 100 may include a rigid substrate such as glass, metal foil, etc. commonly used rigid substrates, or a flexible substrate such as polyimide (PI), polycarbonate (PC), polystyrene ( PS), polyethylene (PE), polyvinyl chloride (PV), polyvinylpyrrolidone (PVP), polyethylene terephthalate (PET) and other similar materials, which mainly play a supporting role.
- a rigid substrate such as glass, metal foil, etc. commonly used rigid substrates
- a flexible substrate such as polyimide (PI), polycarbonate (PC), polystyrene ( PS), polyethylene (PE), polyvinyl chloride (PV), polyvinylpyrrolidone (PVP), polyethylene terephthalate (PET) and other similar materials, which mainly play a supporting role.
- the anode 10 may adopt common anode materials and thicknesses, which are not limited in the embodiments of the present application.
- the anode material can be indium tin oxide (ITO), indium zinc oxide (IZO) conductive glass or indium tin oxide, indium zinc oxide electrodes, or other metal materials such as gold, silver, aluminum, and the like.
- anode 10 is an ITO electrode.
- the hole injection layer including the two-dimensional black phosphorus material and the metal compound has a high work function and is highly matched to the anode 10; and can exert excellent carrier mobility, which can replace PEDOT:PSS, but Will not cause damage to the anode.
- the quantum dots are group II-VI semiconductor nanocrystals, group III-V semiconductor nanocrystals, group II-V semiconductor nanocrystals, group III-VI semiconductor nanocrystals, group IV-VI semiconductor nanocrystals, - one of group III-VI semiconductor nanocrystals, group I-III-VI core-shell quantum dots, group II-IV-VI semiconductor nanocrystals, group II-IV-VI core-shell structure quantum dots or group IV elements or more.
- the quantum dots can be red light quantum dots, correspondingly, the quantum dot light emitting diodes are red light quantum dot light emitting diodes; the quantum dots can be blue light quantum dots, correspondingly, the quantum dot light emitting diodes are blue light quantum dot light emitting diodes; the quantum dots can be green light quantum dots dot, correspondingly, the quantum dot light-emitting diode is a green light quantum dot light-emitting diode.
- the quantum dots are one or more of CdSe/ZnSe, CdSe/CdS, CdSe/CdS/ZnS, ZnCdSeS, ZnCdSeS/ZnS, ZnCdS/ZnS, ZnSe/ZnS.
- the electronic functional layer 40 includes at least one of an electron transport layer and an electron injection layer.
- the material of the electronic functional layer 40 is selected from inorganic materials with electron transport capability, especially inorganic nanoparticle materials, including one or more of doped or undoped metal oxides.
- the material of the electronic functional layer 40 is selected from one or more of ZnO, TiO 2 , SnO 2 , Ta 2 O 3 , ZrO 2 , NiO, TiLiO, ZnAlO, ZnMgO, ZnSnO, ZnLiO, and InSnO .
- the cathode 50 may adopt common cathode materials, including but not limited to one or more of metal materials, carbon materials, and metal oxides.
- the metal material includes one or more of Al, Ag, Cu, Mo, Au, Ba, Ca, and Mg
- the carbon material includes one or more of graphite, carbon nanotube, graphene, and carbon fiber
- the oxides may be doped or undoped metal oxides including one or more of ITO, FTO, ATO, AZO, GZO, IZO, MZO, AMO.
- the quantum dot light emitting diode is a blue quantum dot light emitting diode or a red light quantum dot light emitting diode
- the positive aging effect of the device is more significant.
- the quantum dot light-emitting diode provided by the present application can be prepared by the following method.
- the embodiments of the present application provide two methods for fabricating quantum dot light-emitting diodes.
- the first method for preparing a quantum dot light-emitting diode includes the following steps:
- the prefabricated device is placed in an atmosphere containing a gaseous active material, and a quantum dot light-emitting layer is prepared on the prefabricated device; wherein, the gaseous active material is selected from organic hydrocarbons with at least one hydrogen atom substituted by a carboxyl group, a carbon-carbon double bond or At least one of carbon-carbon triple bond or organic ester of benzene ring and unsaturated ketone.
- the gaseous active material is selected from organic hydrocarbons with at least one hydrogen atom substituted by a carboxyl group, a carbon-carbon double bond or At least one of carbon-carbon triple bond or organic ester of benzene ring and unsaturated ketone.
- the prefabricated substrate includes at least an anode substrate.
- the prefabricated device includes an anode substrate, a hole functional layer bonded to the anode surface of the anode substrate.
- the prefabricated substrate includes at least a cathode substrate.
- the prefabricated device includes a cathode substrate, an electronic functional layer bonded to the cathode surface of the cathode substrate. The selection of the hole functional layer and the electron functional layer is as described above, and will not be repeated here.
- the prefabricated device is placed in an atmosphere containing a gaseous active material, so that the prefabricated device prepares a quantum dot light-emitting layer in an environment containing a gaseous active material, thereby introducing an active material into the quantum dot light-emitting layer.
- the atmosphere environment containing gaseous active material can be pure gaseous active material atmosphere; it can also be inert atmosphere environment containing gaseous active material, wherein, inert atmosphere includes nitrogen atmosphere, carbon dioxide atmosphere or argon atmosphere and the like.
- the atmospheric environment is a mixed gaseous environment formed by the gaseous active material and at least one of oxygen, nitrogen, argon, and carbon dioxide.
- the gaseous active material accounts for 0.1% to 50% of the total volume of gas in the atmosphere.
- the temperature of the gaseous environment is 25-150° C. and the total pressure is -0.1-4 MPa.
- the gaseous active material is the vapor of the active material.
- the gaseous active material is selected from at least one of organic hydrocarbons with at least one hydrogen atom substituted by carboxyl groups, organic esters containing carbon-carbon double bonds or carbon-carbon triple bonds or benzene rings, and unsaturated ketones.
- the active material is selected from the group consisting of acrylic acid, benzoic acid, methacrylic acid, 3-butenoic acid, crotonic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, hydroxyethyl methacrylate, methacrylic acid At least one of methyl ester, butyl acrylate, trimethylol glycerate and N-vinylpyrrolidone.
- the process of preparing the quantum dot light-emitting layer is carried out with reference to the conventional process.
- the quantum dot light-emitting layer is prepared by solution processing on a prefabricated device.
- the prefabricated substrate is an anode substrate; in the step of preparing the quantum dot light-emitting layer on the prefabricated device, the quantum dot light-emitting layer is prepared on the anode surface of the anode substrate. Further, the method for preparing a quantum dot light-emitting diode further includes: preparing an electronic functional layer on the surface of the quantum dot light-emitting layer away from the anode, and preparing a cathode on the surface of the electronic functional layer away from the quantum dot light-emitting layer.
- the prefabricated device includes an anode substrate and a hole functional layer bound on the anode surface of the anode substrate; in the step of preparing the quantum dot light-emitting layer on the prefabricated device, the quantum dots are prepared on the surface of the hole functional layer facing away from the anode light-emitting layer.
- the method for preparing a quantum dot light-emitting diode further includes: preparing an electronic functional layer on the surface of the quantum dot light-emitting layer away from the anode, and preparing a cathode on the surface of the electronic functional layer away from the quantum dot light-emitting layer.
- the prefabricated substrate is a cathode substrate; in the step of preparing the quantum dot light-emitting layer on the prefabricated device, the quantum dot light-emitting layer is prepared on the cathode surface of the cathode substrate.
- the method for preparing a quantum dot light-emitting diode further includes: preparing an anode on the surface of the quantum dot light-emitting layer facing away from the cathode.
- a hole functional layer is prepared on the surface of the quantum dot light emitting layer facing away from the cathode, and an anode is prepared on the surface of the hole functional layer facing away from the quantum dot light emitting layer.
- the prefabricated device includes a cathode substrate and an electronic functional layer combined on the cathode surface of the cathode substrate; in the step of preparing the quantum dot light-emitting layer on the prefabricated device, the quantum dot light-emitting layer is prepared on the surface of the electronic functional layer facing away from the cathode . Further, the method for preparing a quantum dot light-emitting diode further includes: preparing an anode on the surface of the quantum dot light-emitting layer facing away from the cathode.
- a hole functional layer is prepared on the surface of the quantum dot light emitting layer facing away from the cathode, and an anode is prepared on the surface of the hole functional layer facing away from the quantum dot light emitting layer.
- the second method for preparing a quantum dot light-emitting diode includes the following steps:
- the active material is selected from organic hydrocarbons with at least one hydrogen atom substituted by carboxyl groups, organic esters containing carbon-carbon double bonds or carbon-carbon triple bonds or benzene rings, unsaturated ketones at least one of;
- E02. Provide a prefabricated device for preparing a quantum dot light-emitting layer, deposit a mixed solution on the prefabricated device, and prepare a quantum dot light-emitting layer.
- a solution containing quantum dots may be configured first, then an active material is added, and mixed to form a mixed solution; or a solution containing sexual components may be configured first, and then quantum dots are added to mix A mixed solution is formed; the quantum dots and the active material can also be added simultaneously or successively in the solvent, and mixed to form a mixed solution, and the order of the quantum dots and the active material is not required.
- the quantum dots are selected from the group consisting of II-VI compounds, III-V compounds, II-V compounds, III-VI compounds, IV-VI compounds, I-III-VI compounds, II- One or more of group IV-VI compounds or group IV elements, exemplarily, the quantum dots are CdSe/ZnSe, CdSe/CdS, CdSe/CdS/ZnS, ZnCdSeS, ZnCdSeS/ZnS, ZnCdS/ZnS, One or more of ZnSe/ZnS.
- the active material is selected from at least one of organic hydrocarbons with at least one hydrogen atom substituted by carboxyl groups, organic esters containing carbon-carbon double bonds or carbon-carbon triple bonds or benzene rings, and unsaturated ketones.
- the active material is selected from the group consisting of acrylic acid, benzoic acid, methacrylic acid, 3-butenoic acid, crotonic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, hydroxyethyl methacrylate, methacrylic acid At least one of methyl ester, butyl acrylate, trimethylol glycerate and N-vinylpyrrolidone.
- the total weight of the quantum dots and the active material is 0.0001% to 1%.
- the active material accounts for 0.0001% to 1% of the total weight of the quantum dots and the active material. Since the above-mentioned active materials have a certain degree of quenching effect on the luminescence efficiency of the quantum dot solution, in this case, the content of the active material is relatively small relative to the content of the quantum dots, which can avoid obvious quenching of the luminescence of the quantum dots; however, , can play the role of improving the positive aging effect after introducing the quantum dot light-emitting layer through the subsequent steps.
- the prefabricated substrate includes at least an anode substrate.
- the prefabricated device includes an anode substrate, a hole functional layer bonded to the anode surface of the anode substrate.
- the prefabricated substrate includes at least a cathode substrate.
- the prefabricated device includes a cathode substrate, an electronic functional layer bonded to the cathode surface of the cathode substrate. The selection of the hole functional layer and the electron functional layer is as described above, and will not be repeated here.
- the deposition of the mixed solution on the prefabricated device can be achieved by a conventional method, and after drying, the quantum dot light-emitting layer is prepared.
- the method further includes: drying at a temperature not higher than 150° C. to prepare a quantum dot light-emitting layer, so as to avoid excessive temperature and cause the active material to volatilize , affecting the positive aging effect of quantum dot light-emitting diodes.
- the prefabricated substrate is an anode substrate; in the step of depositing a mixed solution on the prefabricated device to prepare a quantum dot light-emitting layer, the mixed solution is deposited on the anode surface of the anode substrate to prepare a quantum dot light-emitting layer.
- the method for preparing a quantum dot light-emitting diode further includes: preparing an electronic functional layer on the surface of the quantum dot light-emitting layer away from the anode, and preparing a cathode on the surface of the electronic functional layer away from the quantum dot light-emitting layer.
- the prefabricated device includes an anode substrate, and a hole functional layer combined on the anode surface of the anode substrate; in the step of depositing a mixed solution on the prefabricated device to prepare a quantum dot light-emitting layer, the hole functional layer is away from the anode in the step of depositing a mixed solution on the prefabricated device. The mixed solution is deposited on the surface to prepare a quantum dot light-emitting layer.
- the method for preparing a quantum dot light-emitting diode further includes: preparing an electronic functional layer on the surface of the quantum dot light-emitting layer away from the anode, and preparing a cathode on the surface of the electronic functional layer away from the quantum dot light-emitting layer.
- the prefabricated substrate is a cathode substrate; in the step of depositing a mixed solution on the prefabricated device to prepare a quantum dot light-emitting layer, the mixed solution is deposited on the cathode surface of the cathode substrate to prepare a quantum dot light-emitting layer.
- the method for preparing a quantum dot light-emitting diode further includes: preparing an anode on the surface of the quantum dot light-emitting layer facing away from the cathode.
- a hole functional layer is prepared on the surface of the quantum dot light emitting layer facing away from the cathode, and an anode is prepared on the surface of the hole functional layer facing away from the quantum dot light emitting layer.
- the prefabricated device includes a cathode substrate, and an electronic functional layer combined on the cathode surface of the cathode substrate; in the step of depositing a mixed solution on the prefabricated device to prepare a quantum dot light-emitting layer, the electronic functional layer is prepared on the surface away from the cathode.
- Quantum dot light-emitting layer Further, the method for preparing a quantum dot light-emitting diode further includes: preparing an anode on the surface of the quantum dot light-emitting layer facing away from the cathode.
- a hole functional layer is prepared on the surface of the quantum dot light emitting layer facing away from the cathode, and an anode is prepared on the surface of the hole functional layer facing away from the quantum dot light emitting layer.
- the quantum dot light-emitting diode is obtained by introducing active material into the quantum dot light-emitting layer by gas phase method or mild solution processing method.
- the active material can modify/passivate the quantum dots and the surface defects of the electronic functional layer adjacent to the quantum dot light-emitting layer, suppress the quenching of surface excitons, reduce the charge accumulation of the electronic functional layer, increase the exciton radiation recombination probability, and reduce the quantum dots.
- the electron injection potential barrier between the light-emitting layer and the electronic functional layer can block or promote electron injection, which is beneficial to the balance of charge injection, thereby significantly improving the positive aging effect of the device.
- the gas phase method or the solution processing method has simple process technology and low equipment requirements, which can effectively reduce the preparation cost.
- a red quantum dot light-emitting diode, a substrate 100, an anode 110 located on the substrate 100, and a hole functional layer 120, a quantum dot light-emitting layer 130, an electron functional layer 140 and a cathode are sequentially stacked 150, wherein the material of the substrate 100 is silicon glass, the material of the anode 110 is ITO, the material of the hole function layer 120 is TFB, the material of the quantum dot light-emitting layer 130 includes quantum dots CdZnSe/ZnSe/ZnS and acrylic acid, and acrylic acid accounts for The total weight of the quantum dot light-emitting layer is 0.005%, and the material of the cathode 150 is Ag.
- a preparation method of a quantum dot light-emitting diode comprising:
- the obtained prefabricated device is placed in an atmosphere composed of N2 or Ar and the vapor of the active material, and the content of acrylic acid in the total gas volume is 1%, the temperature of the gaseous environment is 40 ° C, and the total pressure is 1 MPa;
- the quantum dot light-emitting layer was prepared by the method, and the rotating speed was 3000 rpm/s.
- a cathode is vapor-deposited on the surface of the electronic functional layer 140 .
- Embodiment 1 The difference from Embodiment 1 is that in the process of preparing the red quantum dot light-emitting diode, the preparation method of the quantum dot light-emitting layer 130 is as follows:
- the mixed solution of the active material and the quantum dots is spin-coated on the obtained prefabricated device to prepare the quantum dot light-emitting layer 130 .
- the current efficiency (cd/A) of the red quantum dot light-emitting diode prepared in Test Example 1-2 is as follows: scan from 0V to 7V with a 0.2V step, monitor the current with a Keithley source meter and an integrating sphere ( A) and brightness (nit/m 2 ), the current efficiency test value is obtained.
- the current efficiency of the red quantum dot light-emitting diode provided in Example 1 was increased by 117% after 6 days; the current efficiency of the red quantum dot light-emitting diode provided by Example 2 was increased after 6 days. 85%. It can be seen that the positive aging efficiency of the red quantum dot light-emitting diode provided in the embodiment of the present application is significantly improved.
- the material of the anode is ITO
- the material of the hole functional layer is TFB
- the material of the quantum dot light-emitting layer includes quantum dots CdZnSe/ZnS and acrylic acid
- the content of acrylic acid is 0.01%
- the material of the cathode is Ag.
- a preparation method of a quantum dot light-emitting diode comprising:
- the obtained prefabricated device is placed in an atmosphere composed of N2 or Ar and the vapor of the active material, and the content of acrylic acid in the total gas volume is 1%, the temperature of the gaseous environment is 40 ° C, and the total pressure is 1 MPa;
- the quantum dot light-emitting layer was prepared by the method, and the rotating speed was 3000 rpm/s. Spin-coating electronic functional materials on the surface of the quantum dot light-emitting layer to prepare electronic functional layers;
- a cathode is vapor-deposited on the surface of the electronic functional layer.
- Example 3 The difference from Example 3 is that in the preparation method of the blue quantum dot light-emitting diode, the preparation method of the quantum dot light-emitting layer is:
- a mixed solution of active material and quantum dots is spin-coated on the obtained prefabricated device to prepare a quantum dot light-emitting layer.
- the current efficiency (cd/A) of the red quantum dot light-emitting diodes prepared in Test Example 3-4, the test method is as follows: scan from 0V to 7V with a step size of 0.2V, monitor the current with a Keithley source meter and an integrating sphere ( A) and brightness (nit/m 2 ), the current efficiency test value is obtained.
- the current efficiency of the red quantum dot light-emitting diode provided in Example 3 was improved by 87.6% after 6 days; the current efficiency of the red quantum dot light-emitting diode provided by Example 4 was improved after 6 days. 80.9%. It can be seen that the positive aging efficiency of the red quantum dot light-emitting diode provided in the embodiment of the present application is significantly increased.
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Abstract
Disclosed in the present application are a quantum dot light-emitting diode and a preparation method therefor. The quantum dot light-emitting diode comprises an anode and a cathode provided opposite to each other, a quantum dot light-emitting layer provided between the anode and the cathode, and an electronic functional layer provided between the quantum dot light-emitting layer and the cathode. The quantum dot light-emitting layer comprises an active material selected from at least one of organic hydrocarbon having at least one hydrogen atom substituted by a carboxyl group, an organic ester comprising a carbon-carbon double bond or a carbon-carbon triple bond or a benzene ring, and an unsaturated ketone. By introducing the active material to the quantum dot light-emitting layer, the present application improves a positive aging effect of the quantum dot light-emitting diode.
Description
本申请要求于2020年12月31日在中国专利局提交的、申请号为202011639233.8、发明名称为“量子点发光二极管及其制备方法”的中国专利申请的优先权,其全部内容通过引用结合在本申请中。This application claims the priority of the Chinese patent application with the application number 202011639233.8 and the invention titled "Quantum Dot Light Emitting Diode and its Preparation Method" filed in the China Patent Office on December 31, 2020, the entire contents of which are incorporated by reference in in this application.
本申请涉及显示技术领域,尤其涉及一种量子点发光二极管及其制备方法。The present application relates to the field of display technology, and in particular, to a quantum dot light-emitting diode and a preparation method thereof.
量子点发光二极管(Quantum Dot
Light Emitting Diodes,QLED)是基于量子点(quantum dots,QDs)技术的电致发光器件,具有自发光、无需背光模组、视角宽、对比度高、全固化、适用于挠曲性面板、温度特性好、响应速度快和节能环保等一系列优异特性,已经成为新型显示技术的研究热点和重点发展方向。Quantum Dot Light Emitting Diode
Light Emitting Diodes, QLED) is an electroluminescent device based on quantum dots (QDs) technology, with self-luminescence, no backlight module, wide viewing angle, high contrast, full curing, suitable for flexible panels, temperature characteristics A series of excellent features, such as good performance, fast response speed, energy saving and environmental protection, have become the research hotspot and key development direction of new display technology.
QLED器件虽然借鉴和利用了有机发光二极管(Organic Light-Emitting
Diode,OLED)器件结构,但因其材料构成的差异,两者的老化现象和老化机理差异巨大。如QLED器件存在各种效率(电流、功率或外量子效率)随时间而衰减或提升的现象,即“负老化效应”或“正老化效应”。目前,老化效应的机理尚不明确,诸多研究总结指出,引起器件效率变化主要源于空穴功能层退化、界面电荷聚集、电子功能层表面缺陷态抑制或电荷迁移率改变等因素。此外,不同发光颜色量子点的材料本身与其他功能层材料匹配性差异同样会造成器件老化机理的不同,如红色QLED器件老化效应更多由有机空穴功能层的退化引起,而蓝色QLED器件老化效应则更多是因为量子点发光层与电子功能层的导带最大能级 (conduction-band maximum,CBM)失配导致的电子在电子功能层聚集。Although QLED devices borrow and utilize organic light-emitting diodes (Organic Light-Emitting Diodes)
Diode, OLED) device structure, but due to the difference in material composition, the aging phenomenon and aging mechanism of the two are very different. For example, QLED devices have various efficiencies (current, power or external quantum efficiency) that decay or increase over time, that is, "negative aging effect" or "positive aging effect". At present, the mechanism of the aging effect is still unclear. Many studies have concluded that the changes in device efficiency are mainly caused by factors such as the degradation of the hole functional layer, the accumulation of interface charges, the suppression of surface defect states in the electronic functional layer, or the change of charge mobility. In addition, the difference in the matching between the materials of different light-emitting color quantum dots and other functional layer materials will also cause different device aging mechanisms. For example, the aging effect of red QLED devices is more caused by the degradation of the organic hole functional layer, while blue QLED devices The aging effect is more due to the mismatch between the conduction-band maximum (CBM) of the quantum dot light-emitting layer and the electronic functional layer, which leads to the accumulation of electrons in the electronic functional layer.
有研究人员提出了一种提升量子点二极管的正老化效应和稳定性的方法和结构,其揭露:含有饱和/不饱和羧酸等活性材料的可固化树脂封装的QLED器件,其正老化效应显著,且对封装后器件加热处理能进一步提升效率和加速正向老化过程(正老化效应一般4~8天左右完成,效率趋于稳定)。该技术通过将活性材料混入可固化封装树脂中,或将QLED器件暴露于包含活性材料的环境中,或用包含活性材料的溶液清洗QLED堆叠层将活性材料引入QLED器件实现。该技术对绿色QLED器件正老化效应最为显著,效率提升可达175%(效率提升比例为最大器件效率和第一天测试效率差值与第一天测试效率比值的百分数),但蓝色和红色QLED器件正老化效应的程度较小,最高效率提升仅20%。Some researchers have proposed a method and structure for improving the positive aging effect and stability of quantum dot diodes, which revealed that the curable resin-encapsulated QLED device containing active materials such as saturated/unsaturated carboxylic acids has a significant positive aging effect. , and the heat treatment of the packaged device can further improve the efficiency and accelerate the forward aging process (the positive aging effect is generally completed in about 4 to 8 days, and the efficiency tends to be stable). This technology is achieved by incorporating active materials into a curable encapsulation resin, or by exposing the QLED device to an environment containing the active material, or by cleaning the QLED stack with a solution containing the active material to introduce the active material into the QLED device. This technology has the most significant positive aging effect on green QLED devices, and the efficiency can be improved by 175% (the efficiency improvement ratio is the percentage of the difference between the maximum device efficiency and the first-day test efficiency and the first-day test efficiency ratio), but blue and red The positive aging effect of QLED devices is small, and the maximum efficiency is only increased by 20%.
本申请实施例的目的之一在于:提供一种量子点发光二极管及其制备方法。One of the objectives of the embodiments of the present application is to provide a quantum dot light-emitting diode and a method for preparing the same.
本申请实施例采用的技术方案是:The technical scheme adopted in the embodiment of the present application is:
第一方面,提供了一种量子点发光二极管,包括相对设置的阳极和阴极,设置在所述阳极和所述阴极之间的量子点发光层,以及设置在所述量子点发光层和所述阴极之间的电子功能层;其中,所述量子点发光层中含有活性材料,所述活性材料选自至少一个氢原子被羧基取代的有机烃、含有碳碳双键或碳碳三键或苯环的有机酯、不饱和酮中的至少一种。In a first aspect, a quantum dot light-emitting diode is provided, comprising an anode and a cathode disposed opposite to each other, a quantum dot light-emitting layer disposed between the anode and the cathode, and a quantum dot light-emitting layer disposed between the quantum dot light-emitting layer and the cathode. The electronic functional layer between the cathodes; wherein, the quantum dot light-emitting layer contains active materials, and the active materials are selected from organic hydrocarbons with at least one hydrogen atom substituted by carboxyl groups, carbon-carbon double bonds or carbon-carbon triple bonds, or benzene At least one of cyclic organic esters and unsaturated ketones.
在一些实施例中,所述活性材料选自丙烯酸、苯甲酸、甲基丙烯酸、3-丁烯酸、巴豆酸、乙酸、丙酸、丁酸、异丁酸、甲基丙烯酸羟乙酯、甲基丙烯酸甲酯、丙烯酸丁酯、三羟甲基丙三烯酸酯以及N-乙烯基吡咯烷酮中的至少一种。In some embodiments, the active material is selected from the group consisting of acrylic acid, benzoic acid, methacrylic acid, 3-butenoic acid, crotonic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, hydroxyethyl methacrylate, methyl methacrylate At least one of methyl methacrylate, butyl acrylate, trimethylol glycerate and N-vinylpyrrolidone.
在一些实施例中,所述活性材料占所述量子点发光层的总重量的0.0001%~1%。In some embodiments, the active material accounts for 0.0001% to 1% of the total weight of the quantum dot light-emitting layer.
在一些实施例中,所述量子点发光层由量子点和所述活性材料组成。In some embodiments, the quantum dot light-emitting layer consists of quantum dots and the active material.
在一些实施例中,所述量子点选自为II-VI族化合物、III-V族化合物、II-V族化合物、III-VI化合物、IV-VI族化合物、I-III-VI族化合物、II-IV-VI族化合物或IV族单质中的一种或多种。In some embodiments, the quantum dots are selected from the group consisting of II-VI compounds, III-V compounds, II-V compounds, III-VI compounds, IV-VI compounds, I-III-VI compounds, One or more of II-IV-VI compounds or IV elements.
在一些实施例中,所述量子点为CdSe/ZnSe、CdSe/CdS、CdSe/CdS/ZnS、ZnCdSeS、ZnCdSeS/ZnS、ZnCdS/ZnS、ZnSe/ZnS中的一种或多种。In some embodiments, the quantum dots are one or more of CdSe/ZnSe, CdSe/CdS, CdSe/CdS/ZnS, ZnCdSeS, ZnCdSeS/ZnS, ZnCdS/ZnS, ZnSe/ZnS.
在一些实施例中,所述量子点发光二极管还包括设置在所述阳极和所述量子点发光层之间的空穴功能层。In some embodiments, the quantum dot light emitting diode further includes a hole functional layer disposed between the anode and the quantum dot light emitting layer.
第二方面,提供了两种量子点发光二极管的制备方法。In a second aspect, two preparation methods of quantum dot light-emitting diodes are provided.
第一种量子点发光二极管的制备方法,包括以下步骤:The first method for preparing a quantum dot light-emitting diode comprises the following steps:
提供待制备量子点发光层的预制器件;Provide a prefabricated device for preparing a quantum dot light-emitting layer;
将所述预制器件置于含有气态活性材料的气氛环境中,在所述预制器件上制备量子点发光层;其中,所述气态活性材料选自至少一个氢原子被羧基取代的有机烃、含有碳碳双键或碳碳三键或苯环的有机酯、不饱和酮中的至少一种。The prefabricated device is placed in an atmosphere containing a gaseous active material, and a quantum dot light-emitting layer is prepared on the prefabricated device; wherein the gaseous active material is selected from organic hydrocarbons whose at least one hydrogen atom is substituted by a carboxyl group, a carbon-containing At least one of carbon double bond or carbon-carbon triple bond or organic ester of benzene ring and unsaturated ketone.
在一些实施例中,所述气氛环境为气态活性材料与氧气、氮气、氩气、二氧化碳中至少一种形成的混合气态环境。In some embodiments, the atmospheric environment is a mixed gaseous environment formed by the gaseous active material and at least one of oxygen, nitrogen, argon, and carbon dioxide.
在一些实施例中,所述活性材料选自丙烯酸、苯甲酸、甲基丙烯酸、3-丁烯酸、巴豆酸、乙酸、丙酸、丁酸、异丁酸、甲基丙烯酸羟乙酯、甲基丙烯酸甲酯、丙烯酸丁酯、三羟甲基丙三烯酸酯以及N-乙烯基吡咯烷酮中的至少一种。In some embodiments, the active material is selected from the group consisting of acrylic acid, benzoic acid, methacrylic acid, 3-butenoic acid, crotonic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, hydroxyethyl methacrylate, methyl methacrylate At least one of methyl methacrylate, butyl acrylate, trimethylol glycerate and N-vinylpyrrolidone.
在一些实施例中,所述气态活性材料占所述气氛环境中气体总体积的0.1%~50%。In some embodiments, the gaseous active material accounts for 0.1% to 50% of the total volume of gas in the atmosphere.
在一些实施例中,所述气态环境的温度为25~150℃,总压力为-0.1~4MPa。In some embodiments, the temperature of the gaseous environment is 25-150° C., and the total pressure is -0.1-4 MPa.
第二种量子点发光二极管的制备方法,包括以下步骤:The preparation method of the second quantum dot light-emitting diode comprises the following steps:
配置量子点和活性材料的混合溶液,其中,所述活性材料选自至少一个氢原子被羧基取代的有机烃、含有碳碳双键或碳碳三键或苯环的有机酯、不饱和酮中的至少一种;A mixed solution of quantum dots and active materials is configured, wherein the active materials are selected from organic hydrocarbons with at least one hydrogen atom substituted by carboxyl groups, organic esters containing carbon-carbon double bonds or carbon-carbon triple bonds or benzene rings, and unsaturated ketones at least one of;
提供待制备量子点发光层的预制器件,在所述预制器件上沉积所述混合溶液,制备量子点发光层。A prefabricated device on which a quantum dot light-emitting layer is to be prepared is provided, and the mixed solution is deposited on the prefabricated device to prepare a quantum dot light-emitting layer.
在一些实施例中,所述混合溶液中,所述活性材料占所述量子点和所述活性材料的总重量的0.0001%~1%。In some embodiments, in the mixed solution, the active material accounts for 0.0001% to 1% of the total weight of the quantum dots and the active material.
在一些实施例中,在所述预制器件上沉积所述混合溶液的步骤之后,还包括:在温度不高于150℃的条件下干燥处理,制备所述量子点发光层。In some embodiments, after the step of depositing the mixed solution on the prefabricated device, the method further includes: drying at a temperature not higher than 150° C. to prepare the quantum dot light-emitting layer.
在一些实施例中,所述活性材料选自丙烯酸、苯甲酸、甲基丙烯酸、3-丁烯酸、巴豆酸、乙酸、丙酸、丁酸、异丁酸、甲基丙烯酸羟乙酯、甲基丙烯酸甲酯、丙烯酸丁酯、三羟甲基丙三烯酸酯以及N-乙烯基吡咯烷酮中的至少一种。In some embodiments, the active material is selected from the group consisting of acrylic acid, benzoic acid, methacrylic acid, 3-butenoic acid, crotonic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, hydroxyethyl methacrylate, methyl methacrylate At least one of methyl methacrylate, butyl acrylate, trimethylol glycerate and N-vinylpyrrolidone.
在一些实施例中,所述量子点选自为II-VI族化合物、III-V族化合物、II-V族化合物、III-VI化合物、IV-VI族化合物、I-III-VI族化合物、II-IV-VI族化合物或IV族单质中的一种或多种。In some embodiments, the quantum dots are selected from the group consisting of II-VI compounds, III-V compounds, II-V compounds, III-VI compounds, IV-VI compounds, I-III-VI compounds, One or more of II-IV-VI compounds or IV elements.
在一些实施例中,所述量子点为CdSe/ZnSe、CdSe/CdS、CdSe/CdS/ZnS、ZnCdSeS、ZnCdSeS/ZnS、ZnCdS/ZnS、ZnSe/ZnS中的一种或多种。In some embodiments, the quantum dots are one or more of CdSe/ZnSe, CdSe/CdS, CdSe/CdS/ZnS, ZnCdSeS, ZnCdSeS/ZnS, ZnCdS/ZnS, ZnSe/ZnS.
本申请实施例提供的量子点发光二极管的有益效果在于:量子点发光层中含有活性材料,且活性材料选自至少一个氢原子被羧基取代的有机烃、含有碳碳双键或碳碳三键或苯环的有机酯、不饱和酮中的至少一种。活性材料中含有的羧酸、离域π键和/或H
+,从而可以通过配位和/或H
+反应等方式钝化量子点材料及相邻电子功能材料薄膜上呈现离散、纳米尺度团簇分布的缺陷态,有效抑制表面激子淬灭,增加激子辐射复合几率;同时,活性材料通过界面接触或渗透方式引入与量子点发光层相邻的电子功能层界面后,其含有羧酸、离域π键和/或H
+对电子功能层/量子点发光层界面起到修饰作用,调控量子点发光层与电子功能层间的电子注入势垒,实现阻挡或促进电子注入,有利于电荷注入平衡。由此提供的蓝色和红色量子点发光二极管,6天后其正向老化效应效率最高提升分别达到87.6%和117%,显著提升了器件的正老化效应。
The beneficial effect of the quantum dot light-emitting diode provided by the embodiments of the present application is that the quantum dot light-emitting layer contains an active material, and the active material is selected from organic hydrocarbons in which at least one hydrogen atom is substituted by a carboxyl group, a carbon-carbon double bond or a carbon-carbon triple bond. Or at least one of organic esters of benzene rings and unsaturated ketones. The carboxylic acid, delocalized π bond and/or H + contained in the active material can passivate the quantum dot material and the adjacent electronic functional material thin film by means of coordination and/or H + reaction etc. The cluster-distributed defect states can effectively suppress the quenching of surface excitons and increase the probability of exciton radiation recombination. At the same time, after the active material is introduced into the interface of the electronic functional layer adjacent to the quantum dot light-emitting layer through interface contact or infiltration, it contains carboxylic acid. , delocalized π bonds and/or H + play a role in modifying the interface of the electronic functional layer/quantum dot light-emitting layer, regulating the electron injection barrier between the quantum dot light-emitting layer and the electronic functional layer, and blocking or promoting electron injection, which is beneficial to Charge injection balance. The blue and red quantum dot light-emitting diodes thus provided have the highest forward aging effect efficiencies of 87.6% and 117%, respectively, after 6 days, which significantly improves the positive aging effect of the device.
本申请实施例提供的量子点发光二极管的制备方法的有益效果在于:通过气相法或温和的溶液加工法,在量子点发光层中引入活性材料,得到的量子点发光二极管。其中的活性材料可以修饰/钝化量子点及与量子点发光层相邻的电子功能层界面表面缺陷,抑制表面激子淬灭,减少电子功能层的电荷聚集,增加激子辐射复合几率,并量子点发光层与电子功能层间的电子注入势垒,实现阻挡或促进电子注入,有利于电荷注入平衡,从而显著提高器件的正老化效应。此外气相法或溶液加工法制程工艺简单、对设备要求低,可有效降低制备成本。The beneficial effect of the method for preparing a quantum dot light-emitting diode provided by the embodiments of the present application is that the quantum dot light-emitting diode is obtained by introducing an active material into the quantum dot light-emitting layer by a gas phase method or a mild solution processing method. The active material can modify/passivate the quantum dots and the interface surface defects of the electronic functional layer adjacent to the quantum dot light-emitting layer, suppress the quenching of surface excitons, reduce the charge accumulation of the electronic functional layer, increase the exciton radiation recombination probability, and The electron injection potential barrier between the quantum dot light-emitting layer and the electronic functional layer can block or promote electron injection, which is beneficial to the balance of charge injection, thereby significantly improving the positive aging effect of the device. In addition, the gas phase method or the solution processing method has simple process technology and low equipment requirements, which can effectively reduce the preparation cost.
为了更清楚地说明本申请实施例中的技术方案,下面将对实施例或示范性技术描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本申请的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其它的附图。In order to illustrate the technical solutions in the embodiments of the present application more clearly, the following briefly introduces the accompanying drawings that are used in the description of the embodiments or exemplary technologies. Obviously, the drawings in the following description are only for the present application. In some embodiments, for those of ordinary skill in the art, other drawings can also be obtained according to these drawings without any creative effort.
图1是本申请实施例提供的量子点发光二极管的结构示意图;1 is a schematic structural diagram of a quantum dot light-emitting diode provided by an embodiment of the present application;
图2是本申请实施例提供的含有空穴功能才的量子点发光二极管的结构示意图;2 is a schematic structural diagram of a quantum dot light-emitting diode containing a hole function provided by an embodiment of the present application;
图3是本申请实施例提供的一种正型结构量子点发光二极管的结构示意图;3 is a schematic structural diagram of a positive structure quantum dot light-emitting diode provided by an embodiment of the present application;
图4是本申请实施例提供的另一种正型结构量子点发光二极管的结构示意图;FIG. 4 is a schematic structural diagram of another positive structure quantum dot light-emitting diode provided by an embodiment of the present application;
图5是本申请实施例提供的一种反型结构量子点发光二极管的结构示意图;5 is a schematic structural diagram of a quantum dot light-emitting diode with an inversion structure provided by an embodiment of the present application;
图6是本申请实施例提供的另一种反型结构量子点发光二极管的结构示意图;6 is a schematic structural diagram of another inversion structure quantum dot light-emitting diode provided by an embodiment of the present application;
图7是本申请实施例提供的量子点发光二极管的第一种制备工艺流程图;FIG. 7 is a flow chart of the first preparation process of the quantum dot light-emitting diode provided by the embodiment of the present application;
图8是本申请实施例提供的量子点发光二极管的第二种制备工艺流程图;FIG. 8 is a flow chart of the second preparation process of the quantum dot light-emitting diode provided by the embodiment of the present application;
图9是本申请实施例1提供的量子点发光二极管的结构示意图。FIG. 9 is a schematic structural diagram of the quantum dot light-emitting diode provided in Embodiment 1 of the present application.
为了使本申请的目的、技术方案及优点更加清楚明白,以下结合附图及实施例,对本申请进行进一步详细说明。应当理解,此处所描述的具体实施例仅用以解释本申请,并不用于限定本申请。In order to make the purpose, technical solutions and advantages of the present application more clearly understood, the present application will be described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present application, but not to limit the present application.
本申请权利要求和具体实施方式中,术语“和/或”,描述关联对象的关联关系,表示可以存在三种关系。例如,A和/或B,可以表示:单独存在A,同时存在A和B,单独存在B的三种情况。其中A,B可以是单数或者复数。字符“/”一般表示前后关联对象是一种“或”的关系。In the claims and specific embodiments of the present application, the term "and/or" describes the association relationship of associated objects, indicating that there can be three kinds of relationships. For example, A and/or B can represent three cases where A exists alone, A and B exist simultaneously, and B exists alone. where A and B can be singular or plural. The character "/" generally indicates that the associated objects are an "or" relationship.
本申请中,“至少一个”是指一个或者多个,“多个”是指两个或两个以上。“以下至少一项(个)”或其类似表达,是指的这些项中的任意组合,包括单项(个)或复数项(个)的任意组合。例如,“a,b,或c中的至少一项(个)”,或,“a,b,和c中的至少一项(个)”,均可以表示:a, b, c, a-b(即a和b), a-c, b-c, 或a-b-c,其中a,b,c分别可以是单个,也可以是多个。In this application, "at least one" means one or more, and "plurality" means two or more. "At least one item(s) below" or similar expressions refer to any combination of these items, including any combination of single item(s) or plural items(s). For example, "at least one (one) of a, b, or c", or "at least one (one) of a, b, and c", can mean: a, b, c, a-b ( That is, a and b), a-c, b-c, or a-b-c, where a, b, and c can be single or multiple respectively.
应理解,在本申请的各种实施例中,上述各过程的序号的大小并不意味着执行顺序的先后,部分或全部步骤可以并行执行或先后执行,各过程的执行顺序应以其功能和内在逻辑确定,而不应对本申请实施例的实施过程构成任何限定。It should be understood that, in various embodiments of the present application, the size of the sequence numbers of the above-mentioned processes does not imply the sequence of execution, some or all of the steps may be executed in parallel or sequentially, and the execution sequence of each process should be based on its functions and It is determined by the internal logic and should not constitute any limitation on the implementation process of the embodiments of the present application.
在本申请实施例中使用的术语是仅仅出于描述特定实施例的目的,而非旨在限制本申请。在本申请实施例和所附权利要求书中所使用的单数形式的“一种”、“所述”和“该”也旨在包括多数形式,除非上下文清楚地表示其他含义。The terms used in the embodiments of the present application are only for the purpose of describing specific embodiments, and are not intended to limit the present application. As used in the embodiments of this application and the appended claims, the singular forms "a," "the," and "the" are intended to include the plural forms as well, unless the context clearly dictates otherwise.
采用饱和/不饱和羧酸等活性材料封装器件时,对蓝色和红色QLED器件正老化效应不明显的问题。通过低温溶液法加工而来的薄膜器件伴随着普遍的晶体缺陷(如点缺陷),这些晶体缺陷能够引发相关功能层带隙深层次的电子态,捕获电荷载流子,影响器件性能。When encapsulating devices with active materials such as saturated/unsaturated carboxylic acids, the positive aging effect of blue and red QLED devices is not obvious. Thin-film devices processed by low-temperature solution methods are accompanied by common crystal defects (such as point defects), which can induce electronic states deep in the band gap of the relevant functional layers, trap charge carriers, and affect device performance.
有鉴于此,如图1所示,本申请实施例第一方面提供一种量子点发光二极管,包括相对设置的阳极10和阴极50,设置在阳极10和阴极50之间的量子点发光层30,以及设置在量子点发光层和阴极之间的电子功能层40;其中,量子点发光层30中含有活性材料,活性材料选自至少一个氢原子被羧基取代的有机烃、含有碳碳双键或碳碳三键或苯环的有机酯、不饱和酮中的至少一种。In view of this, as shown in FIG. 1 , a first aspect of the embodiment of the present application provides a quantum dot light-emitting diode, comprising an anode 10 and a cathode 50 arranged opposite to each other, and a quantum dot light-emitting layer 30 arranged between the anode 10 and the cathode 50 , and the electronic functional layer 40 arranged between the quantum dot light-emitting layer and the cathode; wherein, the quantum dot light-emitting layer 30 contains active materials, and the active materials are selected from organic hydrocarbons with at least one hydrogen atom substituted by carboxyl groups, and carbon-carbon double bonds. Or at least one of carbon-carbon triple bond or organic ester of benzene ring and unsaturated ketone.
本申请实施例提供的量子点发光二极管,量子点发光层30中含有活性材料,且活性材料选自至少一个氢原子被羧基取代的有机烃、含有碳碳双键或碳碳三键或苯环的有机酯、不饱和酮中的至少一种。活性材料中含有的羧酸、离域π键和/或H
+,通过配位和/或H
+反应等方式钝化量子点材料及相邻电子功能材料薄膜上呈现离散、纳米尺度团簇分布的缺陷态,有效抑制表面激子淬灭,增加激子辐射复合几率;同时,活性材料通过界面接触或渗透方式引入与量子点发光层相邻的电子功能层界面后,其含有羧酸、离域π键和/或H
+对电子功能层/量子点发光层界面起到修饰作用,调控量子点发光层与电子功能层间的电子注入势垒,实现阻挡或促进电子注入,有利于电荷注入平衡。相比目前蓝色和红色QLED器件的正老化效应效率最高提升20%,本申请提供的蓝色和红色量子点发光二极管,6天后其正向老化效应效率最高提升分别达到87.6%和117%,显著提升了器件的正老化效应。
In the quantum dot light-emitting diode provided in the embodiment of the present application, the quantum dot light-emitting layer 30 contains an active material, and the active material is selected from organic hydrocarbons with at least one hydrogen atom substituted by a carboxyl group, a carbon-carbon double bond or a carbon-carbon triple bond, or a benzene ring. At least one of organic esters and unsaturated ketones. The carboxylic acid, delocalized π bond and/or H + contained in the active material passivate the quantum dot material and the adjacent electronic functional material film by means of coordination and/or H + reaction, showing discrete, nano-scale cluster distribution on the thin film The defect state can effectively suppress the quenching of surface excitons and increase the probability of exciton radiation recombination; at the same time, after the active material is introduced into the interface of the electronic functional layer adjacent to the quantum dot light-emitting layer through interface contact or infiltration, it contains carboxylic acid, ionic The domain π bond and/or H + play a role in modifying the interface of the electronic functional layer/quantum dot light-emitting layer, regulating the electron injection barrier between the quantum dot light-emitting layer and the electronic functional layer, blocking or promoting electron injection, which is beneficial to charge injection balance. Compared with the current positive aging effect efficiency of blue and red QLED devices, the efficiency of the positive aging effect is increased by up to 20%. The positive aging effect of the device is significantly improved.
量子点发光器件中,量子点发光层30为产生光的功能层,至少包括发光材料-量子点。本申请实施例中,量子点发光层30中除了含有量子点外,还含有用于提高正老化效应的活性材料。在一些实施例中,量子点发光层30由量子点和所述活性材料组成。In the quantum dot light-emitting device, the quantum dot light-emitting layer 30 is a functional layer that generates light, and at least includes a light-emitting material—quantum dots. In the embodiment of the present application, in addition to quantum dots, the quantum dot light-emitting layer 30 also contains an active material for improving the positive aging effect. In some embodiments, the quantum dot light-emitting layer 30 consists of quantum dots and the active material.
本申请实施例中,活性材料选自至少一个氢原子被羧基取代的有机烃、含有碳碳双键或碳碳三键或苯环的有机酯、不饱和酮中的至少一种。具体的,至少一个氢原子被羧基取代的有机烃是指饱和/或不饱和有机羧酸,且有机羧酸中,不含除羧酸、碳碳双键、碳碳三键、芳香环以外的其他活性官能团。In the embodiments of the present application, the active material is selected from at least one of organic hydrocarbons with at least one hydrogen atom substituted by carboxyl groups, organic esters containing carbon-carbon double bonds or carbon-carbon triple bonds or benzene rings, and unsaturated ketones. Specifically, organic hydrocarbons in which at least one hydrogen atom is substituted by a carboxyl group refers to saturated/or unsaturated organic carboxylic acids, and the organic carboxylic acids do not contain carboxylic acids, carbon-carbon double bonds, carbon-carbon triple bonds, and aromatic rings. other reactive functional groups.
在一些实施例中,至少一个氢原子被羧基取代的有机烃包括:乙酸、丙酸、丁酸、异丁酸、丙烯酸、苯甲酸、甲基丙烯酸、3-丁烯酸、巴豆酸,但不限于此;含有碳碳双键或碳碳三键或苯环的有机酯包括:甲基丙烯酸羟乙酯、甲基丙烯酸甲酯、丙烯酸丁酯、三羟甲基丙三烯酸酯,但不限于此;不饱和酮包括N-乙烯基吡咯烷酮,但不限于此。In some embodiments, organic hydrocarbons having at least one hydrogen atom replaced by a carboxyl group include: acetic acid, propionic acid, butyric acid, isobutyric acid, acrylic acid, benzoic acid, methacrylic acid, 3-butenoic acid, crotonic acid, but not Limited to this; organic esters containing carbon-carbon double bonds or carbon-carbon triple bonds or benzene rings include: hydroxyethyl methacrylate, methyl methacrylate, butyl acrylate, trimethylol acrylate, but not limited thereto; unsaturated ketones include, but are not limited to, N-vinylpyrrolidone.
在一些实施例中,活性材料选自丙烯酸、苯甲酸、甲基丙烯酸、3-丁烯酸、巴豆酸、乙酸、丙酸、丁酸、异丁酸、甲基丙烯酸羟乙酯、甲基丙烯酸甲酯、丙烯酸丁酯、三羟甲基丙三烯酸酯以及N-乙烯基吡咯烷酮中的至少一种。由于这些活性材料具有羧酸、离域π键和/或H
+,通过配位和/或H
+反应等方式钝化量子点材料及相邻电子功能材料薄膜上呈现离散、纳米尺度团簇分布的缺陷态,有效抑制表面激子淬灭,增加激子辐射复合几率;同时,活性材料通过界面接触或渗透方式引入与量子点发光层30相邻的电子功能层40界面后,其含有羧酸、离域π键和/或H
+对电子功能层40/量子点发光层30界面起到修饰作用,调控量子点发光层30与电子功能层40间的电子注入势垒,实现阻挡或促进电子注入,有利于电荷注入平衡,从而显著提高器件的正老化效应。
In some embodiments, the active material is selected from the group consisting of acrylic acid, benzoic acid, methacrylic acid, 3-butenoic acid, crotonic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, hydroxyethyl methacrylate, methacrylic acid At least one of methyl ester, butyl acrylate, trimethylol glycerate and N-vinylpyrrolidone. Since these active materials have carboxylic acids, delocalized π bonds and/or H + , passivated quantum dot materials and adjacent electronic functional material films exhibit discrete, nano-scale cluster distributions through coordination and/or H + reactions, etc. It can effectively suppress the quenching of surface excitons and increase the probability of exciton radiation recombination; at the same time, after the active material is introduced into the interface of the electronic functional layer 40 adjacent to the quantum dot light-emitting layer 30 through interface contact or infiltration, it contains carboxylic acid. , delocalized π bonds and/or H + play a role in modifying the interface of the electronic functional layer 40/quantum dot light-emitting layer 30, regulating the electron injection barrier between the quantum dot light-emitting layer 30 and the electronic functional layer 40, and realizing blocking or promoting electrons injection, which is beneficial to the balance of charge injection, thereby significantly improving the positive aging effect of the device.
在一些实施例中,活性材料占量子点发光层30的总重量的0.0001%~1%。活性材料中含有的羧基、H
+等物质一定程度上会造成量子点发光淬灭,但活性材料在量子点发光层30中的含量在上述范围内时,活性材料能够显著提高量子点发光二极管特别是蓝色量子点发光二极管和红色量子点发光二极管的正老化效应,且对量子点的发光影响控制在较小范围内,使其发光效率仍然能够强于没有添加活性材料的量子点发光二极管。在一些实施例中,活性材料占量子点发光层的总重量可以为0.0001%、0.0005%、0.001%、0.005%、0.01%、0.05%、0.1%、0.5%、1%。
In some embodiments, the active material accounts for 0.0001% to 1% of the total weight of the quantum dot light-emitting layer 30 . The carboxyl group, H + and other substances contained in the active material will cause the quenching of quantum dot light emission to a certain extent, but when the content of the active material in the quantum dot light-emitting layer 30 is within the above range, the active material can significantly improve the quantum dot light-emitting diode. It is the positive aging effect of blue quantum dot light-emitting diodes and red quantum dot light-emitting diodes, and the luminescence effect of quantum dots is controlled in a small range, so that the luminous efficiency can still be stronger than that of quantum dot light-emitting diodes without active materials. In some embodiments, the active material may account for 0.0001%, 0.0005%, 0.001%, 0.005%, 0.01%, 0.05%, 0.1%, 0.5%, 1% of the total weight of the quantum dot light-emitting layer.
在一些实施例中,如图2所示,量子点发光二极管还包括设置在阳极10和量子点发光层30之间的空穴功能层20。其中,空穴功能层20包括空穴传输层、空穴注入层、电子阻挡层中的至少一种。In some embodiments, as shown in FIG. 2 , the quantum dot light emitting diode further includes a hole functional layer 20 disposed between the anode 10 and the quantum dot light emitting layer 30 . The hole functional layer 20 includes at least one of a hole transport layer, a hole injection layer, and an electron blocking layer.
本申请实施例中,量子点发光二极管还可以包括衬底,阳极10或阴极50设置在衬底上。In this embodiment of the present application, the quantum dot light-emitting diode may further include a substrate, and the anode 10 or the cathode 50 is disposed on the substrate.
本申请实施例提供的量子点发光二极管分为正型结构量子点发光二极管和反型结构量子点发光二极管。The quantum dot light emitting diodes provided in the embodiments of the present application are classified into positive structure quantum dot light emitting diodes and inverse structure quantum dot light emitting diodes.
在一种实施方式中,如图3所示,正型结构量子点发光二极管包括相对设置的阳极10和阴极50,设置在阳极10和阴极50之间的量子点发光层30,以及设置在阴极50和量子点发光层30之间的电子传输层、电子注入层等电子功能层40,且阳极10设置在衬底100上。进一步的,在阳极10和量子点发光层30之间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20。在一些正型结构量子点发光二极管的实施例中,如图4所示,量子点发光二极管包括衬底100,设置在衬底100表面的阳极10,设置在阳极10表面的空穴注入层21,设置在空穴注入层21表面的空穴传输层22,设置在空穴传输层22表面的量子点发光层30,设置在量子点发光层30表面的电子传输层41和设置在电子传输层41表面的阴极50。In one embodiment, as shown in FIG. 3 , the positive-type quantum dot light-emitting diode includes an anode 10 and a cathode 50 disposed opposite to each other, a quantum dot light-emitting layer 30 disposed between the anode 10 and the cathode 50, and a cathode disposed on the cathode. An electron functional layer 40 such as an electron transport layer and an electron injection layer between the quantum dot light-emitting layer 30 and the quantum dot light-emitting layer 30 , and the anode 10 is arranged on the substrate 100 . Further, a hole functional layer 20 such as a hole transport layer, a hole injection layer, and an electron blocking layer can be provided between the anode 10 and the quantum dot light-emitting layer 30 . In some positive structure quantum dot light emitting diode embodiments, as shown in FIG. 4 , the quantum dot light emitting diode includes a substrate 100 , an anode 10 disposed on the surface of the substrate 100 , and a hole injection layer 21 disposed on the surface of the anode 10 . , the hole transport layer 22 arranged on the surface of the hole injection layer 21, the quantum dot light-emitting layer 30 arranged on the surface of the hole transport layer 22, the electron transport layer 41 arranged on the surface of the quantum dot light-emitting layer 30, and the electron transport layer 41 arranged on the surface of the electron transport layer 22. Cathode 50 on the surface of 41.
在一种实施方式中,如图5所示,反型结构量子点发光二极管包括相对设置的阳极10和阴极50的叠层结构,设置在阳极10和阴极50之间的量子点发光层30,以及设置在阴极50和量子点发光层30之间的电子传输层、电子注入层等电子注入层40,且阴极设置在衬底100上。进一步的,在阳极10和量子点发光层30之间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20。在一些反型结构量子点发光二极管的实施例中,如图6所示,量子点发光二极管包括衬底100,设置在衬底100表面的阴极50,设置在阴极50表面的电子传输层41,设置在电子传输层41表面的量子点发光层30,设置在量子点发光层30表面的空穴传输层22,设置在空穴传输层22表面的空穴注入层21和设置在空穴注入层21表面的阳极10。In one embodiment, as shown in FIG. 5 , the quantum dot light-emitting diode of the inversion structure includes a stacked structure of an anode 10 and a cathode 50 arranged oppositely, and a quantum dot light-emitting layer 30 arranged between the anode 10 and the cathode 50, and an electron injection layer 40 such as an electron transport layer and an electron injection layer disposed between the cathode 50 and the quantum dot light-emitting layer 30 , and the cathode is disposed on the substrate 100 . Further, a hole functional layer 20 such as a hole transport layer, a hole injection layer, and an electron blocking layer can be provided between the anode 10 and the quantum dot light-emitting layer 30 . In some embodiments of quantum dot light emitting diodes with inversion structure, as shown in FIG. 6 , the quantum dot light emitting diodes include a substrate 100 , a cathode 50 disposed on the surface of the substrate 100 , an electron transport layer 41 disposed on the surface of the cathode 50 , The quantum dot light-emitting layer 30 provided on the surface of the electron transport layer 41, the hole transport layer 22 provided on the surface of the quantum dot light-emitting layer 30, the hole injection layer 21 provided on the surface of the hole transport layer 22, and the hole injection layer 21 Anode 10 on the surface.
上述实施例中,衬底100可包括刚性衬底如玻璃、金属箔片等常用的刚性衬底,或柔性衬底如聚酰亚胺(PI)、聚碳酸酯(PC)、聚苯乙烯(PS)、聚乙烯(PE)、聚氯乙烯(PV)、聚乙烯吡咯烷酮(PVP)、聚对苯二甲酸乙二醇酯(PET)等类似材料,其主要起到支撑作用。In the above-mentioned embodiment, the substrate 100 may include a rigid substrate such as glass, metal foil, etc. commonly used rigid substrates, or a flexible substrate such as polyimide (PI), polycarbonate (PC), polystyrene ( PS), polyethylene (PE), polyvinyl chloride (PV), polyvinylpyrrolidone (PVP), polyethylene terephthalate (PET) and other similar materials, which mainly play a supporting role.
阳极10可以采用常见的阳极材料和厚度,本申请实施例不作限定。例如,阳极材料可以为氧化铟锡(ITO)、氧化铟锌(IZO)导电玻璃或氧化铟锡、氧化铟锌电极,也可以是其他金属材料例如金、银、铝等。在一些实施例中,阳极10为ITO电极。在这种情况下,包括二维黑磷材料和金属化合物的空穴注入层具有高功函数,与阳极10匹配度高;而且能够发挥优异的载流子迁移率,可以替代PEDOT:PSS,但不会对阳极产生破坏作用。The anode 10 may adopt common anode materials and thicknesses, which are not limited in the embodiments of the present application. For example, the anode material can be indium tin oxide (ITO), indium zinc oxide (IZO) conductive glass or indium tin oxide, indium zinc oxide electrodes, or other metal materials such as gold, silver, aluminum, and the like. In some embodiments, anode 10 is an ITO electrode. In this case, the hole injection layer including the two-dimensional black phosphorus material and the metal compound has a high work function and is highly matched to the anode 10; and can exert excellent carrier mobility, which can replace PEDOT:PSS, but Will not cause damage to the anode.
本申请实施例中,量子点为II-VI族半导体纳米晶、III-V族半导体纳米晶、II-V族半导体纳米晶、III-VI族半导体纳米晶、IV-VI族半导体纳米晶、I-III-VI族半导体纳米晶、I-III-VI族核壳结构量子点、II-IV-VI族半导体纳米晶、II-IV-VI族核壳结构量子点或IV族单质中的一种或多种。量子点可以为红光量子点,对应的,量子点发光二极管为红光量子点发光二极管;量子点可以为蓝光量子点,对应的,量子点发光二极管为蓝光量子点发光二极管;量子点可以为绿光量子点,对应的,量子点发光二极管为绿光量子点发光二极管。在一些实施例中,量子点为CdSe/ZnSe、CdSe/CdS、CdSe/CdS/ZnS、ZnCdSeS、ZnCdSeS/ZnS、ZnCdS/ZnS、ZnSe/ZnS中的一种或多种。In the embodiments of the present application, the quantum dots are group II-VI semiconductor nanocrystals, group III-V semiconductor nanocrystals, group II-V semiconductor nanocrystals, group III-VI semiconductor nanocrystals, group IV-VI semiconductor nanocrystals, - one of group III-VI semiconductor nanocrystals, group I-III-VI core-shell quantum dots, group II-IV-VI semiconductor nanocrystals, group II-IV-VI core-shell structure quantum dots or group IV elements or more. The quantum dots can be red light quantum dots, correspondingly, the quantum dot light emitting diodes are red light quantum dot light emitting diodes; the quantum dots can be blue light quantum dots, correspondingly, the quantum dot light emitting diodes are blue light quantum dot light emitting diodes; the quantum dots can be green light quantum dots dot, correspondingly, the quantum dot light-emitting diode is a green light quantum dot light-emitting diode. In some embodiments, the quantum dots are one or more of CdSe/ZnSe, CdSe/CdS, CdSe/CdS/ZnS, ZnCdSeS, ZnCdSeS/ZnS, ZnCdS/ZnS, ZnSe/ZnS.
本申请实施例中,电子功能层40包括电子传输层、电子注入层中的至少一种。电子功能层40的材料选自具有电子传输能力的无机材料,特别是无机纳米颗粒材料,包括:掺杂或非掺杂的金属氧化物中的一种或多种。在一些实施例中,电子功能层40的材料选自ZnO、TiO
2、SnO
2、Ta
2O
3、ZrO
2、NiO、TiLiO、ZnAlO、ZnMgO、ZnSnO、ZnLiO、InSnO中的一种或多种。
In the embodiment of the present application, the electronic functional layer 40 includes at least one of an electron transport layer and an electron injection layer. The material of the electronic functional layer 40 is selected from inorganic materials with electron transport capability, especially inorganic nanoparticle materials, including one or more of doped or undoped metal oxides. In some embodiments, the material of the electronic functional layer 40 is selected from one or more of ZnO, TiO 2 , SnO 2 , Ta 2 O 3 , ZrO 2 , NiO, TiLiO, ZnAlO, ZnMgO, ZnSnO, ZnLiO, and InSnO .
本申请实施例中,阴极50可以采用常见的阴极材料,包括但不限于金属材料、碳材料、金属氧化物中的一种或多种。其中,金属材料包括Al、Ag、Cu、Mo、Au、Ba、Ca、Mg中的一种或多种;碳材料包括石墨、碳纳米管、石墨烯、碳纤维中的一种或多种;金属氧化物可以是掺杂或非掺杂金属氧化物,包括ITO、FTO、ATO、AZO、GZO、IZO、MZO、AMO中的一种或多种。In the embodiments of the present application, the cathode 50 may adopt common cathode materials, including but not limited to one or more of metal materials, carbon materials, and metal oxides. Wherein, the metal material includes one or more of Al, Ag, Cu, Mo, Au, Ba, Ca, and Mg; the carbon material includes one or more of graphite, carbon nanotube, graphene, and carbon fiber; The oxides may be doped or undoped metal oxides including one or more of ITO, FTO, ATO, AZO, GZO, IZO, MZO, AMO.
当量子点发光二极管为蓝光量子点发光二极管或红光量子点发光二极管时,在量子点发光层中引入活性材料后,器件正老化效应更加显著。When the quantum dot light emitting diode is a blue quantum dot light emitting diode or a red light quantum dot light emitting diode, after the active material is introduced into the quantum dot light emitting layer, the positive aging effect of the device is more significant.
本申请提供的量子点发光二极管,可以通过下述方法制备获得。The quantum dot light-emitting diode provided by the present application can be prepared by the following method.
第二方面,本申请实施例提供两种量子点发光二极管的制备方法。In a second aspect, the embodiments of the present application provide two methods for fabricating quantum dot light-emitting diodes.
如图7所示,第一种量子点发光二极管的制备方法,包括以下步骤:As shown in Figure 7, the first method for preparing a quantum dot light-emitting diode includes the following steps:
S01. 提供待制备量子点发光层的预制器件;S01. Provide a prefabricated device for the quantum dot light-emitting layer to be prepared;
S02. 将预制器件置于含有气态活性材料的气氛环境中,在预制器件上制备量子点发光层;其中,气态活性材料选自至少一个氢原子被羧基取代的有机烃、含有碳碳双键或碳碳三键或苯环的有机酯、不饱和酮中的至少一种。S02. The prefabricated device is placed in an atmosphere containing a gaseous active material, and a quantum dot light-emitting layer is prepared on the prefabricated device; wherein, the gaseous active material is selected from organic hydrocarbons with at least one hydrogen atom substituted by a carboxyl group, a carbon-carbon double bond or At least one of carbon-carbon triple bond or organic ester of benzene ring and unsaturated ketone.
上述步骤S01中,提供待制备量子点发光层的预制器件。在一种实施情形中,预制基板至少包括阳极基板。在一些实施例中,预制器件为包括阳极基板,在阳极基板的阳极表面结合的空穴功能层。在另一种实施情形中,预制基板至少包括阴极基板。在一些实施例中,预制器件包括阴极基板,在阴极基板的阴极表面结合的电子功能层。空穴功能层和电子功能层的选择如上文所述,此处不再赘述。In the above step S01, a prefabricated device for preparing a quantum dot light-emitting layer is provided. In one embodiment, the prefabricated substrate includes at least an anode substrate. In some embodiments, the prefabricated device includes an anode substrate, a hole functional layer bonded to the anode surface of the anode substrate. In another embodiment, the prefabricated substrate includes at least a cathode substrate. In some embodiments, the prefabricated device includes a cathode substrate, an electronic functional layer bonded to the cathode surface of the cathode substrate. The selection of the hole functional layer and the electron functional layer is as described above, and will not be repeated here.
上述步骤S02中,将预制器件置于含有气态活性材料的气氛环境中,使预制器件在含有气态活性材料的环境中制备量子点发光层,从而在量子点发光层中引入活性材料。其中,含有气态活性材料的气氛环境可以为纯气态活性材料的气氛环境;也可以是含有气态活性材料的惰性气氛环境,其中,惰性气氛包括氮气气氛、二氧化碳气氛或氩气气氛等。所述气氛环境为气态活性材料与氧气、氮气、氩气、二氧化碳中至少一种形成的混合气态环境。In the above step S02, the prefabricated device is placed in an atmosphere containing a gaseous active material, so that the prefabricated device prepares a quantum dot light-emitting layer in an environment containing a gaseous active material, thereby introducing an active material into the quantum dot light-emitting layer. Wherein, the atmosphere environment containing gaseous active material can be pure gaseous active material atmosphere; it can also be inert atmosphere environment containing gaseous active material, wherein, inert atmosphere includes nitrogen atmosphere, carbon dioxide atmosphere or argon atmosphere and the like. The atmospheric environment is a mixed gaseous environment formed by the gaseous active material and at least one of oxygen, nitrogen, argon, and carbon dioxide.
在一些实施例中,气态活性材料占气氛环境中气体总体积的0.1%~50%。在一些实施例中,所述气态环境的温度为25~150℃、总压力为-0.1~4MPa。In some embodiments, the gaseous active material accounts for 0.1% to 50% of the total volume of gas in the atmosphere. In some embodiments, the temperature of the gaseous environment is 25-150° C. and the total pressure is -0.1-4 MPa.
其中,气态活性材料为活性材料的蒸气。具体的,气态活性材料选自至少一个氢原子被羧基取代的有机烃、含有碳碳双键或碳碳三键或苯环的有机酯、不饱和酮中的至少一种。Among them, the gaseous active material is the vapor of the active material. Specifically, the gaseous active material is selected from at least one of organic hydrocarbons with at least one hydrogen atom substituted by carboxyl groups, organic esters containing carbon-carbon double bonds or carbon-carbon triple bonds or benzene rings, and unsaturated ketones.
在一些实施例中,活性材料选自丙烯酸、苯甲酸、甲基丙烯酸、3-丁烯酸、巴豆酸、乙酸、丙酸、丁酸、异丁酸、甲基丙烯酸羟乙酯、甲基丙烯酸甲酯、丙烯酸丁酯、三羟甲基丙三烯酸酯以及N-乙烯基吡咯烷酮中的至少一种。In some embodiments, the active material is selected from the group consisting of acrylic acid, benzoic acid, methacrylic acid, 3-butenoic acid, crotonic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, hydroxyethyl methacrylate, methacrylic acid At least one of methyl ester, butyl acrylate, trimethylol glycerate and N-vinylpyrrolidone.
在预制器件上制备量子点发光层,除了制备环境受限于含有气态活性材料的气氛环境外,制备量子点发光层的流程参照常规流程进行。在一些实施例中,在预制器件上通过溶液加工法制备量子点发光层。To prepare a quantum dot light-emitting layer on a prefabricated device, except that the preparation environment is limited by an atmosphere containing gaseous active materials, the process of preparing the quantum dot light-emitting layer is carried out with reference to the conventional process. In some embodiments, the quantum dot light-emitting layer is prepared by solution processing on a prefabricated device.
在一些实施例中,预制基板为阳极基板;在预制器件上制备量子点发光层的步骤中,在阳极基板的阳极表面制备量子点发光层。进一步的,量子点发光二极管的制备方法,还包括:在量子点发光层背离阳极的表面制备电子功能层,在电子功能层背离量子点发光层的表面制备阴极。In some embodiments, the prefabricated substrate is an anode substrate; in the step of preparing the quantum dot light-emitting layer on the prefabricated device, the quantum dot light-emitting layer is prepared on the anode surface of the anode substrate. Further, the method for preparing a quantum dot light-emitting diode further includes: preparing an electronic functional layer on the surface of the quantum dot light-emitting layer away from the anode, and preparing a cathode on the surface of the electronic functional layer away from the quantum dot light-emitting layer.
在一些实施例中,预制器件包括阳极基板,在阳极基板的阳极表面结合的空穴功能层;在预制器件上制备量子点发光层的步骤中,在空穴功能层背离阳极的表面制备量子点发光层。进一步的,量子点发光二极管的制备方法,还包括:在量子点发光层背离阳极的表面制备电子功能层,在电子功能层背离量子点发光层的表面制备阴极。In some embodiments, the prefabricated device includes an anode substrate and a hole functional layer bound on the anode surface of the anode substrate; in the step of preparing the quantum dot light-emitting layer on the prefabricated device, the quantum dots are prepared on the surface of the hole functional layer facing away from the anode light-emitting layer. Further, the method for preparing a quantum dot light-emitting diode further includes: preparing an electronic functional layer on the surface of the quantum dot light-emitting layer away from the anode, and preparing a cathode on the surface of the electronic functional layer away from the quantum dot light-emitting layer.
在一些实施例中,预制基板为阴极基板;在预制器件上制备量子点发光层的步骤中,在阴极基板的阴极表面制备量子点发光层。进一步的,量子点发光二极管的制备方法,还包括:在量子点发光层背离阴极的表面制备阳极。在一些实施例中,在制备阳极之前,在量子点发光层背离阴极的表面制备空穴功能层,在空穴功能层背离量子点发光层的表面制备阳极。In some embodiments, the prefabricated substrate is a cathode substrate; in the step of preparing the quantum dot light-emitting layer on the prefabricated device, the quantum dot light-emitting layer is prepared on the cathode surface of the cathode substrate. Further, the method for preparing a quantum dot light-emitting diode further includes: preparing an anode on the surface of the quantum dot light-emitting layer facing away from the cathode. In some embodiments, before preparing the anode, a hole functional layer is prepared on the surface of the quantum dot light emitting layer facing away from the cathode, and an anode is prepared on the surface of the hole functional layer facing away from the quantum dot light emitting layer.
在一些实施例中,预制器件包括阴极基板,在阴极基板的阴极表面结合的电子功能层;在预制器件上制备量子点发光层的步骤中,在电子功能层背离阴极的表面制备量子点发光层。进一步的,量子点发光二极管的制备方法,还包括:在量子点发光层背离阴极的表面制备阳极。在一些实施例中,在制备阳极之前,在量子点发光层背离阴极的表面制备空穴功能层,在空穴功能层背离量子点发光层的表面制备阳极。In some embodiments, the prefabricated device includes a cathode substrate and an electronic functional layer combined on the cathode surface of the cathode substrate; in the step of preparing the quantum dot light-emitting layer on the prefabricated device, the quantum dot light-emitting layer is prepared on the surface of the electronic functional layer facing away from the cathode . Further, the method for preparing a quantum dot light-emitting diode further includes: preparing an anode on the surface of the quantum dot light-emitting layer facing away from the cathode. In some embodiments, before preparing the anode, a hole functional layer is prepared on the surface of the quantum dot light emitting layer facing away from the cathode, and an anode is prepared on the surface of the hole functional layer facing away from the quantum dot light emitting layer.
如图8所示,第二种量子点发光二极管的制备方法,包括以下步骤:As shown in Figure 8, the second method for preparing a quantum dot light-emitting diode includes the following steps:
E01. 配置量子点和活性材料的混合溶液,其中,活性材料选自至少一个氢原子被羧基取代的有机烃、含有碳碳双键或碳碳三键或苯环的有机酯、不饱和酮中的至少一种;E01. Configure the mixed solution of quantum dots and active material, wherein the active material is selected from organic hydrocarbons with at least one hydrogen atom substituted by carboxyl groups, organic esters containing carbon-carbon double bonds or carbon-carbon triple bonds or benzene rings, unsaturated ketones at least one of;
E02. 提供待制备量子点发光层的预制器件,在预制器件上沉积混合溶液,制备量子点发光层。E02. Provide a prefabricated device for preparing a quantum dot light-emitting layer, deposit a mixed solution on the prefabricated device, and prepare a quantum dot light-emitting layer.
上述步骤E01中,配置量子点和活性材料的混合溶液,可以先配置含有量子点的溶液,然后加入活性材料,混合形成混合溶液;也可以先配置含有性成分的溶液,然后加入量子点,混合形成混合溶液;还可以在溶剂中同时或先后加入量子点和活性材料,混合形成混合溶液,且量子点和活性材料的先后顺序没有要求。In the above-mentioned step E01, to configure a mixed solution of quantum dots and active materials, a solution containing quantum dots may be configured first, then an active material is added, and mixed to form a mixed solution; or a solution containing sexual components may be configured first, and then quantum dots are added to mix A mixed solution is formed; the quantum dots and the active material can also be added simultaneously or successively in the solvent, and mixed to form a mixed solution, and the order of the quantum dots and the active material is not required.
在一些实施例中,量子点选自为II-VI族化合物、III-V族化合物、II-V族化合物、III-VI化合物、IV-VI族化合物、I-III-VI族化合物、II-IV-VI族化合物或IV族单质中的一种或多种,示例性的,所述量子点为CdSe/ZnSe、CdSe/CdS、CdSe/CdS/ZnS、ZnCdSeS、ZnCdSeS/ZnS、ZnCdS/ZnS、ZnSe/ZnS中的一种或多种。In some embodiments, the quantum dots are selected from the group consisting of II-VI compounds, III-V compounds, II-V compounds, III-VI compounds, IV-VI compounds, I-III-VI compounds, II- One or more of group IV-VI compounds or group IV elements, exemplarily, the quantum dots are CdSe/ZnSe, CdSe/CdS, CdSe/CdS/ZnS, ZnCdSeS, ZnCdSeS/ZnS, ZnCdS/ZnS, One or more of ZnSe/ZnS.
其中,活性材料选自至少一个氢原子被羧基取代的有机烃、含有碳碳双键或碳碳三键或苯环的有机酯、不饱和酮中的至少一种。在一些实施例中,活性材料选自丙烯酸、苯甲酸、甲基丙烯酸、3-丁烯酸、巴豆酸、乙酸、丙酸、丁酸、异丁酸、甲基丙烯酸羟乙酯、甲基丙烯酸甲酯、丙烯酸丁酯、三羟甲基丙三烯酸酯以及N-乙烯基吡咯烷酮中的至少一种。所述混合溶液中,所述活性材料中,量子点和活性材料的总重量的0.0001%~1%。Wherein, the active material is selected from at least one of organic hydrocarbons with at least one hydrogen atom substituted by carboxyl groups, organic esters containing carbon-carbon double bonds or carbon-carbon triple bonds or benzene rings, and unsaturated ketones. In some embodiments, the active material is selected from the group consisting of acrylic acid, benzoic acid, methacrylic acid, 3-butenoic acid, crotonic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, hydroxyethyl methacrylate, methacrylic acid At least one of methyl ester, butyl acrylate, trimethylol glycerate and N-vinylpyrrolidone. In the mixed solution, in the active material, the total weight of the quantum dots and the active material is 0.0001% to 1%.
在一些实施例中,量子点和活性材料混合溶液中,活性材料占量子点和活性材料总重量的0.0001%~1%。由于上述活性材料对量子点溶液具有一定程度的发光效率淬灭作用,因此,这种情况下,活性材料的含量相对量子点的含量较小,可以避免对量子点造成明显的发光淬灭;但是,能够通过后续步骤引入量子点发光层后,发挥提高正老化效应的作用。In some embodiments, in the mixed solution of the quantum dots and the active material, the active material accounts for 0.0001% to 1% of the total weight of the quantum dots and the active material. Since the above-mentioned active materials have a certain degree of quenching effect on the luminescence efficiency of the quantum dot solution, in this case, the content of the active material is relatively small relative to the content of the quantum dots, which can avoid obvious quenching of the luminescence of the quantum dots; however, , can play the role of improving the positive aging effect after introducing the quantum dot light-emitting layer through the subsequent steps.
上述步骤E02中,提供待制备量子点发光层的预制器件。在一种实施情形中,预制基板至少包括阳极基板。在一些实施例中,预制器件为包括阳极基板,在阳极基板的阳极表面结合的空穴功能层。在另一种实施情形中,预制基板至少包括阴极基板。在一些实施例中,预制器件包括阴极基板,在阴极基板的阴极表面结合的电子功能层。空穴功能层和电子功能层的选择如上文所述,此处不再赘述。In the above step E02, a prefabricated device for preparing the quantum dot light-emitting layer is provided. In one embodiment, the prefabricated substrate includes at least an anode substrate. In some embodiments, the prefabricated device includes an anode substrate, a hole functional layer bonded to the anode surface of the anode substrate. In another embodiment, the prefabricated substrate includes at least a cathode substrate. In some embodiments, the prefabricated device includes a cathode substrate, an electronic functional layer bonded to the cathode surface of the cathode substrate. The selection of the hole functional layer and the electron functional layer is as described above, and will not be repeated here.
在预制器件上沉积混合溶液,可以采用常规的方法实现,经过干燥,制备量子点发光层。在一些实施例中,在预制器件上沉积混合溶液的步骤之后,还包括:在温度不高于150℃的条件下干燥处理,制备量子点发光层,以避免过高的温度,导致活性材料挥发,影响量子点发光二极管的正老化效果。The deposition of the mixed solution on the prefabricated device can be achieved by a conventional method, and after drying, the quantum dot light-emitting layer is prepared. In some embodiments, after the step of depositing the mixed solution on the prefabricated device, the method further includes: drying at a temperature not higher than 150° C. to prepare a quantum dot light-emitting layer, so as to avoid excessive temperature and cause the active material to volatilize , affecting the positive aging effect of quantum dot light-emitting diodes.
在一些实施例中,预制基板为阳极基板;在预制器件上沉积混合溶液,制备量子点发光层的步骤中,在阳极基板的阳极表面沉积混合溶液,制备量子点发光层。进一步的,量子点发光二极管的制备方法,还包括:在量子点发光层背离阳极的表面制备电子功能层,在电子功能层背离量子点发光层的表面制备阴极。In some embodiments, the prefabricated substrate is an anode substrate; in the step of depositing a mixed solution on the prefabricated device to prepare a quantum dot light-emitting layer, the mixed solution is deposited on the anode surface of the anode substrate to prepare a quantum dot light-emitting layer. Further, the method for preparing a quantum dot light-emitting diode further includes: preparing an electronic functional layer on the surface of the quantum dot light-emitting layer away from the anode, and preparing a cathode on the surface of the electronic functional layer away from the quantum dot light-emitting layer.
在一些实施例中,预制器件包括阳极基板,在阳极基板的阳极表面结合的空穴功能层;在预制器件上沉积混合溶液,制备量子点发光层的步骤中,在空穴功能层背离阳极的表面沉积混合溶液,制备量子点发光层。进一步的,量子点发光二极管的制备方法,还包括:在量子点发光层背离阳极的表面制备电子功能层,在电子功能层背离量子点发光层的表面制备阴极。In some embodiments, the prefabricated device includes an anode substrate, and a hole functional layer combined on the anode surface of the anode substrate; in the step of depositing a mixed solution on the prefabricated device to prepare a quantum dot light-emitting layer, the hole functional layer is away from the anode in the step of depositing a mixed solution on the prefabricated device. The mixed solution is deposited on the surface to prepare a quantum dot light-emitting layer. Further, the method for preparing a quantum dot light-emitting diode further includes: preparing an electronic functional layer on the surface of the quantum dot light-emitting layer away from the anode, and preparing a cathode on the surface of the electronic functional layer away from the quantum dot light-emitting layer.
在一些实施例中,预制基板为阴极基板;在预制器件上沉积混合溶液,制备量子点发光层的步骤中,在阴极基板的阴极表面沉积混合溶液,制备量子点发光层。进一步的,量子点发光二极管的制备方法,还包括:在量子点发光层背离阴极的表面制备阳极。在一些实施例中,在制备阳极之前,在量子点发光层背离阴极的表面制备空穴功能层,在空穴功能层背离量子点发光层的表面制备阳极。In some embodiments, the prefabricated substrate is a cathode substrate; in the step of depositing a mixed solution on the prefabricated device to prepare a quantum dot light-emitting layer, the mixed solution is deposited on the cathode surface of the cathode substrate to prepare a quantum dot light-emitting layer. Further, the method for preparing a quantum dot light-emitting diode further includes: preparing an anode on the surface of the quantum dot light-emitting layer facing away from the cathode. In some embodiments, before preparing the anode, a hole functional layer is prepared on the surface of the quantum dot light emitting layer facing away from the cathode, and an anode is prepared on the surface of the hole functional layer facing away from the quantum dot light emitting layer.
在一些实施例中,预制器件包括阴极基板,在阴极基板的阴极表面结合的电子功能层;在预制器件上沉积混合溶液,制备量子点发光层的步骤中,在电子功能层背离阴极的表面制备量子点发光层。进一步的,量子点发光二极管的制备方法,还包括:在量子点发光层背离阴极的表面制备阳极。在一些实施例中,在制备阳极之前,在量子点发光层背离阴极的表面制备空穴功能层,在空穴功能层背离量子点发光层的表面制备阳极。In some embodiments, the prefabricated device includes a cathode substrate, and an electronic functional layer combined on the cathode surface of the cathode substrate; in the step of depositing a mixed solution on the prefabricated device to prepare a quantum dot light-emitting layer, the electronic functional layer is prepared on the surface away from the cathode. Quantum dot light-emitting layer. Further, the method for preparing a quantum dot light-emitting diode further includes: preparing an anode on the surface of the quantum dot light-emitting layer facing away from the cathode. In some embodiments, before preparing the anode, a hole functional layer is prepared on the surface of the quantum dot light emitting layer facing away from the cathode, and an anode is prepared on the surface of the hole functional layer facing away from the quantum dot light emitting layer.
本申请实施例提供的量子点发光二极管的制备方法,通过气相法或温和的溶液加工法,在量子点发光层中引入活性材料,得到的量子点发光二极管。活性材料可以修饰/钝化量子点及与量子点发光层相邻的电子功能层界面表面缺陷,抑制表面激子淬灭,减少电子功能层的电荷聚集,增加激子辐射复合几率,并量子点发光层与电子功能层间的电子注入势垒,实现阻挡或促进电子注入,有利于电荷注入平衡,从而显著提高器件的正老化效应。此外气相法或溶液加工法制程工艺简单、对设备要求低,可有效降低制备成本。In the preparation method of quantum dot light-emitting diode provided in the embodiment of the present application, the quantum dot light-emitting diode is obtained by introducing active material into the quantum dot light-emitting layer by gas phase method or mild solution processing method. The active material can modify/passivate the quantum dots and the surface defects of the electronic functional layer adjacent to the quantum dot light-emitting layer, suppress the quenching of surface excitons, reduce the charge accumulation of the electronic functional layer, increase the exciton radiation recombination probability, and reduce the quantum dots. The electron injection potential barrier between the light-emitting layer and the electronic functional layer can block or promote electron injection, which is beneficial to the balance of charge injection, thereby significantly improving the positive aging effect of the device. In addition, the gas phase method or the solution processing method has simple process technology and low equipment requirements, which can effectively reduce the preparation cost.
下面结合具体实施例进行说明。The following description will be given in conjunction with specific embodiments.
实施例1Example 1
如图9所示,一种红色量子点发光二极管,衬底100,位于衬底100上的阳极110,以及依次层叠设置的空穴功能层120、量子点发光层130、电子功能层140和阴极150,其中,衬底100的材料为硅玻璃,阳极110的材料为ITO,空穴功能层120的材料为TFB,量子点发光层130的材料包括量子点CdZnSe/ZnSe/ZnS和丙烯酸,丙烯酸占量子点发光层的总重量的0.005%,阴极150的材料为Ag。As shown in FIG. 9, a red quantum dot light-emitting diode, a substrate 100, an anode 110 located on the substrate 100, and a hole functional layer 120, a quantum dot light-emitting layer 130, an electron functional layer 140 and a cathode are sequentially stacked 150, wherein the material of the substrate 100 is silicon glass, the material of the anode 110 is ITO, the material of the hole function layer 120 is TFB, the material of the quantum dot light-emitting layer 130 includes quantum dots CdZnSe/ZnSe/ZnS and acrylic acid, and acrylic acid accounts for The total weight of the quantum dot light-emitting layer is 0.005%, and the material of the cathode 150 is Ag.
量子点发光二极管的制备方法,包括:A preparation method of a quantum dot light-emitting diode, comprising:
在阳极基板上,旋涂空穴功能材料,制备空穴功能层120,得到预制器件;On the anode substrate, spin-coating a hole functional material to prepare a hole functional layer 120 to obtain a prefabricated device;
将得到的预制器件置于N
2或Ar与活性材料的蒸气构成的气氛中,且丙烯酸所占气体总体积的含量为1%,气态环境的温度为40℃,总压力为1MPa;通过旋涂法制备量子点发光层,转速为3000rpm/s。
The obtained prefabricated device is placed in an atmosphere composed of N2 or Ar and the vapor of the active material, and the content of acrylic acid in the total gas volume is 1%, the temperature of the gaseous environment is 40 ° C, and the total pressure is 1 MPa; The quantum dot light-emitting layer was prepared by the method, and the rotating speed was 3000 rpm/s.
在量子点发光层130的表面旋涂电子功能材料,制备电子功能层140;Spin-coating electronic functional material on the surface of quantum dot light-emitting layer 130 to prepare electronic functional layer 140;
在电子功能层140的表面蒸镀阴极。A cathode is vapor-deposited on the surface of the electronic functional layer 140 .
实施例2Example 2
与实施例1的不同之处在于,红色量子点发光二极管的制备方法过程中,量子点发光层130的制备方法为:The difference from Embodiment 1 is that in the process of preparing the red quantum dot light-emitting diode, the preparation method of the quantum dot light-emitting layer 130 is as follows:
按照丙烯酸占丙烯酸与量子点总重量的0.005%比例,配置活性材料与量子点的混合溶液;According to the proportion of acrylic acid accounting for 0.005% of the total weight of acrylic acid and quantum dots, configure the mixed solution of active material and quantum dots;
在得到预制器件上旋涂活性材料与量子点的混合溶液,制备量子点发光层130。The mixed solution of the active material and the quantum dots is spin-coated on the obtained prefabricated device to prepare the quantum dot light-emitting layer 130 .
测试实施例1-2制备的红色量子点发光二极管的电流效率(cd/A),测试方法如下:以0.2V步长从0V扫描至7V,用吉时利源表和积分球分别监测电流(A)和亮度(nit/m
2),得到电流效率测试值。
The current efficiency (cd/A) of the red quantum dot light-emitting diode prepared in Test Example 1-2, the test method is as follows: scan from 0V to 7V with a 0.2V step, monitor the current with a Keithley source meter and an integrating sphere ( A) and brightness (nit/m 2 ), the current efficiency test value is obtained.
测试结果如下表1所示。The test results are shown in Table 1 below.
表1Table 1
电流效率(cd/A) Current efficiency (cd/A) | 1天后 1 day later | 3天后 3 days later | 6天后 6 days later |
实施例1 Example 1 | 8.6 8.6 | 14.6 14.6 | 18.7 18.7 |
实施例2 Example 2 | 7.6 7.6 | 10.2 10.2 | 14.1 14.1 |
由表1可见,相较于第一天的电流效率,实施例1提供的红色量子点发光二极管,6天后电流效率提升117%;实施例2提供的红色量子点发光二极管,6天后电流效率提升85%。可见,本申请实施例提供的红色量子点发光二极管,正老化效率明显提高。As can be seen from Table 1, compared with the current efficiency of the first day, the current efficiency of the red quantum dot light-emitting diode provided in Example 1 was increased by 117% after 6 days; the current efficiency of the red quantum dot light-emitting diode provided by Example 2 was increased after 6 days. 85%. It can be seen that the positive aging efficiency of the red quantum dot light-emitting diode provided in the embodiment of the present application is significantly improved.
实施例3Example 3
一种蓝色量子点发光二极管,衬底,位于衬底上的阳极,以及依次层叠设置的空穴功能层、量子点发光层、电子功能层和阴极,其中,衬底的材料为硅玻璃,阳极的材料为ITO,空穴功能层的材料为TFB,量子点发光层的材料包括量子点CdZnSe/ZnS和丙烯酸,丙烯酸的含量比例0.01%,阴极的材料为Ag。A blue quantum dot light-emitting diode, a substrate, an anode located on the substrate, and a hole functional layer, a quantum dot light-emitting layer, an electronic functional layer and a cathode that are stacked in sequence, wherein the material of the substrate is silicon glass, The material of the anode is ITO, the material of the hole functional layer is TFB, the material of the quantum dot light-emitting layer includes quantum dots CdZnSe/ZnS and acrylic acid, the content of acrylic acid is 0.01%, and the material of the cathode is Ag.
量子点发光二极管的制备方法,包括:A preparation method of a quantum dot light-emitting diode, comprising:
在阳极基板上,旋涂空穴功能材料,制备空穴功能层,得到预制器件;On the anode substrate, spin-coating the hole functional material to prepare a hole functional layer to obtain a prefabricated device;
将得到的预制器件置于N
2或Ar与活性材料的蒸气构成的气氛中,且丙烯酸所占气体总体积的含量为1%,气态环境的温度为40℃,总压力为1MPa;通过旋涂法制备量子点发光层,转速为3000rpm/s。在量子点发光层的表面旋涂电子功能材料,制备电子功能层;
The obtained prefabricated device is placed in an atmosphere composed of N2 or Ar and the vapor of the active material, and the content of acrylic acid in the total gas volume is 1%, the temperature of the gaseous environment is 40 ° C, and the total pressure is 1 MPa; The quantum dot light-emitting layer was prepared by the method, and the rotating speed was 3000 rpm/s. Spin-coating electronic functional materials on the surface of the quantum dot light-emitting layer to prepare electronic functional layers;
在电子功能层的表面蒸镀阴极。A cathode is vapor-deposited on the surface of the electronic functional layer.
实施例4Example 4
与实施例3的不同之处在于,蓝色量子点发光二极管的制备方法过程中,量子点发光层的制备方法为:The difference from Example 3 is that in the preparation method of the blue quantum dot light-emitting diode, the preparation method of the quantum dot light-emitting layer is:
按照丙烯酸占丙烯酸与量子点总重量的0.005%比例,配置活性材料与量子点的混合溶液;According to the proportion of acrylic acid accounting for 0.005% of the total weight of acrylic acid and quantum dots, configure the mixed solution of active material and quantum dots;
在得到预制器件上旋涂活性材料与量子点的混合溶液,制备量子点发光层。A mixed solution of active material and quantum dots is spin-coated on the obtained prefabricated device to prepare a quantum dot light-emitting layer.
测试实施例3-4制备的红色量子点发光二极管的电流效率(cd/A),测试方法如下:以0.2V步长从0V扫描至7V,用吉时利源表和积分球分别监测电流(A)和亮度(nit/m
2),得到电流效率测试值。
The current efficiency (cd/A) of the red quantum dot light-emitting diodes prepared in Test Example 3-4, the test method is as follows: scan from 0V to 7V with a step size of 0.2V, monitor the current with a Keithley source meter and an integrating sphere ( A) and brightness (nit/m 2 ), the current efficiency test value is obtained.
测试结果如下表1所示。The test results are shown in Table 1 below.
表2Table 2
电流效率(cd/A) Current efficiency (cd/A) | 1天后 1 day later | 3天后 3 days later | 6天后 6 days later |
实施例4 Example 4 | 4.8 4.8 | 6.3 6.3 | 9.0 9.0 |
实施例5 Example 5 | 4.2 4.2 | 5.8 5.8 | 7.6 7.6 |
由表2可见,相较于第一天的电流效率,实施例3提供的红色量子点发光二极管,6天后电流效率提升87.6%;实施例4提供的红色量子点发光二极管,6天后电流效率提升80.9%。可见,本申请实施例提供的红色量子点发光二极管,正老化效率明显增加。As can be seen from Table 2, compared with the current efficiency of the first day, the current efficiency of the red quantum dot light-emitting diode provided in Example 3 was improved by 87.6% after 6 days; the current efficiency of the red quantum dot light-emitting diode provided by Example 4 was improved after 6 days. 80.9%. It can be seen that the positive aging efficiency of the red quantum dot light-emitting diode provided in the embodiment of the present application is significantly increased.
以上仅为本申请的较佳实施例而已,并不用以限制本申请,凡在本申请的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本申请的保护范围之内。The above are only preferred embodiments of the present application and are not intended to limit the present application. Any modifications, equivalent replacements and improvements made within the spirit and principles of the present application shall be included in the protection scope of the present application. Inside.
Claims (18)
- 一种量子点发光二极管,其特征在于,包括相对设置的阳极和阴极,设置在所述阳极和所述阴极之间的量子点发光层,以及设置在所述量子点发光层和所述阴极之间的电子功能层;其中,所述量子点发光层中含有活性材料,所述活性材料选自至少一个氢原子被羧基取代的有机烃、含有碳碳双键或碳碳三键或苯环的有机酯、不饱和酮中的至少一种。 A quantum dot light emitting diode is characterized in that it comprises 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 quantum dot light emitting layer and the cathode The electronic functional layer in between; wherein, the quantum dot light-emitting layer contains active materials, and the active materials are selected from organic hydrocarbons with at least one hydrogen atom substituted by carboxyl groups, carbon-carbon double bonds or carbon-carbon triple bonds or benzene rings. At least one of organic ester and unsaturated ketone.
- 如权利要求1所述的量子点发光二极管,其特征在于,所述活性材料选自丙烯酸、苯甲酸、甲基丙烯酸、3-丁烯酸、巴豆酸、乙酸、丙酸、丁酸、异丁酸、甲基丙烯酸羟乙酯、甲基丙烯酸甲酯、丙烯酸丁酯、三羟甲基丙三烯酸酯以及N-乙烯基吡咯烷酮中的至少一种。 The quantum dot light-emitting diode according to claim 1, wherein the active material is selected from the group consisting of acrylic acid, benzoic acid, methacrylic acid, 3-butenoic acid, crotonic acid, acetic acid, propionic acid, butyric acid, isobutyric acid at least one of acid, hydroxyethyl methacrylate, methyl methacrylate, butyl acrylate, trimethylol glycerate, and N-vinylpyrrolidone.
- 如权利要求1所述的量子点发光二极管,其特征在于,所述活性材料占所述量子点发光层的总重量的0.0001%~1%。 The quantum dot light-emitting diode according to claim 1, wherein the active material accounts for 0.0001%-1% of the total weight of the quantum dot light-emitting layer.
- 如权利要求1所述的量子点发光二极管,其特征在于,所述量子点发光层由量子点和所述活性材料组成。 The quantum dot light-emitting diode according to claim 1, wherein the quantum dot light-emitting layer is composed of quantum dots and the active material.
- 如权利要求4所述的量子点发光二极管,其特征在于,所述量子点选自为II-VI族化合物、III-V族化合物、II-V族化合物、III-VI化合物、IV-VI族化合物、I-III-VI族化合物、II-IV-VI族化合物或IV族单质中的一种或多种。 The quantum dot light-emitting diode of claim 4, wherein the quantum dots are selected from the group consisting of II-VI compounds, III-V compounds, II-V compounds, III-VI compounds, and IV-VI compounds One or more of compounds, I-III-VI group compounds, II-IV-VI group compounds or group IV elements.
- 如权利要求5所述的量子点发光二极管,其特征在于,所述量子点为CdSe/ZnSe、CdSe/CdS、CdSe/CdS/ZnS、ZnCdSeS、ZnCdSeS/ZnS、ZnCdS/ZnS、ZnSe/ZnS中的一种或多种。 The quantum dot light-emitting diode according to claim 5, wherein the quantum dots are CdSe/ZnSe, CdSe/CdS, CdSe/CdS/ZnS, ZnCdSeS, ZnCdSeS/ZnS, ZnCdS/ZnS, ZnSe/ZnS one or more.
- 如权利要求1至6任一项所述的量子点发光二极管,其特征在于,所述量子点发光二极管还包括设置在所述阳极和所述量子点发光层之间的空穴功能层。 The quantum dot light emitting diode according to any one of claims 1 to 6, wherein the quantum dot light emitting diode further comprises a hole function layer disposed between the anode and the quantum dot light emitting layer.
- 一种量子点发光二极管的制备方法,其特征在于,包括以下步骤: A method for preparing a quantum dot light-emitting diode, comprising the following steps:提供待制备量子点发光层的预制器件;Provide a prefabricated device for preparing a quantum dot light-emitting layer;将所述预制器件置于含有气态活性材料的气氛环境中,在所述预制器件上制备量子点发光层;其中,所述气态活性材料选自至少一个氢原子被羧基取代的有机烃、含有碳碳双键或碳碳三键或苯环的有机酯、不饱和酮中的至少一种。The prefabricated device is placed in an atmosphere containing a gaseous active material, and a quantum dot light-emitting layer is prepared on the prefabricated device; wherein the gaseous active material is selected from organic hydrocarbons whose at least one hydrogen atom is substituted by a carboxyl group, a carbon-containing At least one of carbon double bond or carbon-carbon triple bond or organic ester of benzene ring and unsaturated ketone.
- 如权利要求8所述的量子点发光二极管的制备方法,其特征在于,所述气氛环境为气态活性材料与氧气、氮气、氩气、二氧化碳中至少一种形成的混合气态环境。 The method for manufacturing a quantum dot light-emitting diode according to claim 8, wherein the atmosphere is a mixed gaseous environment formed by a gaseous active material and at least one of oxygen, nitrogen, argon, and carbon dioxide.
- 如权利要求8所述的量子点发光二极管的制备方法,其特征在于,所述活性材料选自丙烯酸、苯甲酸、甲基丙烯酸、3-丁烯酸、巴豆酸、乙酸、丙酸、丁酸、异丁酸、甲基丙烯酸羟乙酯、甲基丙烯酸甲酯、丙烯酸丁酯、三羟甲基丙三烯酸酯以及N-乙烯基吡咯烷酮中的至少一种。 The method for preparing a quantum dot light-emitting diode according to claim 8, wherein the active material is selected from the group consisting of acrylic acid, benzoic acid, methacrylic acid, 3-butenoic acid, crotonic acid, acetic acid, propionic acid, butyric acid , at least one of isobutyric acid, hydroxyethyl methacrylate, methyl methacrylate, butyl acrylate, trimethylol acrylate and N-vinylpyrrolidone.
- 如权利要求8至10任一项所述的量子点发光二极管的制备方法,其特征在于,所述气态活性材料占所述气氛环境中气体总体积的0.1%~50%。 The method for manufacturing a quantum dot light-emitting diode according to any one of claims 8 to 10, wherein the gaseous active material accounts for 0.1% to 50% of the total volume of the gas in the atmosphere.
- 如权利要求8至10任一项所述的量子点发光二极管的制备方法,其特征在于,所述气态环境的温度为25~150℃,总压力为-0.1~4MPa。 The method for preparing a quantum dot light-emitting diode according to any one of claims 8 to 10, wherein the temperature of the gaseous environment is 25-150° C., and the total pressure is -0.1-4 MPa.
- 一种量子点发光二极管的制备方法,其特征在于,包括以下步骤: A method for preparing a quantum dot light-emitting diode, comprising the following steps:配置量子点和活性材料的混合溶液,其中,所述活性材料选自至少一个氢原子被羧基取代的有机烃、含有碳碳双键或碳碳三键或苯环的有机酯、不饱和酮中的至少一种;A mixed solution of quantum dots and active materials is configured, wherein the active materials are selected from organic hydrocarbons with at least one hydrogen atom substituted by carboxyl groups, organic esters containing carbon-carbon double bonds or carbon-carbon triple bonds or benzene rings, and unsaturated ketones at least one of;提供待制备量子点发光层的预制器件,在所述预制器件上沉积所述混合溶液,制备量子点发光层。A prefabricated device on which a quantum dot light-emitting layer is to be prepared is provided, and the mixed solution is deposited on the prefabricated device to prepare a quantum dot light-emitting layer.
- 如权利要求13所述的量子点发光二极管的制备方法,其特征在于,所述混合溶液中,所述活性材料占所述量子点和所述活性材料的总重量的0.0001%~1%。 The method for preparing a quantum dot light-emitting diode according to claim 13, wherein, in the mixed solution, the active material accounts for 0.0001% to 1% of the total weight of the quantum dots and the active material.
- 如权利要求13或14所述的量子点发光二极管的制备方法,其特征在于,在所述预制器件上沉积所述混合溶液的步骤之后,还包括:在温度不高于150℃的条件下干燥处理,制备所述量子点发光层。 The method for preparing a quantum dot light-emitting diode according to claim 13 or 14, wherein after the step of depositing the mixed solution on the prefabricated device, the method further comprises: drying at a temperature not higher than 150°C treatment to prepare the quantum dot light-emitting layer.
- 如权利要求13或14所述的量子点发光二极管的制备方法,其特征在于,所述活性材料选自丙烯酸、苯甲酸、甲基丙烯酸、3-丁烯酸、巴豆酸、乙酸、丙酸、丁酸、异丁酸、甲基丙烯酸羟乙酯、甲基丙烯酸甲酯、丙烯酸丁酯、三羟甲基丙三烯酸酯以及N-乙烯基吡咯烷酮中的至少一种。 The method for preparing a quantum dot light-emitting diode according to claim 13 or 14, wherein the active material is selected from the group consisting of acrylic acid, benzoic acid, methacrylic acid, 3-butenoic acid, crotonic acid, acetic acid, propionic acid, At least one of butyric acid, isobutyric acid, hydroxyethyl methacrylate, methyl methacrylate, butyl acrylate, trimethylol acrylate, and N-vinylpyrrolidone.
- 如权利要求13或14所述的量子点发光二极管的制备方法,其特征在于,所述量子点选自为II-VI族化合物、III-V族化合物、II-V族化合物、III-VI化合物、IV-VI族化合物、I-III-VI族化合物、II-IV-VI族化合物或IV族单质中的一种或多种。 The method for preparing a quantum dot light-emitting diode according to claim 13 or 14, wherein the quantum dots are selected from the group consisting of II-VI compounds, III-V compounds, II-V compounds, and III-VI compounds , one or more of IV-VI group compounds, I-III-VI group compounds, II-IV-VI group compounds or group IV elements.
- 如权利要求17所述的量子点发光二极管的制备方法,其特征在于,所述量子点为CdSe/ZnSe、CdSe/CdS、CdSe/CdS/ZnS、ZnCdSeS、ZnCdSeS/ZnS、ZnCdS/ZnS、ZnSe/ZnS中的一种或多种。 The method for preparing a quantum dot light-emitting diode according to claim 17, wherein the quantum dots are CdSe/ZnSe, CdSe/CdS, CdSe/CdS/ZnS, ZnCdSeS, ZnCdSeS/ZnS, ZnCdS/ZnS, ZnSe/ One or more of ZnS.
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