WO2020134201A1 - 量子点发光二极管的制备方法 - Google Patents
量子点发光二极管的制备方法 Download PDFInfo
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- C09K11/56—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing sulfur
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- C09K11/88—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
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- H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
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- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
- H10K71/15—Deposition of organic active material using liquid deposition, e.g. spin coating characterised by the solvent used
Definitions
- the present application relates to the field of display technology, and in particular to a method for manufacturing a quantum dot light emitting diode.
- Quantum dots also known as semiconductor nanocrystals, whose three-dimensional dimensions are in the nanometer range (l-100nm), is a kind of nanoparticle theory between bulk materials and molecules.
- Quantum dots have excellent optical properties such as high quantum yield, large molar extinction coefficient, good light stability, narrow half-width, broad excitation spectrum and controllable emission spectrum, and are very suitable for use as light-emitting materials for light-emitting devices.
- quantum dot fluorescent materials have been widely used in the field of flat panel displays due to their advantages of high light color purity, adjustable luminous color, and long service life. They have become a promising next-generation display and solid-state lighting source.
- Quantum dot light emitting diodes are light-emitting devices based on quantum dot materials as luminescent materials. Due to their advantages of tunable wavelength, narrow emission spectrum, high stability, high electroluminescence quantum yield, etc. A strong competitor of a generation of display technology.
- the solution processing method is a common method for preparing QLED devices. In particular, with the development of technology, it has become conventional to prepare quantum dot light-emitting layers using inkjet printing technology.
- the quantum dot light-emitting layer is prepared by a solution processing method such as inkjet printing
- part of the solvent of the quantum dot ink remains during film formation, especially during inkjet printing, in order to slow down the printing drying speed, a high boiling point is added to the quantum dot ink Solvent, high boiling Point solvent residues also contribute to the luminous efficiency and service life of quantum dot LEDs.
- One of the purposes of the embodiments of the present application is to provide a method for preparing a quantum dot light-emitting diode, which aims to solve the problem And/or impurities formed by residual solvent), a problem that affects the luminous efficiency and service life of quantum dot light-emitting diodes.
- a method for manufacturing a quantum dot light emitting diode including the following steps:
- the substrate is immersed in a solvent system for ultrasonic treatment, the solvent system includes a host solvent and a doping solvent dissolved in the host solvent, the polarity of the doping solvent is less than that of the host solvent And the host solvent is an organic solvent that does not dissolve quantum dots.
- the host solvent is selected from alcohols with a linear number of carbon atoms less than 20, esters with a linear number of carbon atoms less than 20, and carbon numbers with a linear number of less than 20 One or a combination of two or more ketones.
- the alcohols having less than 20 carbon atoms in the linear chain are selected from 1-propanol, 1-butanol, 1-pentanol, 2-pentanol, 1,5-pentanol One or more of diol and 2,3-butanediol;
- esters having less than 20 carbon atoms in the linear chain are selected from ethyl acetate, ethyl propionate, ethyl methacrylate, and ethyl benzoate;
- ketones having less than 20 carbon atoms in the linear chain are selected from acetone, methyl ethyl ketone, 3-pentanone, 2-methyl 4-octanone.
- the alcohol derivative having less than 10 carbon atoms in the linear chain is selected from one or more of methoxyethanol, ethoxyethanol, ethyl mandelic acid, and the like.
- the doping solvent is selected from unsaturated fatty acids with less than 10 carbon atoms in the linear chain, alcohol derivatives with less than 10 carbon atoms in the linear chain, and carbon in the linear chain
- unsaturated fatty acids with less than 10 carbon atoms in the linear chain alcohol derivatives with less than 10 carbon atoms in the linear chain, and carbon in the linear chain
- the unsaturated fatty acid having less than 10 carbon atoms is selected from one or more of acrylic acid, crotonic acid, methacrylic acid, and 3-pentenoic acid;
- the alcohol derivative having a carbon number of less than 10 in the linear chain is selected from one of methoxyethanol, ethoxyethanol, ethyl 2-hydroxy-2-phenylacetate and acetol Multiple
- the saturated acids having less than 10 carbon atoms in the linear chain are selected from one or more of acetic acid, propionic acid, butyric acid and valeric acid;
- the acid derivatives having less than 15 carbon atoms in the linear chain are selected from one or more of perfluorooctanoic acid, perfluorodecylphosphonic acid, perchlorodecylcarboxylic acid and perfluorododecanoic acid ;
- halogenated hydrocarbons having less than 20 carbon atoms in the linear chain are selected from fluoropropane, 1-chlorobutane, 1-chlorohexane and 3
- the weight percentage of the doping solvent is 0.001-0.5%.
- the frequency of the ultrasonic treatment is 20 kHz-10 9 kHz.
- the frequency of the ultrasonic treatment is 20 kHz-100 kHz.
- the power density of the ultrasonic treatment is 0.3-200 w/cm 2 .
- the power density of the ultrasonic treatment is 5-100 w/cm 2 .
- the step of immersing the quantum dot light-emitting layer in a solvent system for ultrasonic treatment is 20 minutes-48 hours.
- the ultrasonic treatment time is 1 hour -10 hours.
- the substrate is a substrate provided with a bottom electrode.
- the bottom electrode is an anode, and before preparing the quantum dot light emitting layer, a step of preparing a hole functional layer on the anode surface of the substrate is further included; the hole functional layer includes holes At least one layer of the injection layer, the hole transport layer, and the electron blocking layer.
- the bottom electrode is an anode, and before preparing the cathode, the method further includes a step of preparing an electronic functional layer on a side of the quantum dot light-emitting layer facing away from the anode; the electronic functional layer includes At least one of the electron injection layer, the electron transport layer, and the hole blocking layer.
- the beneficial effects of the preparation method of the quantum dot light emitting diode are as follows: After the quantum dot light emitting layer is prepared, the quantum dot light emitting layer is immersed in a solvent system for ultrasonic treatment.
- the solvent system includes a host solvent and a doping solvent dissolved in the host solvent, the polarity of the doping solvent is less than the polarity of the host solvent, and the host solvent is insoluble in quantum dots Organic solvents.
- the solvent system penetrates into the quantum dot light-emitting layer to dissolve impurities in the quantum dot light-emitting layer (impurities introduced by the quantum dot itself and/or impurities formed by residual solvent), thereby removing residual impurities to the quantum dot light-emitting diode
- impurities introduced by the quantum dot itself and/or impurities formed by residual solvent impurities introduced by the quantum dot itself and/or impurities formed by residual solvent
- FIG. 1 is a schematic flowchart of a method for manufacturing a quantum dot light emitting diode according to an embodiment of the present application.
- first and second are used for descriptive purposes only, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, the features defined as “first” and “second” may explicitly or implicitly include one or more of the features. In the description of this application , “Multiple” means two or more, unless otherwise specifically limited.
- some embodiments of the present application provide a method for manufacturing a quantum dot light emitting diode, including the following steps:
- S 10 provides a substrate on which a quantum dot light emitting layer is provided
- the solvent system includes a host solvent and a doping solvent dissolved in the host solvent, the doping solvent has a polarity less than that of the host solvent Polarity, and the host solvent is an organic solvent that does not dissolve quantum dots.
- the preparation method of the quantum dot light emitting diode provided in the embodiments of the present application, after the quantum dot light emitting layer is prepared, the quantum dot light emitting layer is immersed in a solvent system for ultrasonic treatment.
- the solvent system includes a host solvent and a doping solvent dissolved in the host solvent, the polarity of the doping solvent is less than the polarity of the host solvent, and the host solvent is insoluble in quantum dots Organic solvents.
- the solvent system penetrates into the quantum dot light-emitting layer to dissolve impurities in the quantum dot light-emitting layer (impurities introduced by the quantum dot itself and/or impurities formed by residual solvent), thereby removing residual impurities to the quantum dot light-emitting diode
- impurities introduced by the quantum dot itself and/or impurities formed by residual solvent impurities introduced by the quantum dot itself and/or impurities formed by residual solvent
- the quantum dot light emitting diode is divided into a positive structure and an inverse structure.
- the positive structure includes an anode, a cathode, and a quantum dot light emitting layer disposed between the anode and the cathode.
- the anode of the positive structure is disposed on the substrate, and hole transport may be provided between the anode and the quantum dot light emitting layer.
- the hole functional layer such as a layer, a hole injection layer, and an electron blocking layer may be provided with an electron functional layer such as an electron transport layer, an electron injection layer, and a hole blocking layer between the cathode and the quantum dot light emitting layer.
- the inversion structure includes an anode, a cathode, and a quantum dot light emitting layer disposed between the anode and the cathode.
- the cathode of the inversion structure is disposed on the substrate, and hole transport can also be provided between the anode and the quantum dot light emitting layer.
- the hole functional layer such as a layer, a hole injection layer, and an electron blocking layer may be provided with an electron functional layer such as an electron transport layer, an electron injection layer, and a hole blocking layer between the cathode and the quantum dot light emitting layer.
- the bottom electrode provided on the substrate is an anode.
- the substrate may be provided with a bottom electrode on the substrate and a A quantum dot light emitting layer on the surface of the bottom electrode; in yet another embodiment of the present application, the substrate may include a substrate and a layer A bottom electrode stacked on the surface of the substrate, a hole transport layer stacked on the surface of the substrate, and a quantum dot light emitting layer disposed on the surface of the hole transport layer; in yet another embodiment of the present application, the substrate may It includes a substrate, a bottom electrode stacked on the surface of the substrate, a hole injection layer stacked on the surface of the substrate, a hole transport layer stacked on the surface of the hole injection layer, and quantum dots provided on the surface of the hole transport layer Light emitting layer; in still another embodiment of the present application, the substrate may include a substrate, a bottom electrode stacked on the surface of the substrate, a hole injection layer stacked on the surface
- the bottom electrode provided on the substrate is a cathode.
- the substrate may be provided with a bottom electrode on the substrate; in another embodiment of the present application, the substrate may include a substrate, a bottom electrode stacked on the surface of the substrate, an electron transport layer stacked on the surface of the substrate, and a quantum dot light emitting layer disposed on the surface of the electron transport layer;
- the substrate may include a substrate, a bottom electrode stacked on the surface of the substrate, an electron injection layer stacked on the surface of the substrate, a hole transport layer stacked on the surface of the electron injection layer, and A quantum dot light emitting layer on the surface of the electron transport layer; in still another embodiment of the present application, the substrate may include a substrate, a bottom electrode stacked on the surface of the substrate, an electron injection layer stacked on the surface of the substrate, An electron transport layer provided on the surface of the electron injection layer, a hole blocking layer provided on the surface of the electron transport
- a substrate provided with a bottom electrode is provided, that is, a bottom electrode is provided on the substrate.
- the selection of the substrate is not strictly limited, and a rigid substrate such as a glass substrate may be used; a flexible substrate such as a polyimide substrate or a polynorbornene substrate may also be used, but it is not limited thereto.
- the bottom electrode is an electrode opposite to the top electrode, and the bottom electrode may be a cathode or an anode. Specifically, when the bottom electrode is an anode, the top electrode is a cathode; when the bottom electrode is a cathode, the top electrode is an anode.
- the anode may use ITO, but it is not limited thereto.
- the cathode may use metal electrodes, including but not limited to silver electrodes and aluminum electrodes.
- the thickness of the cathode is 60-120nm. In some embodiments of the present application, it is 100nm.
- the method for preparing the quantum dot light-emitting layer on the bottom electrode is not strictly limited, and the quantum dot light-emitting layer may be prepared by a conventional method in the art.
- a solution processing method is used on the bottom electrode A quantum dot solution is deposited to prepare a quantum dot light-emitting layer.
- the quantum dot light-emitting layer prepared by the solution processing method is subjected to ultrasonic treatment in a specific solvent system through the following steps, and the quantum dot impurities and solvent impurities remaining in the quantum dot light-emitting layer, especially the remaining high-boiling solvent, can be further removed Together, it significantly improves the impurity removal effect of the quantum dot light-emitting layer.
- an inkjet printing method is used to deposit quantum dot ink on the bottom electrode to prepare a quantum dot light emitting layer.
- the quantum dots in the quantum dot light-emitting layer are conventional quantum dots in the art.
- the thickness of the quantum dot light-emitting layer is 30-50 nm
- the quantum dot light emitting layer is immersed in a solvent system for ultrasonic treatment, and by ultrasonic treatment, a small amount of doping solvent present in the solvent system penetrates into the quantum dot light emitting layer to dissolve the quantum dot Impurities in the light-emitting layer (impurities introduced by quantum dots and/or impurities formed by residual solvents), thereby removing the influence of residual impurities on the luminous efficiency and service life of quantum dot light-emitting diodes, and ultimately improving the luminous efficiency and use of quantum dot light-emitting diodes life.
- a solvent system for ultrasonic treatment a small amount of doping solvent present in the solvent system penetrates into the quantum dot light emitting layer to dissolve the quantum dot Impurities in the light-emitting layer (impurities introduced by quantum dots and/or impurities formed by residual solvents), thereby removing the influence of residual impurities on the luminous efficiency and service life of quantum dot light-emitting diodes, and ultimately improving the
- the quantum dot light emitting layer is immersed in a solvent system to perform ultrasonic treatment, and the quantum dot light emitting layer is subjected to ultrasonic treatment to remove impurities.
- the entire substrate prepared with the quantum dot light-emitting layer is placed in a solvent system for ultrasonic treatment.
- the solvent system includes a host solvent and a doping solvent dissolved in the host solvent to form a uniform solvent system.
- the polarity of the doping solvent is less than the polarity of the host solvent, and the host solvent is an organic solvent that does not dissolve quantum dots.
- the solvent system thus formed can effectively remove residual impurities in the quantum dot light-emitting layer.
- the host solvent does not dissolve the light-emitting layer
- the doping solvent can dissolve the quantum dot light-emitting layer
- the low concentration of the dopant solvent in the host solvent can dissolve impurities of relatively low molecular weight without destroying the nanoparticles of the light-emitting layer.
- the host solvent is selected from alcohols with less than 20 carbon atoms in the linear chain, esters with less than 20 carbon atoms in the linear chain, and fewer than 20 carbon atoms in the linear chain One or a combination of two or more ketones and alcohol derivatives with a linear number of carbon atoms less than 10.
- the alcohols in the linear chain having less than 20 carbon atoms are selected from 1-propanol and 1-butanol
- the esters with less than 20 carbon atoms in the linear chain are selected from ethyl acetate, ethyl propionate, ethyl methacrylate, and ethyl benzoate.
- the ketones having less than 20 carbon atoms in the linear chain It is selected from acetone, methyl ethyl ketone, 3-pentanone, 2-methyl 4-octanone.
- the alcohol derivative having a carbon number of less than 10 in the linear chain is selected from the group consisting of methoxyethanol, ethoxyethanol, ethyl 2-hydroxy-2-phenylacetate and acetone alcohol One or more.
- the doping solvent is selected from unsaturated fatty acids with less than 10 carbon atoms in the straight chain, alcohol derivatives with less than 10 carbon atoms in the straight chain, and less than 10 carbon atoms in the straight chain One or a combination of two or more of saturated acids of 10, acid derivatives with less than 15 carbon atoms in the linear chain, and halogenated hydrocarbons with less than 20 carbon atoms in the linear chain.
- the polarity of the solute is less than or equal to the polarity of the host solvent, and may even have a certain solubility in quantum dots, but after mixing with the host solvent to form a solution, due to the amount of added Low, will not cause the dissolution of quantum dots.
- the unsaturated fatty acid having a carbon number of less than 10 is selected from acrylic acid, crotonic acid, methacrylic acid, and 3-pentenoic acid.
- the alcohol derivative having a carbon number of less than 10 in the linear chain is selected from methoxyethanol, ethoxyethanol, phenoxyethanol, and 1-methoxy-1,2-propanediol One or more of them.
- the saturated acids with less than 10 carbon atoms in the linear chain are selected from one or more of acetic acid, propionic acid, butyric acid, and valeric acid.
- the acid derivative having less than 15 carbon atoms in the linear chain is selected from one of perfluorooctanoic acid, perfluorodecylphosphonic acid, perchlorodecylcarboxylic acid, and perfluorododecanoic acid Or more.
- the halogenated hydrocarbon with a carbon number of less than 20 in the linear chain is selected from one or more of fluoropropane, 1-chlorobutane, 1-chlorohexane, and 3-fluorohexane
- the weight percentage of the doping solvent is 0-0.5%, but not 0. If the content of the low-polarity doping solvent in the solvent system is too high, part of the quantum dots in the quantum dot light-emitting layer may be dissolved, thereby affecting the function of the quantum dot light-emitting layer. In some embodiments of the present application, the weight percentage of the doping solvent is 0.001-0.05%
- the frequency of the ultrasonic treatment is 20 kHz-10 9 kHz. If the frequency of the ultrasonic treatment is too high, it will affect the stability of the formed film layer including the quantum dot light-emitting layer, and the film layer is easily detached from the substrate, thereby destroying the stability of the device structure. If the frequency of the ultrasonic treatment is too low, the effect of removing impurities in the quantum dot light-emitting layer is not obvious, and the effect of improving the service life and luminous efficiency of the quantum dot light-emitting diode is not significant . In some embodiments of the present application, in the step of immersing the quantum dot light emitting layer in a solvent system for ultrasonic treatment, the frequency of the ultrasonic treatment is 20 kHz-100 kHz
- the power density of the ultrasonic treatment is 0.3-200 w/cm 2 if the power density of the ultrasonic treatment is excessive High, it will affect the stability of the formed film layer including the quantum dot light-emitting layer, the film layer is easily detached from the substrate, thereby destroying the stability of the device structure. If the power density of the ultrasonic treatment is too low, the effect of removing impurities in the quantum dot light-emitting layer is not obvious, and the effect of improving the service life and luminous efficiency of the quantum dot light-emitting diode is not significant.
- the power density of the ultrasonic treatment is 5-100 w/cm
- the step of immersing the quantum dot light emitting layer in a solvent system for ultrasonic treatment the ultrasonic treatment time is 20 minutes-48 hours. If the ultrasonic treatment time is too long, the ultrasonic treatment for a long time will affect the stability of the formed film layer including the quantum dot light-emitting layer, and the film layer is easily detached from the substrate, thereby destroying the stability of the device structure. If the time of the ultrasonic treatment is too short, a better effect of removing impurities in the quantum dot light-emitting layer cannot be achieved. In some embodiments of the present application, in the step of immersing the quantum dot light emitting layer in a solvent system to perform ultrasonic treatment, the ultrasonic treatment time is 1 hour to 10 hours.
- the top electrode is prepared on the surface of the quantum dot light-emitting layer after ultrasonic treatment away from the bottom electrode, which can be prepared by a conventional method in the art. It is worth noting that the top electrode in the embodiment of the present application is an electrode opposite to the top electrode, and may specifically be an anode or a cathode.
- a quantum dot light-emitting diode having a basic structure including a cathode and an anode disposed oppositely, and a quantum dot light-emitting layer disposed between the cathode and the anode
- a basic structure including a cathode and an anode disposed oppositely, and a quantum dot light-emitting layer disposed between the cathode and the anode
- different functional layers can be introduced on the basic structure of the quantum dot light-emitting diode to balance carriers.
- the bottom electrode when the bottom electrode is an anode, that is, the anode is provided on the substrate to form an anode substrate, before preparing the quantum dot light emitting layer, it further includes preparing a hole function layer on the anode surface of the substrate ( The step of providing the hole functional layer between the anode and the quantum dot light-emitting layer).
- the hole functional layer includes at least one of a hole injection layer, a hole transport layer, and an electron blocking layer.
- the hole injection layer and the hole transport layer are used to reduce the difficulty of hole injection, and the electron blocking layer is used to block excess Electrons, so that excessive electrons cannot reach the anode to form a leakage current, thereby improving the current efficiency of the quantum dot light-emitting diode.
- the method when the anode is provided on the substrate to form the anode substrate, before preparing the quantum dot light emitting layer, the method further includes: preparing a hole injection layer on the anode surface of the substrate, and injecting the hole The step of preparing a hole transport layer on the side of the layer facing away from the anode.
- the material of the hole injection layer may be a conventional hole injection material, including but not limited to PEDOT:PSS.
- the material of the hole transport layer may be employed conventional hole transporting materials, including but not limited to NPB, TFB and other organic materials, and N iO, Mo0 3 inorganic composite materials and the thickness of the hole transport layer 10-100nm.
- the bottom electrode is an anode
- the anode is provided on the substrate to form an anode substrate
- the step of preparing an electronic functional layer on one side of the anode (the electronic functional layer is provided between the cathode and the quantum dot light-emitting layer).
- the electron functional layer includes at least one of an electron injection layer, an electron transport layer, and a hole blocking layer.
- the electron injection layer and the electron transport layer are used to reduce the difficulty of electron injection, and the hole blocking layer is used to block excess holes, so that the excess holes cannot reach the cathode to form a leakage current, thereby improving the quantum dot light emitting diode Current efficiency.
- the method when the anode substrate is formed on the substrate to form the anode substrate, after preparing the quantum dot light-emitting layer, and before preparing the cathode, the method further includes: a part of the quantum dot light-emitting layer facing away from the anode An electron transport layer is prepared on the side, and an electron injection layer is prepared on the side of the electron injection layer facing away from the anode.
- the material of the electron injection layer can be a conventional electron hole injection material, including but not limited to LiF and CsF, and the thickness of the electron transport layer is 10-100 nm.
- the material of the electron transport layer may be a conventional electron transport material, including but not limited to n-type zinc oxide, and the thickness of the electron transport layer is HMOOnm.
- the method further includes the step of preparing an electronic functional layer on the cathode surface of the substrate .
- the electron functional layer includes at least one of an electron injection layer, an electron transport layer, and a hole blocking layer.
- the method when the cathode is provided on the substrate to form the cathode substrate, before preparing the quantum dot light emitting layer, the method further includes: preparing an electron injection layer on the cathode surface of the substrate, and the electron injection layer is away from The step of preparing an electron transport layer on one side of the cathode.
- the bottom electrode is a cathode
- the cathode is provided on the substrate to form a cathode substrate
- a step of preparing a hole function layer on the side of the quantum dot light-emitting layer facing away from the cathode is further included.
- the hole functional layer includes at least one of a hole injection layer, a hole transport layer, and an electron blocking layer.
- the method when the cathode is provided on the substrate to form the cathode substrate, after preparing the quantum dot light-emitting layer and before preparing the anode, the method further includes: a side of the quantum dot light-emitting layer facing away from the cathode A hole transport layer is prepared, and a hole injection layer is prepared on the side of the hole transport layer facing away from the cathode.
- a method for manufacturing a quantum dot light emitting diode includes the following steps:
- a substrate provided with an anode is provided, a hole injection layer (PEDOT:PSS) is prepared on the anode, and a hole transport layer (TFB) is prepared on the hole transport layer on the side of the hole injection layer facing away from the anode
- the quantum dot light-emitting layer (CdSe/ZnS QDs) is prepared on the side facing away from the anode;
- the quantum dot light-emitting layer is immersed in a 1-chlorobutane content of 1-ppm 1-butanol solution, ultrasonic treatment at 20kHz power lOOmin;
- a method for preparing a quantum dot light emitting diode the difference from Example 1 is that: the quantum dot light emitting layer is immersed in 1-chlorobutane content is 100
- a method for preparing a quantum dot light emitting diode the difference from Example 1 is that: the quantum dot light emitting layer is immersed in 1-chlorobutane content is 100
- a method for preparing a quantum dot light-emitting diode is different from that in Example 1 in that: the quantum dot light-emitting layer is immersed in 1-butanol, and ultrasonically processed at a power of 20 kHz for 100 min.
- a method for preparing a quantum dot light-emitting diode is different from Example 1 in that: an electron transport layer (ZnO) is directly prepared on the surface of the prepared quantum dot light-emitting layer, and the electron transport layer faces away from the anode An electron injection layer (LiF) is prepared on the surface, and an aluminum cathode is prepared on the surface of the electron injection layer facing away from the anode. That is, without "dipping the quantum dot light-emitting layer into 1-chlorobutane content of 1
- a method for preparing a quantum dot light emitting diode includes the following steps: [0084] A substrate provided with an anode (ITO) is provided, a hole injection layer (PEDOT:PSS) is prepared on the anode, a hole transport layer (TFB) is prepared on the side of the hole injection layer facing away from the anode, and the hole The quantum dot light-emitting layer (CdSe/ZnS QDs) is prepared on the side of the transport layer facing away from the anode;
- the quantum dot light-emitting layer is immersed in the solvent system of Example 2 in Table 2 below, ultrasonic treatment at 20kHz power lOOmin;
- An electron transport layer (ZnO) is prepared on the surface of the quantum dot light-emitting layer after ultrasonic treatment facing away from the anode
- An electron injection layer (LiF) is prepared on the surface of the electron transport layer facing away from the anode, and an aluminum cathode is prepared on the surface of the electron injection layer facing away from the anode.
- a method for preparing a quantum dot light-emitting diode is different from Example 3 in that: the quantum dot light-emitting layer is immersed in the solvent system of Example 4 in Table 2 below, and is sonicated for 100 min at a power of 20 kHz.
- a method for preparing a quantum dot light-emitting diode which is different from Example 3 in that: the quantum dot light-emitting layer is immersed in the solvent system of Example 5 in Table 2 below, and is sonicated at a power of 20 kHz for 100 min.
- a method for preparing a quantum dot light-emitting diode is different from Example 3 in that: the quantum dot light-emitting layer is immersed in the solvent system of Example 6 in Table 2 below, and is sonicated for 100 min at a power of 20 kHz.
- Example 3 and Example 5 significantly improve the external quantum efficiency of quantum dot light-emitting diodes
- Example 4 improves the external quantum efficiency of the quantum dot light emitting diode, and at the same time improves the ripening time of the quantum dot light emitting diode to reach the highest external quantum efficiency.
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Abstract
一种量子点发光二极管的制备方法,包括以下步骤:提供基板,基板上表面设置有量子点发光层(S10);将基板浸入溶剂体系中进行超声处理,溶剂体系包括主体溶剂和溶于主体溶剂中的掺杂溶剂,掺杂溶剂的极性小于主体溶剂的极性,且主体溶剂为不溶解量子点的有机溶剂(S20)。
Description
量子点发光二极管的制备方法
[0001] 本申请要求于 2018年 12月 29日在中国专利局提交的、 申请号为 201811639647.3 、 申请名称为“量子点发光二极管的制备方法”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。
技术领域
[0002] 本申请涉及显示技术领域, 具体涉及一种量子点发光二极管的制备方法。
背景技术
[0003] 量子点 (quantum
dots) , 又称半导体纳米晶, 其三维尺寸均在纳米范围内 (l-100nm) , 是一种 介于体相材料和分子间的纳米颗粒论。 量子点具有量子产率高、 摩尔消光系数 大、 光稳定性好、 窄半峰宽、 宽激发光谱和发射光谱可控等优异的光学性能, 非常适合用作发光器件的发光材料。 近年来, 量子点荧光材料由于其光色纯度 高、 发光颜色可调、 使用寿命长等优点, 广泛被看好用于平板显示领域, 成为 极具潜力的下一代显示和固态照明光源。 量子点发光二极管 (Quantum Dot Light Emitting Diodes QLED)是基于量子点材料作为发光材料的发光器件, 由于其具有 波长可调、 发射光谱窄、 稳定性高、 电致发光量子产率高等优点, 成为下一代 显示技术的有力竞争者。
[0004] 然而, 目前的量子点发光二极管的制备方法, 仍有待改进。
发明概述
技术问题
[0005] 发明人发现, QLED器件制备过程中, 由于量子点本身不可避免地含有杂质, 最终得到的量子点发光层中会引入杂质, 影响量子点发光二极管的发光效率和 使用寿命。 溶液加工法是制备 QLED器件的常见方法, 特别是随着技术的发展, 采用喷墨打印技术制备量子点发光层变得常规。 但是, 采用溶液加工法如喷墨 打印技术制备量子点发光层时, 成膜过程中量子点墨水部分溶剂残留, 特别是 喷墨打印时, 为了减缓打印干燥速度, 量子点墨水中会添加高沸点溶剂, 高沸
点溶剂残留也会量子点发光二极管的发光效率和使用寿命。
[0006] 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的制备方法, 旨在 解决制备量子点发光二极管时, 由于量子点发光层中存在杂质 (量子点本身引 入的杂质和 /或溶剂残留形成的杂质) , 影响量子点发光二极管的发光效率和使 用寿命的问题。
问题的解决方案
技术解决方案
[0007] 为解决上述技术问题, 本申请实施例采用的技术方案是:
[0008] 第一方面, 提供了一种量子点发光二极管的制备方法, 包括以下步骤:
[0009] 提供基板, 所述基板上设置有量子点发光层;
[0010] 将所述基板浸入溶剂体系中进行超声处理, 所述溶剂体系包括主体溶剂和溶于 所述主体溶剂中的掺杂溶剂, 所述掺杂溶剂的极性小于所述主体溶剂的极性, 且所述主体溶剂为不溶解量子点的有机溶剂。
[0011] 在一个实施例中, 所述主体溶剂选自直链中的碳原子数目小于 20的醇类、 直链 中的碳原子数目小于 20的酯类、 直链中的碳原子数目小于 20的酮类中的一种或 两种以上的组合。
[0012] 在一个实施例中, 所述直链中的碳原子数目小于 20的醇类选自 1-丙醇、 1-丁醇 、 1-戊醇、 2 -戊醇、 1,5 -戊二醇和 2, 3 -丁二醇中的一种或多种;
[0013] 所述直链中的碳原子数目小于 20的酯类选自乙酸乙酯、 丙酸乙酯、 甲基丙烯酸 乙酯、 苯甲酸乙酯;
[0014] 所述直链中的碳原子数目小于 20的酮类选自丙酮、 丁酮、 3 -戊酮、 2 -甲基 4 -辛 酮。
[0015] 所述直链中的碳原子数目小于 10的醇类衍生物选自甲氧基乙醇、 乙氧基乙醇、 扁桃酸乙酯和中的一种或多种。
[0016] 在一个实施例中, 所述掺杂溶剂选自直链中的碳原子数目小于 10的不饱和脂肪 酸、 直链中的碳原子数小于 10的醇类衍生物、 直链中的碳原子数目小于 10的饱 和酸类、 直链中的碳原子数目小于 15的酸类衍生物和直链中的碳原子数目小于 2 0的卤代烃中的一种或两种以上的组合。
[0017] 在一个实施例中, 所述碳原子数目小于 10的不饱和脂肪酸选自丙烯酸、 丁烯酸 、 甲基丙烯酸和 3 -戊烯酸中的一种或多种;
[0018] 所述直链中的碳原子数小于 10的醇类衍生物选自甲氧基乙醇、 乙氧基乙醇、 2- 羟基 -2 -苯基乙酸乙酯和丙酮醇中的一种或多种;
[0019] 所述直链中的碳原子数目小于 10的饱和酸类选自乙酸、 丙酸、 丁酸和戊酸中的 一种或多种;
[0020] 所述直链中的碳原子数目小于 15的酸类衍生物选自全氟辛酸、 全氟癸基膦酸、 全氯癸基羧酸和全氟十二烷酸中的一种或多种;
[0021] 所述直链中的碳原子数目小于 20的卤代烃选自氟丙烷、 1-氯丁烷、 1-氯己烷和 3
-氟己烷中的一种或多种。
[0022] 在一个实施例中, 以所述溶剂体系的总重量为 100%计, 所述掺杂溶剂的重量 百分含量为 0.001-0.5%。
[0023] 将所述基板浸入溶剂体系中进行超声处理的步骤中, 所述超声处理的频率为 20 kHz- 10 9 kHz。
[0024] 在一个实施例中, 将所述基板浸入溶剂体系中进行超声处理的步骤中, 所述超 声处理的频率为 20kHz- 100 kHz。
[0025] 在一个实施例中, 将所述量子点发光层浸入溶剂体系中进行超声处理的步骤中 , 所述超声处理的功率密度为 0.3-200w/cm 2。
[0026] 在一个实施例中, 将所述量子点发光层浸入溶剂体系中进行超声处理的步骤中 , 所述超声处理的功率密度为 5-100w/cm 2。
[0027] 在一个实施例中, 将所述量子点发光层浸入溶剂体系中进行超声处理的步骤中 , 所述超声处理的时间为 20分钟 -48小时。
[0028] 在一个实施例中, 将所述量子点发光层浸入溶剂体系中进行超声处理的步骤中 , 所述超声处理的时间为 1小时 -10小时。
[0029] 在一个实施例中, 所述基板为设置有底电极的基板。
[0030] 在一个实施例中, 所述底电极为阳极, 在制备量子点发光层之前, 还包括在所 述基板的阳极表面制备空穴功能层的步骤; 所述空穴功能层包括空穴注入层、 空穴传输层、 电子阻挡层中的至少一层。
[0031] 在一个实施例中, 所述底电极为阳极, 在制备阴极之前, 还包括在所述量子点 发光层背离所述阳极的一侧制备电子功能层的步骤; 所述电子功能层包括电子 注入层、 电子传输层、 空穴阻挡层中的至少一层。
[0032] 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: 在制备完 量子点发光层后, 将所述量子点发光层浸入溶剂体系中进行超声处理。 其中, 所述溶剂体系包括主体溶剂和溶于所述主体溶剂中的掺杂溶剂, 所述掺杂溶剂 的极性小于所述主体溶剂的极性, 且所述主体溶剂为不溶解量子点的有机溶剂 。 通过超声处理, 所述溶剂体系渗透进入量子点发光层内部, 溶解量子点发光 层中的杂质 (量子点本身引入的杂质和 /或溶剂残留形成的杂质) , 从而去除残 留杂质对量子点发光二极管发光效率和使用寿命的影响, 最终提高量子点发光 二极管的发光效率和使用寿命。
发明的有益效果
对附图的简要说明
附图说明
[0033] 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。
[0034] 图 1是本申请一实施例提供的量子点发光二极管的制备方法的流程示意图。
发明实施例
本发明的实施方式
[0035] 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。
[0036] 需说明的是, 术语“第一”、 “第二”仅用于描述目的, 而不能理解为指示或暗示 相对重要性或者隐含指明所指示的技术特征的数量。 由此, 限定有“第一”、 “第 二”的特征可以明示或者隐含地包括一个或者更多个该特征。 在本申请的描述中
, “多个”的含义是两个或两个以上, 除非另有明确具体的限定。
[0037] 为了说明本申请所述的技术方案, 以下结合具体附图及实施例进行详细说明。
[0038] 如附图 1所示, 本申请一些实施例提供一种量子点发光二极管的制备方法, 包 括以下步骤:
[0039] S 10提供基板, 所述基板上设置有量子点发光层;
[0040] S20将所述基板浸入溶剂体系中进行超声处理, 所述溶剂体系包括主体溶剂和 溶于所述主体溶剂中的掺杂溶剂, 所述掺杂溶剂的极性小于所述主体溶剂的极 性, 且所述主体溶剂为不溶解量子点的有机溶剂。
[0041] 本申请实施例提供的量子点发光二极管的制备方法, 在制备完量子点发光层后 , 将所述量子点发光层浸入溶剂体系中进行超声处理。 其中, 所述溶剂体系包 括主体溶剂和溶于所述主体溶剂中的掺杂溶剂, 所述掺杂溶剂的极性小于所述 主体溶剂的极性, 且所述主体溶剂为不溶解量子点的有机溶剂。 通过超声处理 , 所述溶剂体系渗透进入量子点发光层内部, 溶解量子点发光层中的杂质 (量 子点本身引入的杂质和 /或溶剂残留形成的杂质) , 从而去除残留杂质对量子点 发光二极管发光效率和使用寿命的影响, 最终提高量子点发光二极管的发光效 率和使用寿命。
[0042] 具体的, 量子点发光二极管分正型结构和反型结构。 正型结构包括层叠设置的 阳极、 阴极和设置在阳极和阴极之间的量子点发光层, 正型结构的阳极设置在 衬底上, 在阳极和量子点发光层之间还可以设置空穴传输层、 空穴注入层和电 子阻挡层等空穴功能层, 在阴极和量子点发光层之间还可以设置电子传输层、 电子注入层和空穴阻挡层等电子功能层。 反型结构包括层叠设置的阳极、 阴极 和设置在阳极和阴极之间的量子点发光层, 反型结构的阴极设置在衬底上, 在 阳极和量子点发光层之间还可以设置空穴传输层、 空穴注入层和电子阻挡层等 空穴功能层, 在阴极和量子点发光层之间还可以设置电子传输层、 电子注入层 和空穴阻挡层等电子功能层。
[0043] 上述步骤 S10中, 对于正型器件而言, 设置在衬底上的底电极为阳极, 在本申 请的一种实施方式中, 所述基板可以为衬底上设置底电极和设置在底电极表面 的量子点发光层; 在本申请的又一种实施方式中, 所述基板可以包括衬底、 层
叠设置在衬底表面的底电极、 层叠设置在衬底表面的空穴传输层和设置在空穴 传输层表面的量子点发光层; 在本申请的又一种实施方式中, 所述基板可以包 括衬底、 层叠设置在衬底表面的底电极、 层叠设置在衬底表面的空穴注入层、 层叠设置在空穴注入层表面的空穴传输层和设置在空穴传输层表面的量子点发 光层; 在本申请的还一种实施方式中, 所述基板可以包括衬底、 层叠设置在衬 底表面的底电极、 层叠设置在衬底表面的空穴注入层、 层叠设置在空穴注入层 表面的空穴传输层、 层叠设置在空穴传输层表面的电子阻挡层和设置在电子阻 挡层表面的量子点发光层。
[0044] 对于反型器件而言, 设置在衬底上的底电极为阴极, 在本申请的一种实施方式 中, 所述基板可以为衬底上设置底电极; 在本申请的又一种实施方式中, 所述 基板可以包括衬底、 层叠设置在衬底表面的底电极、 层叠设置在衬底表面的电 子传输层和设置在电子传输层表面的量子点发光层; 在本申请的又一种实施方 式中, 所述基板可以包括衬底、 层叠设置在衬底表面的底电极、 层叠设置在衬 底表面的电子注入层、 层叠设置在电子注入层表面的空穴传输层和设置在电子 传输层表面的量子点发光层; 在本申请的还一种实施方式中, 所述基板可以包 括衬底、 层叠设置在衬底表面的底电极、 层叠设置在衬底表面的电子注入层、 层叠设置在电子注入层表面的电子传输层、 层叠设置在电子传输层表面的空穴 阻挡层和设置在空穴阻挡表面的量子点发光层。
[0045] 具体的, 上述步骤 S10中, 提供设置有底电极的基板, 即在基板上设置底电极 。 所述基板的选择没有严格限制, 可以采用硬质基板, 如玻璃基板; 也可以采 用柔性基板, 如聚酰亚胺基板、 聚降冰片烯基板, 但不限于此。 所述底电极为 与顶电极相对的电极, 所述底电极可为阴极, 也可为阳极。 具体的, 当所述底 电极为阳极时, 所述顶电极为阴极; 当所述底电极为阴极时, 所述顶电极为阳 极。 在一些实施例中, 所述阳极可以选用 ITO, 但不限于此。 在一些实施例中, 所述阴极可以选用金属电极, 包括但不限于银电极、 铝电极。 所述阴极的厚度 为 60- 120nm 本申请的一些实施例中为 100nm
[0046] 在所述底电极上制备量子点发光层的方法没有严格限定, 可以采用本领域常规 的方法制备量子点发光层。 在一些实施例中, 采用溶液加工法在所述底电极上
沉积量子点溶液, 制备量子点发光层。 通过溶液加工法制备的量子点发光层, 经过下述步骤在特定溶剂体系中进行超声处理, 可以同时将进一步将残留在量 子点发光层中的量子点杂质和溶剂杂质特别是残留的高沸点溶剂一并去除, 显 著提高量子点发光层的除杂效果。 本申请的一些实施例中, 采用喷墨打印方法 在所述底电极上沉积量子点墨水, 制备量子点发光层。 本申请实施例中, 所述 量子点发光层中的量子点为本领域常规的量子点。 在一些实施例中, 所述量子 点发光层的厚度为 30-50nm
[0047] 上述步骤 S20中, 将所述量子点发光层浸入溶剂体系中进行超声处理, 通过超 声处理, 在所述溶剂体系中微量存在的掺杂溶剂渗透进入量子点发光层内部, 溶解量子点发光层中的杂质 (量子点本身引入的杂质和 /或溶剂残留形成的杂质 ) , 从而去除残留杂质对量子点发光二极管发光效率和使用寿命的影响, 最终 提高量子点发光二极管的发光效率和使用寿命。
[0048] 本申请实施例中, 将所述量子点发光层浸入溶剂体系中进行超声处理, 对量子 点发光层进行超声处理除杂。 为了便于操作, 在一些实施例中, 将制备有量子 点发光层的整个基板置于溶剂体系中进行超声处理。
[0049] 本申请实施例中, 所述溶剂体系包括主体溶剂和溶于所述主体溶剂中的掺杂溶 齐 1J, 形成均一溶剂体系。 所述掺杂溶剂的极性小于所述主体溶剂的极性, 且所 述主体溶剂为不溶解量子点的有机溶剂。 由此形成的溶剂体系, 可以有效去除 量子点发光层中的残余杂质。 所述主体溶剂不溶解发光层, 掺杂溶剂可以溶解 量子点发光层, 主体溶剂中低浓度的掺杂溶剂可以在不破坏发光层纳米粒子成 膜的情况下溶解相对低分子量的杂质。
[0050] 在一些实施例中, 所述主体溶剂选自直链中的碳原子数目小于 20的醇类、 直链 中的碳原子数目小于 20的酯类、 直链中的碳原子数目小于 20的酮类、 直链中的 碳原子数目小于 10的醇类衍生物中的一种或两种以上的组合。
[0051] 在一些实施例中, 所述直链中的碳原子数目小于 20的醇类选自 1-丙醇、 1-丁醇
、 1-戊醇、 2 -戊醇、 1,5 -戊二醇和 2, 3 -丁二醇中的一种或多种。 在一些实施例中, 所述直链中的碳原子数目小于 20的酯类选自乙酸乙醋、 丙酸乙酯、 甲基丙烯酸 乙醋、 苯甲酸乙酯。 在一些实施例中, 所述直链中的碳原子数目小于 20的酮类
选自丙酮、 丁酮、 3 -戊酮、 2 -甲基 4 -辛酮。 在一些实施例中, 所述直链中的碳原 子数目小于 10的醇类衍生物选自甲氧基乙醇、 乙氧基乙醇、 2 -羟基 -2 -苯基乙酸 乙酯和丙酮醇中的一种或多种。 在一些实施例中, 所述掺杂溶剂选自直链中的 碳原子数目小于 10的不饱和脂肪酸、 直链中的碳原子数小于 10的醇类衍生物、 直链中的碳原子数目小于 10的饱和酸类、 直链中的碳原子数目小于 15的酸类衍 生物、 直链中的碳原子数目小于 20的卤代烃中的一种或两种以上的组合。
[0052] 本申请实施例中, 所述溶质的极性小于等于所述主体溶剂的极性, 甚至可以对 量子点有一定的溶解性, 但其与主体溶剂混合形成溶液后, 由于添加量极低, 不会造成量子点的溶解。
[0053] 在一些实施例中, 所述碳原子数目小于 10的不饱和脂肪酸选自丙烯酸、 丁烯酸 、 甲基丙烯酸、 3 -戊烯酸。 在一些实施例中, 所述直链中的碳原子数小于 10的醇 类衍生物选自甲氧基乙醇、 乙氧基乙醇、 苯氧基乙醇和 1-甲氧基 -1, 2 -丙二醇中 的一种或多种。 在一些实施例中, 所述直链中的碳原子数目小于 10的饱和酸类 选自乙酸、 丙酸、 丁酸和戊酸中的一种或多种。 在一些实施例中, 所述直链中 的碳原子数目小于 15的酸类衍生物选自全氟辛酸、 全氟癸基膦酸、 全氯癸基羧 酸和全氟十二烷酸中的一种或多种。 在一些实施例中, 所述直链中的碳原子数 目小于 20的卤代烃选自氟丙烷、 1-氯丁烷、 1-氯己烷和 3 -氟己烷中的一种或多种
[0054] 在上述实施例的基础上, 以所述溶剂体系的总重量为 100%计, 所述掺杂溶剂 的重量百分含量为 0-0.5%, 但不为 0。 若所述溶剂体系中极性偏低的掺杂溶剂的 含量过高, 则可能溶解量子点发光层中的部分量子点, 进而影响量子点发光层 的功能。 本申请的一些实施例中, 所述掺杂溶剂的重量百分含量为 0.001-0.05%
[0055] 在一些实施例中, 将所述量子点发光层浸入溶剂体系中进行超声处理的步骤中 , 所述超声处理的频率为 20 kHz-10 9kHz。 若所述超声处理的频率过高, 则会影 响已经形成的膜层包括量子点发光层的稳定性, 膜层容易从基板上脱离, 从而 破坏器件结构的稳定性。 若所述超声处理的频率过低, 清除量子点发光层中杂 质的效果不明显, 对量子点发光二极管使用寿命和发光效率的提高作用不显著
。 本申请的一些实施例中, 将所述量子点发光层浸入溶剂体系中进行超声处理 的步骤中, 所述超声处理的频率为 20 kHz- 100 kHz
[0056] 在一些实施例中, 将所述量子点发光层浸入溶剂体系中进行超声处理的步骤中 , 所述超声处理的功率密度为 0.3-200w/cm 2 若所述超声处理的功率密度过高, 则会影响已经形成的膜层包括量子点发光层的稳定性, 膜层容易从基板上脱离 , 从而破坏器件结构的稳定性。 若所述超声处理的功率密度过低, 清除量子点 发光层中杂质的效果不明显, 对量子点发光二极管使用寿命和发光效率的提高 作用不显著。 本申请的一些实施例中, 将所述量子点发光层浸入溶剂体系中进 行超声处理的步骤中, 所述超声处理的功率密度为 5-100w/cm
[0057] 在一些实施例中, 将所述量子点发光层浸入溶剂体系中进行超声处理的步骤中 , 所述超声处理的时间为 20分钟 -48小时。 若所述超声处理的时间过长, 长时间 的超声处理会影响已经形成的膜层包括量子点发光层的稳定性, 膜层容易从基 板上脱离, 从而破坏器件结构的稳定性。 若所述超声处理的时间过短, 不能达 到较好的量子点发光层中杂质的清除效果。 本申请的一些实施例中, 将所述量 子点发光层浸入溶剂体系中进行超声处理的步骤中, 所述超声处理的时间为 1小 时 -10小时。
[0058] 上述步骤 S20中, 在经超声处理后的量子点发光层背离所述底电极的表面制备 顶电极, 可以采用本领域常规方法制备获得。 值得注意的是, 本申请实施例所 述顶电极为与顶电极相对的电极, 具体可以为阳极, 也可以为阴极。
[0059] 由此, 本申请实施例制备得到具有基础结构的量子点发光二极管 (包括相对设 置的阴极和阳极, 以及设置在所述阴极和所述阳极之间的量子点发光层) 。 为 了获得更佳的器件性能, 可以在量子点发光二极管基础结构上引入不同作用的 功能层以平衡载流子。
[0060] 在一些实施例中, 当底电极为阳极, 即阳极设置所述基板上形成阳极基板时, 在制备量子点发光层之前, 还包括在所述基板的阳极表面制备空穴功能层 (所 述空穴功能层设置在所述阳极与所述量子点发光层之间) 的步骤。 所述空穴功 能层包括空穴注入层、 空穴传输层、 电子阻挡层中的至少一层。 其中, 所述空 穴注入层、 空穴传输层用于降低空穴注入难度, 所述电子阻挡层用于阻挡过量
的电子, 使过量的电子不能到达阳极形成漏电流, 从而提高量子点发光二极管 的电流效率。 本申请的一些实施例中, 当阳极设置所述基板上形成阳极基板时 , 在制备量子点发光层之前, 还包括: 在所述基板的阳极表面制备空穴注入层 , 在所述空穴注入层背离所述阳极的一侧制备空穴传输层的步骤。 其中, 所述 空穴注入层的材料可以采用常规的空穴注入材料, 包括但不限于 PEDOT:PSS。 所述空穴传输层的材料可以采用常规的空穴传输材料, 包括但不限于 NPB、 TFB 等有机材料, 以及 NiO、 Mo0 3等无机材料及其复合物, 所述空穴传输层的厚度 为 10-100nm。
[0061] 在一些实施例中, 当底电极为阳极, 即阳极设置所述基板上形成阳极基板时, 在制备量子点发光层之后, 在制备阴极之前, 还包括在所述量子点发光层背离 所述阳极的一侧制备电子功能层 (所述电子功能层设置在所述阴极与所述量子 点发光层之间) 的步骤。 所述电子功能层包括电子注入层、 电子传输层、 空穴 阻挡层中的至少一层。 其中, 所述电子注入层、 电子传输层用于降低电子注入 难度, 所述空穴阻挡层用于阻挡过量的空穴, 使过量的空穴不能到达阴极形成 漏电流, 从而提高量子点发光二极管的电流效率。 本申请的一些实施例中, 在 当阳极设置所述基板上形成阳极基板时, 在制备量子点发光层之后, 在制备阴 极之前, 还包括: 在所述量子点发光层背离所述阳极的一侧制备电子传输层, 在电子注入层背离所述阳极的一侧制备电子注入层。 其中, 所述电子注入层的 材料可以采用常规的电子穴注入材料, 包括但不限于 LiF、 CsF, 所述电子传输 层的厚度为 10- 100nm。 所述电子传输层的材料可以采用常规的电子传输材料, 包括但不限于 n型氧化锌, 所述电子传输层的厚度为 HMOOnm。
[0062] 在一些实施例中, 当底电极为阴极, 即阴极设置所述基板上形成阴极基板时, 在制备量子点发光层之前, 还包括在所述基板的阴极表面制备电子功能层的步 骤。 所述电子功能层包括电子注入层、 电子传输层、 空穴阻挡层中的至少一层 。 本申请的一些实施例中, 当阴极设置所述基板上形成阴极基板时, 在制备量 子点发光层之前, 还包括: 在所述基板的阴极表面制备电子注入层, 在所述电 子注入层背离所述阴极的一侧制备电子传输层的步骤。
[0063] 在一些实施例中, 当底电极为阴极, 即阴极设置所述基板上形成阴极基板时,
在制备量子点发光层之后, 在制备阳极之前, 还包括在所述量子点发光层背离 所述阴极的一侧制备空穴功能层的步骤。 所述空穴功能层包括空穴注入层、 空 穴传输层、 电子阻挡层中的至少一层。 本申请的一些实施例中, 当阴极设置所 述基板上形成阴极基板时, 在制备量子点发光层之后, 在制备阳极之前, 还包 括: 在所述量子点发光层背离所述阴极的一侧制备空穴传输层, 在空穴传输层 背离所述阴极的一侧制备空穴注入层。
[0064] 上述电子功能层、 空穴功能层的制备, 参考本领域常规方法制备。 本申请的一 些实施例中, 采用溶液加工法在制备获得。
[0065] 下面结合具体实施例进行说明。
[0066] 实施例 1
[0067] 一种量子点发光二极管的制备方法, 包括以下步骤:
[0068] 提供设置有阳极 (ITO) 的基板, 在所述阳极上制备空穴注入层 (PEDOT:PSS ) 在空穴注入层背离阳极一侧制备空穴传输层 (TFB) 在空穴传输层背离阳 极一侧制备量子点发光层 (CdSe/ZnS QDs) ;
[0069] 将所述量子点发光层浸入 1-氯丁烷含量为 1 ppm的 1-丁醇溶液中, 20kHz的功率 下超声处理 lOOmin;
[0070] 在经超声处理后的量子点发光层背离所述阳极的表面制备电子传输层 (ZnO) 在电子传输层背离所述阳极的表面制备电子注入层 (LiF) 电子注入层背离 所述阳极的表面制备铝阴极。
[0071] 实施例 2
[0072] 一种量子点发光二极管的制备方法, 与实施例 1的不同之处在于: 将所述量子 点发光层浸入 1-氯丁烷含量为 100
ppm的 1-丁醇溶液中, 20kHz的功率下超声处理 lOOmin。
[0073] 对比例 1
[0074] 一种量子点发光二极管的制备方法, 与实施例 1的不同之处在于: 将所述量子 点发光层浸入 1-氯丁烷含量为 100
ppm的 1-丁醇溶液中, 20kHz的功率下超声处理 300min。
[0075] 对比例 2
[0076] 一种量子点发光二极管的制备方法, 与实施例 1的不同之处在于: 将所述量子 点发光层浸入 1-丁醇中, 20kHz的功率下超声处理 lOOmin。
[0077] 对比例 3
[0078] 一种量子点发光二极管的制备方法, 与实施例 1的不同之处在于: 直接在制备 得到的量子点发光层表面制备电子传输层 (ZnO) , 在电子传输层背离所述阳极 的表面制备电子注入层 (LiF) , 电子注入层背离所述阳极的表面制备铝阴极。 即不进行“将所述量子点发光层浸入 1-氯丁烷含量为 1
ppm的 1-丁醇溶液中, 20kHz的功率下超声处理 lOOmin”的步骤。
[0079] 分别检测实施例 1-2、 对比例 1-3制备的量子点发光二极管通电熟化后的外量子 效率变化(%), 结果如下表 i所示。
[0080] 表 1
[]
[] [表 1]
[0081] 由上表 1可见, 在 1-氯丁烷的 1-丁醇溶液质量比在一定范围内时, 经过超声处理 的器件外量子效率可以有效提高量子点发光二极管的外量子效率。 特别的, 当 1- 氯丁烷在 1-丁醇中的质量比为 lOOppm时, 量子点发光二极管的外量子效率最高 值提高了 37.3%。
[0082] 实施例 3
[0083] 一种量子点发光二极管的制备方法, 包括以下步骤:
[0084] 提供设置有阳极 (ITO) 的基板, 在所述阳极上制备空穴注入层 (PEDOT:PSS ) , 在空穴注入层背离阳极一侧制备空穴传输层 (TFB) , 在空穴传输层背离阳 极一侧制备量子点发光层 (CdSe/ZnS QDs) ;
[0085] 将所述量子点发光层浸入下表 2实施例 3的溶剂体系中, 20kHz的功率下超声处 理 lOOmin;
[0086] 在经超声处理后的量子点发光层背离所述阳极的表面制备电子传输层 (ZnO)
, 在电子传输层背离所述阳极的表面制备电子注入层 (LiF) , 电子注入层背离 所述阳极的表面制备铝阴极。
[0087] 实施例 4
[0088] 一种量子点发光二极管的制备方法, 与实施例 3的不同之处在于: 将所述量子 点发光层浸入下表 2实施例 4的溶剂体系中, 20kHz的功率下超声处理 lOOmin。
[0089] 实施例 5
[0090] 一种量子点发光二极管的制备方法, 与实施例 3的不同之处在于: 将所述量子 点发光层浸入下表 2实施例 5的溶剂体系中, 20kHz的功率下超声处理 lOOmin。
[0091] 实施例 6
[0092] 一种量子点发光二极管的制备方法, 与实施例 3的不同之处在于: 将所述量子 点发光层浸入下表 2实施例 6的溶剂体系中, 20kHz的功率下超声处理 lOOmin。
[0093] 分别检测实施例 4-6、 对比例 3制备的量子点发光二极管通电熟化后的外量子效 率变化(%), 结果如下表 2所不。
[0094] 表 2
[]
[]
[表 2]
[0095] 由表 2可见, 不同组合的溶剂体系对量子点发光二极管的外量子效率都有不同 程度的影响, 具体的, 实施例 3、 实施例 5显著提高了量子点发光二极管的外量 子效率; 实施例 4提高了量子点发光二极管的外量子效率, 同时提高了量子点发 光二极管达到最高外量子效率的熟化时间。
[0096] 以上仅为本申请的可选实施例而已, 并不用于限制本申请。 对于本领域的技术 人员来说, 本申请可以有各种更改和变化。 凡在本申请的精神和原则之内, 所 作的任何修改、 等同替换、 改进等, 均应包含在本申请的权利要求范围之内。
Claims
[权利要求 1] 量子点发光二极管的制备方法, 其特征在于, 包括以下步骤:
提供基板, 所述基板上表面设置有量子点发光层; 将所述基板浸入溶剂体系中进行超声处理, 所述溶剂体系包括主体溶 剂和溶于所述主体溶剂中的掺杂溶剂, 所述掺杂溶剂的极性小于所述 主体溶剂的极性, 且所述主体溶剂为不溶解量子点的有机溶剂。
[权利要求 2] 根据权利要求 1所述的量子点发光二极管的制备方法, 其特征在于, 所述主体溶剂选自直链中的碳原子数目小于 20的醇类、 直链中的碳原 子数目小于 20的酯类、 直链中的碳原子数目小于 20的酮类中的一种或 两种以上的组合。
[权利要求 3] 根据权利要求 2所述的量子点发光二极管的制备方法, 其特征在于, 所述直链中的碳原子数目小于 20的醇类选自 1-丙醇、 1-丁醇、 1-戊醇 、 2 -戊醇、 1,5 -戊二醇和 2, 3 -丁二醇中的一种或多种。
[权利要求 4] 根据权利要求 2所述的量子点发光二极管的制备方法, 其特征在于, 所述直链中的碳原子数目小于 20的酯类选自乙酸乙醋、 丙酸乙酯、 甲 基丙烯酸乙酯、 苯甲酸乙酯。
[权利要求 5] 根据权利要求 2所述的量子点发光二极管的制备方法, 其特征在于, 所述直链中的碳原子数目小于 20的酮类选自丙酮、 丁酮、 3 -戊酮、 2- 甲基 4 -辛酮。
[权利要求 6] 根据权利要求 2所述的量子点发光二极管的制备方法, 其特征在于, 所述直链中的碳原子数目小于 10的醇类衍生物选自甲氧基乙醇、 乙氧 基乙醇、 扁桃酸乙酯和中的一种或多种。
[权利要求 7] 根据权利要求 1所述的量子点发光二极管的制备方法, 其特征在于, 所述掺杂溶剂选自直链中的碳原子数目小于 10的不饱和脂肪酸、 直链 中的碳原子数小于 10的醇类衍生物、 直链中的碳原子数目小于 10的饱 和酸类、 直链中的碳原子数目小于 15的酸类衍生物和直链中的碳原子 数目小于 20的卤代烃中的一种或两种以上的组合。
[权利要求 8] 根据权利要求 7所述的量子点发光二极管的制备方法, 其特征在于,
所述碳原子数目小于 10的不饱和脂肪酸选自丙烯酸、 丁烯酸、 甲基丙 烯酸和 3 -戊烯酸中的一种或多种。
[权利要求 9] 根据权利要求 7所述的量子点发光二极管的制备方法, 其特征在于, 所述直链中的碳原子数小于 10的醇类衍生物选自甲氧基乙醇、 乙氧基 乙醇、 2 -轻基 -2 -苯基乙酸乙酯和丙酮醇中的一种或多种。
[权利要求 10] 根据权利要求 7所述的量子点发光二极管的制备方法, 其特征在于, 所述直链中的碳原子数目小于 10的饱和酸类选自乙酸、 丙酸、 丁酸和 戊酸中的一种或多种。
[权利要求 11] 根据权利要求 7所述的量子点发光二极管的制备方法, 其特征在于, 所述直链中的碳原子数目小于 15的酸类衍生物选自全氟辛酸、 全氟癸 基膦酸、 全氯癸基羧酸和全氟十二烷酸中的一种或多种。
[权利要求 12] 根据权利要求 7所述的量子点发光二极管的制备方法, 其特征在于, 所述直链中的碳原子数目小于 20的卤代烃选自氟丙烷、 1-氯丁烷、 1- 氯己烷和 3 -氟己烷中的一种或多种。
[权利要求 13] 根据权利要求 1至 12任一项所述的量子点发光二极管的制备方法, 其 特征在于, 以所述溶剂体系的总重量为 100%计, 所述掺杂溶剂的重 量百分含量为 0.001-0.5%。
[权利要求 14] 根据权利要求 1至 12任一项所述的量子点发光二极管的制备方法, 其 特征在于, 将所述基板浸入溶剂体系中进行超声处理的步骤中, 所述 超声处理的频率为 20 kHz- 10 9 kHz。
[权利要求 15] 根据权利要求 14所述的量子点发光二极管的制备方法, 其特征在于, 将所述基板浸入溶剂体系中进行超声处理的步骤中, 所述超声处理的 频率为 20kHz- 100 kHz。
[权利要求 16] 根据权利要求 1至 12任一项所述的量子点发光二极管的制备方法, 其 特征在于, 将所述量子点发光层浸入溶剂体系中进行超声处理的步骤 中, 所述超声处理的功率密度为 0.3-200w/cm 2。
[权利要求 17] 根据权利要求 16所述的量子点发光二极管的制备方法, 其特征在于, 将所述量子点发光层浸入溶剂体系中进行超声处理的步骤中, 所述超
声处理的功率密度为 5-100w/cm 2。
[权利要求 18] 根据权利要求 1至 12任一项所述的量子点发光二极管的制备方法, 其 特征在于, 将所述量子点发光层浸入溶剂体系中进行超声处理的步骤 中, 所述超声处理的时间为 20分钟 -48小时。
[权利要求 19] 根据权利要求 18所述的量子点发光二极管的制备方法, 其特征在于, 将所述量子点发光层浸入溶剂体系中进行超声处理的步骤中, 所述超 声处理的时间为 1小时 - 10小时。
[权利要求 20] 根据权利要求 1至 12任一项所述的量子点发光二极管的制备方法, 其 特征在于, 所述基板为设置有底电极的基板。
[权利要求 21] 根据权利要求 20所述的量子点发光二极管的制备方法, 其特征在于, 所述底电极为阳极, 在制备量子点发光层之前, 还包括在所述基板的 阳极表面制备空穴功能层的步骤; 所述空穴功能层包括空穴注入层、 空穴传输层、 电子阻挡层中的至少一层。
[权利要求 22] 根据权利要求 20所述的量子点发光二极管的制备方法, 其特征在于, 所述底电极为阳极, 在制备阴极之前, 还包括在所述量子点发光层背 离所述阳极的一侧制备电子功能层的步骤; 所述电子功能层包括电子 注入层、 电子传输层、 空穴阻挡层中的至少一层。
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| CN111384308A (zh) | 2020-07-07 |
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