WO2021136367A1 - 量子点发光二极管及其制备方法 - Google Patents

量子点发光二极管及其制备方法 Download PDF

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Publication number
WO2021136367A1
WO2021136367A1 PCT/CN2020/141366 CN2020141366W WO2021136367A1 WO 2021136367 A1 WO2021136367 A1 WO 2021136367A1 CN 2020141366 W CN2020141366 W CN 2020141366W WO 2021136367 A1 WO2021136367 A1 WO 2021136367A1
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quantum dot
emitting diode
bottom electrode
nano
dot light
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PCT/CN2020/141366
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English (en)
French (fr)
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雷卉
刘文勇
杨一行
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Tcl科技集团股份有限公司
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Publication of WO2021136367A1 publication Critical patent/WO2021136367A1/zh

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    • 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
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • 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

Definitions

  • This application relates to the field of display technology, in particular to a quantum dot light-emitting diode and a preparation method thereof.
  • Quantum dot electroluminescent devices have shown great application potential due to their advantages of low starting voltage, narrow emission peak, and adjustable emission wavelength.
  • the QLED adopts a sandwich structure, including an anode and a cathode, and a quantum dot light-emitting layer arranged between the anode and the cathode.
  • QLEDs usually include an anode, a hole injection layer, a hole transport layer, a quantum dot light-emitting layer, an electron transport layer, and a cathode.
  • the preparation of the quantum dot light-emitting layer is particularly important.
  • a typical quantum dot structure consists of a core, a shell (single layer or multiple layers), and chain ligands. The electrons and holes finally recombine in the quantum dot core to emit light. Since quantum dots are prone to agglomeration, long-chain ligands are currently used to effectively prevent quantum dots from aggregation and sedimentation. But also because of the longer chain length of long-chain ligands, the charge injection and transport capabilities of quantum dots still need to be improved. The short-chain ligand can effectively improve the electron and hole injection and transport capabilities, but it is easy to cause the quantum dots to aggregate and settle.
  • One of the objectives of the embodiments of the present application is to provide a quantum dot light-emitting diode and a preparation method thereof, aiming to solve the problem that it is difficult for quantum dots to have both good dispersion and charge injection and transport capabilities.
  • a method for manufacturing a quantum dot light-emitting diode which includes the following steps:
  • the diameter of the quantum dot is marked as d
  • the distance between adjacent first nanopillars is marked as l 1
  • the height of the first nanopillar is marked as h
  • the maximum radial dimension of the first nanopillar is marked as s 1
  • the radius of the common circumscribed circle of the three adjacent first nanopillars is marked as r 1 .
  • a quantum dot light-emitting diode comprising an anode and a cathode arranged oppositely, and a quantum dot film arranged between the anode and the cathode, wherein the surface of the anode or the cathode is arranged
  • the first nano-pillar structure, and the surface of the quantum dot film in contact with the first nano-pillar structure is complementary to the first nano-pillar structure, and the other surface of the quantum dot film is a flat surface; wherein the quantum dot film is a flat surface;
  • the diameter of the dot is marked as d, the distance between adjacent first nanopillars is marked as l 1 , the height of the first nanopillar is marked as h, the maximum radial dimension of the first nanopillar is marked as s 1 , and the adjacent
  • the radius of the common circumscribed circle of the three first nano-pillars is marked as r 1 .
  • the method for preparing a quantum dot light-emitting diode firstly forms a first nano-column structure on the surface of the bottom electrode of the bottom electrode substrate; then combines quantum dots containing an initial ligand on the surface of the first nano-column structure, and combines the initial The quantum dots of the ligand enter the pores of the first nanopillar structure.
  • the quantum dots can be arranged in the form of single particles, which can reduce the aggregation of quantum dots.
  • Sedimentation improves the dispersion and stability of quantum dots; finally, the target ligand is used to exchange ligands on the quantum dots with the initial ligands on the surface, and the target ligands that can improve the charge injection and transport capabilities are combined on the surface of the quantum dots. Finally, a quantum dot film with good dispersibility and charge injection and transport capabilities can be obtained. In addition, the method is simple to operate and low in cost.
  • the quantum dots are arranged in the nano-column structure of the substrate, so that the spacing width between the nano-column structures and the size of the nano-columns can be controlled to at least make the quantum dots arranged in the form of single particles.
  • the aggregation and sedimentation between quantum dots can be avoided, and the dispersion performance and stability of the quantum dots are improved.
  • monodisperse quantum dots increase the flexibility of surface ligand selection, making it easy to combine short-chain ligands on the surface of quantum dots on the premise of avoiding agglomeration, thereby improving hole and electron injection and transport capabilities , Improve the performance of QLED devices.
  • FIG. 1 is a flow chart of the manufacturing process of a quantum dot light-emitting diode provided by an embodiment of the present application
  • Example 2 is a cross-sectional view of a single-layer polystyrene nanosphere film prepared on the surface of an ITO layer provided in Example 1 of the present application;
  • FIG 3 is a plan view of a single-layer polystyrene nanosphere film prepared on the surface of the ITO layer provided in Example 1 of the present application;
  • Example 4 is a cross-sectional view of a polystyrene nanosphere mask formed on the surface of the ITO layer provided in Example 1 of the present application;
  • FIG. 5 is a schematic diagram of using an ITO etching solution to etch ITO covered with a polystyrene nanosphere mask in Example 1 of the present application, and forming a first nanopillar structure on the surface of the ITO;
  • Example 6 is a schematic diagram of forming a first nano-pillar structure on the surface of ITO after etching provided in Example 1 of the present application;
  • FIG. 7 is a structural diagram after preparing a hole injection layer and a hole transport layer on an ITO nanopillar provided in Example 1 of the present application;
  • Example 8 is a schematic diagram of the structure of a quantum dot with oleic acid as the deposited surface ligand provided in Example 1 of the present application;
  • Example 9 is a schematic diagram of the quantum dot provided in Example 1 of the present application after ligand exchange;
  • FIG. 10 is a schematic diagram of the ligand exchange reaction between ethyl mercaptan ligand and oleic acid provided in Example 1 of the present application;
  • FIG. 11 is a schematic diagram of the structure of a quantum dot light-emitting diode prepared in Example 1 of the present application.
  • first and second are only used for description purposes, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of indicated technical features. Thus, the features defined with “first” and “second” may explicitly or implicitly include one or more of these features. In the description of the present application, “multiple” means two or more than two, unless otherwise specifically defined.
  • the weight of the relevant components mentioned in the description of the embodiments of this application can not only refer to the specific content of each component, but also can indicate the proportion of weight between the components. Therefore, as long as it is in accordance with the relevant group of the description of the embodiments of this application, Enlargement or reduction of the content of the fennel in proportion is within the scope disclosed in the specification of the embodiments of the present application.
  • the weight described in the specification of the embodiments of the present application may be a mass unit well-known in the chemical industry, such as ⁇ g, mg, g, and kg.
  • the first aspect of the embodiments of the present application provides a method for manufacturing a quantum dot light-emitting diode, which includes the following steps:
  • a bottom electrode substrate is provided, and a first nano-pillar structure is formed on the bottom electrode surface of the bottom electrode substrate;
  • S02. Combine quantum dots containing initial ligands on the surface of the first nanocolumn structure to provide target ligands for exchange with the initial ligands on the surface of the quantum dots to prepare a quantum dot film bound with the target ligands.
  • a first nano-column structure is formed on the bottom electrode surface of the bottom electrode substrate; then a quantum dot containing an initial ligand is combined on the surface of the first nano-column structure, and the initial The quantum dots of the ligand enter the pores of the first nanopillar structure.
  • the quantum dots can be arranged in the form of single particles, which can reduce the aggregation of quantum dots.
  • Sedimentation improves the dispersion and stability of quantum dots; finally, the target ligand is used to exchange ligands on the quantum dots with the initial ligands on the surface, and the target ligands that can improve the charge injection and transport capabilities are combined on the surface of the quantum dots. Finally, a quantum dot film with good dispersibility and charge injection and transport capabilities can be obtained. In addition, the method is simple to operate and low in cost.
  • a bottom electrode substrate is provided.
  • the bottom electrode substrate includes a substrate and a bottom electrode provided on the substrate.
  • the substrate may be a rigid substrate or a flexible substrate.
  • the bottom electrode can be an anode or a cathode.
  • the bottom electrode is an ITO electrode.
  • the method for preparing the bottom electrode on the substrate is not strictly limited. Conventional sputtering, evaporation and other processes can be used to prepare the bottom electrode on the sink.
  • the method for forming the first nano-pillar structure on the bottom electrode surface of the bottom electrode substrate is: etching the bottom electrode on the bottom electrode substrate. After etching the bottom electrode on the bottom electrode substrate, the surface of the bottom electrode away from the substrate is protruded to form a number of nano-columns to obtain the first nano-column structure.
  • the step of etching the bottom electrode on the bottom electrode substrate includes:
  • the bottom electrode is etched, and the polystyrene nanospheres are removed to prepare a bottom electrode with a first nanocolumn structure.
  • a single-layer polystyrene nanosphere film is prepared on the bottom electrode of the bottom electrode substrate, and the single-layer polystyrene nanosphere film is used to make an etching template for the first nanopillar structure.
  • a single-layer polystyrene nanosphere film is prepared on the bottom electrode of the bottom electrode substrate by a solution processing method, including but not limited to a self-organization method and a spin coating method.
  • the method includes the step of preparing a polystyrene nanosphere suspension.
  • the configuration method of the polystyrene nanosphere suspension is: dispersing the polystyrene nanospheres in a solvent to obtain the polystyrene nanosphere suspension.
  • a suspension of polystyrene nanospheres with a mass percentage of polystyrene nanospheres of 0.1%-10% is configured, and the solvent in the suspension is a mixed solvent of deionized water and ethanol .
  • the content of polystyrene nanospheres is appropriate, and the mixed solvent of deionized water and ethanol is used as the dispersion system, and the obtained polystyrene nanosphere suspension has self-assembly characteristics, which is beneficial to polystyrene.
  • a single-layer polystyrene nanosphere film is formed on the surface of the bottom electrode.
  • single-size polystyrene nanospheres are used to prepare a single-layer polystyrene nanosphere film. At this time, a hexagonal close-packed, periodic and orderly arranged single-layer polystyrene nanosphere film is formed on the surface of the bottom electrode.
  • polystyrene nanospheres of different sizes are used to prepare a single-layer polystyrene nanosphere film, and a single-layer disordered polystyrene nanosphere film is formed on the surface of the bottom electrode.
  • the diameter of the polystyrene nanosphere is 10 nm to 1000 nm.
  • the size of the polystyrene nanospheres and the distance between adjacent polystyrene nanospheres can be adjusted by subsequent RIE etching treatment, so as to use the etched polystyrene nanospheres.
  • the ball is used as a template to obtain a suitable size of the first nano-column structure and the distance between adjacent first nano-columns.
  • the quantum dots are directly deposited on the gap between the first nanopillars and the surface of the first nanopillar.
  • the diameter of the polystyrene nanosphere is selected Usually less than 100nm.
  • the first functional layer is deposited on the surface of the bottom electrode and the quantum dot light-emitting layer is arranged on the first functional layer, at least one film layer is formed on the first nanopillar structure of the bottom electrode. Therefore, as the thickness of the film increases As it increases, the gap between the nanopillars becomes smaller, and the maximum radial dimension of the nanopillars gradually increases.
  • the diameter of the selected polystyrene nanospheres is usually greater than 60nm.
  • the polystyrene nanospheres in the single-layer polystyrene nanosphere film are subjected to RIE etching treatment to reduce the size of the polystyrene nanospheres and increase the distance between adjacent polystyrene nanospheres .
  • the etching parameters can be based on the initial size of the polystyrene nanospheres and the etched size. The expected size is adjusted.
  • the etching atmosphere can be a mixed gas of one or more of oxygen and carbon tetrafluoride
  • the flow rate can be 1 sccm ⁇ 200 sccm
  • the etching power can be 0.1W ⁇ 100W
  • the etching time It can be 1s ⁇ 500s.
  • the etching of the polystyrene nanospheres is adjusted in combination with the distance between adjacent first nanopillar structures in the first nanopillar structure below and the maximum radial dimension of the first nanopillar structure.
  • the bottom electrode is etched using the etched polystyrene nanospheres as a mask.
  • an etching solution that can react with the bottom electrode but has no corrosive activity or weak corrosive effect on the polystyrene nanospheres is used to etch the bottom electrode covered with the polystyrene nanospheres.
  • an inorganic acid etching solution is used to perform the etching treatment on the bottom electrode. Inorganic acid etching solution has no corrosive activity or weak corrosive effect on polystyrene nanospheres.
  • the inorganic acid etching solution covers the polystyrene
  • the bottom electrode area of the vinyl nanospheres has no etching effect, but the area that is not covered by the polystyrene nanospheres is reactively etched, and finally a depression is formed in the bottom electrode area that is not covered by the polystyrene nanospheres.
  • the polystyrene is covered.
  • the area of ethylene nanospheres forms nanopillars.
  • the inorganic acid etching solution is a mixed solution formed by one or more of hydrofluoric acid, nitric acid, phosphoric acid, sulfuric acid, hydrochloric acid, and acetic acid.
  • the mass concentration of the inorganic acid etching solution is adjusted to 0.1% ⁇ 20%, so as to reasonably control the etching speed to prevent the over-etching of the bottom electrode due to the excessively violent etching reaction and the failure to form the first electrode.
  • a nano-pillar structure the etching temperature and the etching time can be adjusted according to the selection of the etching solution. In some embodiments, the etching temperature is 20° C. to 100° C., and the etching time is 1 s to 5 h.
  • the bottom electrode when the bottom electrode is etched with an inorganic acid etching solution, at least one of iron salt, ferrous salt and acetone is added to the inorganic acid etching solution.
  • the wall surface of the depression formed by the etching solution is smoother, that is, the wall surface of the nano-pillar is smoother and smoother, which is beneficial to improve the uniform filling of the quantum dots Sex.
  • the residual polystyrene nanospheres are removed by a solution method, burning, etc., so as to obtain the first nanopillars with the same period and size as the PS nanosphere mask.
  • the step of etching the bottom electrode on the bottom electrode substrate includes:
  • E21 Provide an imprint template with a micro-nano structure complementary to the first nano-pillar structure
  • E22 Form a photoresist on the bottom electrode, and use an imprint template to imprint the photoresist to obtain a photoresist layer with a micro-nano structure formed on the surface;
  • E23 Etch the photoresist layer with the nano-pillar structure, transfer the nano-pillar structure to the surface of the bottom electrode, and prepare the bottom electrode with the first nano-pillar structure.
  • the imprinting template is a micro-nano structure complementary to the first nanopillar structure, and the micro-nano structure is used as the imprinting template and transferred to the film to be processed through the imprinting process.
  • the substrate of the imprint template needs to have a relatively large hardness, so that the imprint can be performed and the shape of the micro-nano structure can be maintained during the imprinting process.
  • the imprinting mold is a quartz imprinting mold with a micro-nano structure.
  • the quartz imprint mold can be prepared by the following method: select quartz glass with good transparency to ultraviolet light as the base material of the imprint template; use alcohol, acetone, and alcohol solution to sequentially process the quartz substrate Ultrasonic cleaning, drying for use; deposit a layer of 5nm ⁇ 50nm metal Cr film on the surface of quartz glass, deposit electron beam photoresist layer on the metal Cr film; use electron beam direct writing technology for photoresist direct writing Expose and develop to form a micro-nano structure on the photoresist layer; use the photoresist with a micro-nano structure as a barrier layer to dry etch the metal Cr film; then use the metal Cr film as a barrier layer to treat the quartz substrate Dry etching is performed to obtain a quartz imprint template of the photonic crystal microstructure on the quartz substrate.
  • the photoresist is formed on the bottom electrode, and the manner of forming the photoresist layer on the bottom electrode is not strictly limited, and can be prepared by a conventional method.
  • the imprinting template is used to imprint the photoresist to obtain a photoresist layer with a micro-nano structure formed on the surface.
  • the above-mentioned quartz imprint mold is used to imprint the photoresist.
  • a quartz imprint mold is used to set the template thickness, substrate thickness, photoresist thickness, vacuum pressure, exposure time and other parameters for imprint processing; after the quartz imprint template is pressed into the photoresist, UV curing is performed. Then, the demolding process is performed to realize the pattern transfer of the nanoimprint mold.
  • the photoresist layer with the micro-nano structure is etched, and the microstructure pattern on the photoresist is transferred to the surface of the bottom electrode, thereby obtaining the first nano-pillar structure.
  • the RIE etching method is used to transfer the microstructure pattern on the photoresist to the surface of the bottom electrode, thereby obtaining the first nanopillar structure.
  • the imprinting template is used to imprint the photoresist to form a nano-column structure on the surface of the photoresist layer.
  • the above-mentioned imprinting template is used to set the thickness of the template
  • gaps between the first nanopillars obtained by etching there are gaps between the first nanopillars obtained by etching, and the gaps are used to directly accommodate the quantum dots with the initial ligands on the surface; or after the first functional layer is deposited, the accommodating surface is bonded with the initial Ligand quantum dots.
  • the following marks are made: mark the diameter of the quantum dot as d, mark the distance between adjacent first nanopillars as l 1 , mark the height of the first nanopillar as h, and mark the height of the first nanopillar as h.
  • the maximum radial dimension of one nano-pillar is marked as s 1
  • the radius of the common circumscribed circle of three adjacent first nano-pillars is marked as r 1 .
  • the maximum radial dimension of the first nano-pillar refers to the maximum width of the first nano-pillar in the direction perpendicular to the axial direction
  • the distance between adjacent first nano-pillars is between two adjacent first nano-pillars. The minimum distance between.
  • the relationship among d, l 1 , s 1 , h, r 1 and the optional situations thereof vary according to the difference in the deposition position of the quantum dots.
  • the quantum dots are deposited directly on the first nano-pillar structure of the bottom electrode, that is, the gaps between the first nano-pillar structures are directly used to accommodate the quantum dots.
  • this application implements In the example, d and l 1 satisfy: d ⁇ l 1 ⁇ 2d; or d, l 1 satisfy: l 1 ⁇ d, and r 1 and d satisfy: d ⁇ 2r 1 ⁇ 2d.
  • the gap between the first nanopillar structure can and can only hold one quantum dot in the radial plane, so that the quantum dots can be arranged in an orderly manner, even if the short-chain ligands are combined after the ligand exchange. There will be no reunion.
  • l 1 is approximately the diameter of a quantum dot, that is, l 1 is 2 nm to 20 nm.
  • h and d satisfy: d ⁇ h ⁇ 5d. That is, the deposition thickness of the quantum dots in the gaps between the first nano-pillar structures is 1 to 5 quantum dots. If the thickness of the quantum dot is too thick, a higher voltage will be generated, which will affect the light-emitting performance of the quantum dot.
  • the relationship between h and d satisfies: 3d ⁇ h ⁇ 4d. That is, the deposition thickness of the quantum dots in the gaps between the first nano-pillar structures is 3 to 4 quantum dots.
  • s 1 and d satisfy: s 1 ⁇ d, that is, the largest radial dimension of the first nano-pillar in the first nano-pillar structure is less than or equal to the diameter of the quantum dot, so that the first nano-pillar structure
  • the upper surface of the nanopillar can accommodate at most one quantum dot to avoid agglomeration of the quantum dots during the ligand exchange process and after the ligand exchange.
  • the quantum dots containing the initial ligands are combined on the surface of the first nanopillar structure, and the quantum dots fall into the gaps between the gaps between the first nanopillars, and are arranged in an orderly manner.
  • the method for manufacturing a quantum dot light-emitting diode further includes: preparing a first functional layer on the surface of the first nanopillar structure, and the first functional layer has a second nanopillar corresponding to the first nanopillar structure Structure; Combine quantum dots containing initial ligands on the surface of the second nanocolumn structure to provide target ligands to exchange with the initial ligands on the surface of the quantum dots to prepare a quantum dot film bound with the target ligands; among them, adjacent
  • the distance between the second nanopillars is marked as l 2
  • the maximum radial dimension of the second nanopillar is marked as s 2
  • the radius of the common circumscribed circle of three adjacent second nanopillars is marked as r 2 .
  • the first functional layer is one of the electronic functional layer and the hole functional layer according to the type of the bottom electrode: when the bottom electrode is an anode, the first functional layer is a hole functional layer; when the bottom electrode is a cathode, the first function The layer is an electronic functional layer.
  • the electron function layer includes at least one of an electron injection layer and an electron transport layer;
  • the hole function layer includes at least one of a hole injection layer and a hole transport layer.
  • the first nano-pillar structure is not used to directly combine the quantum dots and regulate the arrangement of the quantum dots, but to form a second nano-pillar structure corresponding to the first nano-pillar structure on the surface of the first functional layer. Structural basis. It is equivalent to forming a first functional layer with a uniform thickness on the surface of the first nano-pillar structure to obtain a second nano-pillar structure, and the gaps between the second nano-pillar structures are used to accommodate quantum dots. At this time, compared with the first nano-pillars, the gap between the second nano-pillars is smaller, but the maximum radial dimension of the second nano-pillars is increased. Specifically, l 1 and l 2 satisfy: l 2 ⁇ l 1 ; At the same time, s 1 and s 2 satisfy: s 1 ⁇ s 2 .
  • d and l 2 satisfy: d ⁇ l 2 ⁇ 2d; or d and l 2 satisfy: l 2 ⁇ d, and r 2 and d satisfy: d ⁇ 2r 2 ⁇ 2d.
  • the gap between the second nanopillar structure can and can only hold one quantum dot in the radial plane, so that the quantum dots can be arranged in an orderly manner, even if the short-chain ligand is combined after the ligand exchange. There will be no reunion.
  • l 2 is approximately the diameter of a quantum dot, that is, l 2 is 2 nm to 20 nm.
  • h and d satisfy: d ⁇ h ⁇ 5d. That is, the deposition thickness of the quantum dots in the gaps between the second nanopillar structures is 1 to 5 quantum dots. If the thickness of the quantum dot is too thick, a higher voltage will be generated, which will affect the light-emitting performance of the quantum dot.
  • the relationship between h and d satisfies: 3d ⁇ h ⁇ 4d. That is, the deposition thickness of the quantum dots in the gaps between the second nanopillar structures is 3 to 4 quantum dots.
  • s2 and d satisfy: s2 ⁇ d, that is, the maximum radial dimension of the second nanopillar in the second nanopillar structure is less than or equal to the diameter of the quantum dot, so that the second nanopillar At most one quantum dot can be accommodated on the upper surface to avoid agglomeration of quantum dots during the ligand exchange process and after the ligand exchange.
  • the quantum dots containing the initial ligands are combined on the surface of the first nanopillar structure, and the quantum dots fall into the gaps between the first nanopillars or the gaps between the second nanopillars, and are arranged in an orderly manner.
  • the initial ligand is a long-chain ligand.
  • the types of long-chain ligands are not strictly limited.
  • quantum dots containing initial ligands are combined on the surface of the first nanopillar structure, and on the top surface of the first nanopillar structure, the thickness of the quantum dot is 1d-2d, that is, the top surface of the first nanopillar structure At most two quantum dots with a height of quantum dots can be formed.
  • a first functional layer is prepared on the surface of the first nanopillar structure, so that the first functional layer has a second nanopillar structure corresponding to the first nanopillar structure; the deposition surface of the first functional layer is combined with The quantum dots of the initial ligand, and on the top surface of the second nanopillar structure, the thickness of the quantum dots is 1d-2d.
  • the target ligand is provided to exchange the initial ligand on the surface of the quantum dot to obtain a quantum dot film bound with the target ligand.
  • the choice of target ligand is not limited, but in order to improve the hole and electron injection and transport capabilities of quantum dots, the target ligand to be introduced on the quantum dot is selected from short-chain ligands, that is, the carbon in the initial ligand. The number of atoms is greater than the number of carbon atoms in the target ligand.
  • a target ligand solution is used to wash the quantum dots bound with the initial ligand, and the difference in binding force between different ligands and quantum dots is used to achieve ligand exchange between the target ligand and the initial ligand.
  • long-chain ligands such as oleic acid ligands have weak binding force f 1 to quantum dots
  • short-chain ligands such as thiol ligands have strong binding force f 2 to quantum dots.
  • the solvent of the target ligand solution is a solvent of insoluble quantum dots, such as acetonitrile.
  • a top electrode is prepared on the surface of the quantum dot light-emitting film, and the top electrode is an electrode opposite to the bottom electrode.
  • the top electrode is a cathode; when the bottom electrode is a cathode, the top electrode is an anode.
  • the top electrode before preparing the top electrode on the surface of the quantum dot light-emitting film, it further includes: preparing the top electrode on the surface of the quantum dot film away from the bottom electrode; or preparing the second functional layer on the surface of the quantum dot film away from the bottom electrode , The top electrode is prepared on the surface of the second functional layer away from the quantum dot film.
  • the second functional layer is a functional layer opposite to the first functional layer.
  • the top electrode is a hole functional layer; when the first functional layer is a hole functional layer, the top electrode is an electronic functional layer.
  • the second aspect of the embodiments of the present application provides a quantum dot light-emitting diode, which includes an anode and a cathode arranged oppositely, and a quantum dot film arranged between the anode and the cathode, wherein the surface of the anode or the cathode is provided with a first nano-column structure, And the surface of the quantum dot film in contact with the first nano column structure is complementary to the first nano column structure, and the other surface of the quantum dot film is a flat surface.
  • the quantum dots are arranged in the nano-column structure of the substrate, so that the spacing width between the nano-column structures and the size of the nano-columns can be controlled to at least make the quantum dots in the form of single particles.
  • the arrangement can avoid aggregation and settlement between quantum dots, and improve the dispersion performance and stability of quantum dots.
  • monodisperse quantum dots increase the flexibility of surface ligand selection, making it easy to combine short-chain ligands on the surface of quantum dots on the premise of avoiding agglomeration, thereby improving hole and electron injection and transport capabilities , Improve the performance of QLED devices.
  • the following marks are made: mark the diameter of the quantum dot as d, mark the distance between adjacent first nanopillars as l 1 , and mark the distance between the first nanopillars The height is marked as h, the maximum radial dimension of the first nanopillar is marked as s 1 , and the radius of the common circumscribed circle of three adjacent first nanopillars is marked as r 1 .
  • the relationship between d, l 1 , s 1 , and h and their optional situations vary according to the difference in the positions of the quantum dot films.
  • the quantum dot film is directly disposed on the first nano-column structure of the bottom electrode, that is, the gap between the first nano-column structure is directly used to accommodate the quantum dots.
  • d and l 1 satisfy: d ⁇ l 1 ⁇ 2d; Or d and l 1 satisfy: l 1 ⁇ d, and r 1 , d satisfy: d ⁇ 2r 1 ⁇ 2d.
  • the gap between the first nanopillar structure can and can only hold one quantum dot in the radial plane, so that the quantum dots can be arranged in an orderly manner, even if the short-chain ligands are combined after the ligand exchange. There will be no reunion.
  • l 1 is approximately the diameter of a quantum dot, that is, l 1 is 2 nm to 20 nm.
  • h and d satisfy: d ⁇ h ⁇ 5d. That is, the deposition thickness of the quantum dots in the gaps between the first nano-pillar structures is 1 to 5 quantum dots. If the thickness of the quantum dot is too thick, a higher voltage will be generated, which will affect the light-emitting performance of the quantum dot.
  • the relationship between h and d satisfies: 3d ⁇ h ⁇ 4d. That is, the deposition thickness of the quantum dots in the gaps between the first nano-pillar structures is 3 to 4 quantum dots.
  • s 1 and d satisfy: s 1 ⁇ d, that is, the largest radial dimension of the first nano-pillar in the first nano-pillar structure is less than or equal to the diameter of the quantum dot, so that the first nano-pillar structure
  • the upper surface of the nanopillar can accommodate at most one quantum dot to avoid agglomeration between quantum dots when the ligand on the surface of the quantum dot is a short-chain ligand.
  • a hole functional layer is provided between the anode and the quantum dot film, and when the anode is provided with a first nanopillar structure, the hole functional layer is provided with a second nanopillar structure corresponding to the first nanopillar structure.
  • An electronic functional layer is provided between the cathode and the quantum dot film, and when the cathode is provided with a first nano-pillar structure, the electronic functional layer is provided with a second nano-pillar structure corresponding to the first nano-pillar structure; adjacent second nano-pillars The distance between them is marked as l 2 , and the maximum radial dimension of the second nano-pillar is marked as s 2 , and l 1 and l 2 satisfy: l 2 ⁇ l 1 ; s 1 and s 2 satisfy: s 1 ⁇ s 2 .
  • the electron function layer includes at least one of an electron injection layer and an electron transport layer
  • the hole function layer includes at least one of a hole injection layer and a hole transport layer.
  • the first nano-pillar structure is not used to directly combine the quantum dots and regulate the arrangement of the quantum dots, but to form a second nano-pillar structure corresponding to the first nano-pillar structure on the surface of the first functional layer. Structural basis. It is equivalent to forming an electronic functional layer or a hole functional layer with a uniform thickness on the surface of the first nano-pillar structure to obtain a second nano-pillar structure, and the gaps between the second nano-pillar structures are used for accommodating quantum dots. At this time, compared with the first nano-pillars, the gap between the second nano-pillars is smaller, but the maximum radial dimension of the second nano-pillars is increased. Specifically, l 1 and l 2 satisfy: l 2 ⁇ l 1 ; At the same time, s 1 and s 2 satisfy: s 1 ⁇ s 2 .
  • d and l 2 satisfy: d ⁇ l 2 ⁇ 2d; or d and l 2 satisfy: l 2 ⁇ d, and r 2 and d satisfy: d ⁇ 2r 2 ⁇ 2d.
  • the gap between the second nanopillar structure can and can only hold one quantum dot in the radial plane, so that the quantum dots can be arranged in an orderly manner, even if the short-chain ligand is combined after the ligand exchange. There will be no reunion.
  • l 2 is approximately the diameter of a quantum dot, that is, l 2 is 2 nm to 20 nm.
  • h and d satisfy: d ⁇ h ⁇ 5d. That is, the deposition thickness of the quantum dots in the gaps between the second nanopillar structures is 1 to 5 quantum dots. If the thickness of the quantum dot is too thick, a higher voltage will be generated, which will affect the light-emitting performance of the quantum dot.
  • the relationship between h and d satisfies: 3d ⁇ h ⁇ 4d. That is, the deposition thickness of the quantum dots in the gaps between the second nanopillar structures is 3 to 4 quantum dots.
  • s 2 and d satisfy: s 2 ⁇ d, that is, the maximum radial dimension of the second nanopillar in the second nanopillar structure is less than or equal to the diameter of the quantum dot, so that the second nanopillar structure
  • the upper surface of the nanopillar can accommodate at most one quantum dot to avoid agglomeration of the quantum dots during the ligand exchange process and after the ligand exchange.
  • the quantum dots with the initial ligand bound on the surface are deposited on the bottom electrode, and the thickness of the quantum dots on the top surface of the first nanopillar structure is 1d-2d.
  • a first functional layer is prepared on the surface of the bottom electrode so that the first functional layer has a second nanopillar structure corresponding to the first nanopillar structure; the deposition surface of the first functional layer is combined with the initial ligand On the top surface of the second nanopillar structure, the thickness of the quantum dots is 1d-2d.
  • the number of layers of quantum dots on the surface of the nanopillars is small, and the maximum radial dimension of the nanopillars is small. Therefore, the agglomeration of quantum dots on the surface of the nanopillars can be reduced or even slowed down, and the overall dispersion performance can be improved.
  • the surface ligands of the quantum dots in the quantum dot film are short-chain ligands, especially short-chain ligands with no more than 6 carbon atoms, so that the quantum dots have better dispersibility and At the same time of stability, it has good electron and hole injection and transport capabilities, thereby improving the performance of quantum dot light-emitting diodes.
  • a method for manufacturing a quantum dot light-emitting diode includes the following steps:
  • a hole injection layer and a hole transport layer are prepared on the ITO nanopillars, and the hole injection layer and the hole transport layer maintain the nanopillar structure to form a second nanopillar structure and control the second nanopillar structure.
  • the gap of the column is adapted to the size of the quantum dot;
  • a quantum dot luminescent film with surface bound oleic acid ligand is prepared on the second nanopillar structure, and the quantum dots fall into the gap of the second nanopillar; as shown in Figure 9, Figure 10, ethyl mercaptan is used
  • the ligand solution washes the quantum dot film, completes the ligand exchange process, and obtains the quantum dot film with ethyl mercaptan ligand bound on the surface.
  • a method for preparing quantum dot light-emitting diodes includes the following steps:
  • the photoresist on the ITO electrode Form the photoresist on the ITO electrode, set the template thickness, substrate thickness, photoresist thickness, vacuum pressure, exposure time and other parameters, and use the quartz imprint template to imprint the photoresist to obtain a micro-nano structure on the surface
  • the photoresist layer; the photoresist layer with micro-nano structure is RIE etched, and the micro-structure pattern on the photoresist is transferred to the surface of the ITO electrode, thereby obtaining a nano-pillar structure;
  • the preparation of the electron transport layer, the electron injection layer and the cathode is completed on the surface of the quantum dot film to obtain a quantum dot light-emitting diode.
  • a method for preparing quantum dot light-emitting diodes includes the following steps:
  • the preparation of the electron transport layer, the electron injection layer and the cathode is completed on the surface of the quantum dot film to obtain a quantum dot light-emitting diode.

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Abstract

本申请公开一种量子点发光二极管的制备方法，包括以下步骤：提供底电极基板，在所述底电极基板的底电极表面形成第一纳米柱结构；在所述第一纳米柱结构表面结合含有初始配体的量子点，采用目标配体对所述表面结合有初始配体的量子点进行配体交换，制备得到结合有目标配体的量子点薄膜。本申请提供的量子点发光二极管的制备方法，可以得到兼具良好的分散性和电荷注入传输能力的量子点薄膜。

Description

量子点发光二极管及其制备方法
本申请要求于2019年12月31日在中国专利局提交的、申请号为201911423750.9、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。
技术领域
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。
 背景技术
量子点电致发光器件（QLED）因其低启亮电压、窄发光峰、发光波长可调等优势，展示出了巨大的应用潜力。QLED采用三明治结构，包括阳极和阴极，以及在阳极和阴极之间设置的量子点发光层。目前，QLED通常包括阳极、空穴注入层、空穴传输层、量子点发光层、电子传输层和阴极。其中，量子点发光层的制备尤其重要。
在现有的QLED中，电子和空穴由注入层提供，经过传输层，最后在量子点发光层进行复合发光。典型的量子点结构，由核、外壳（单层或多层）、链状配体构成，电子和空穴最终在量子点核内进行复合发光。由于量子点容易发生团聚现象，因此，目前采的长链配体来有效防止量子点聚集沉降。但也因为长链配体链长较长，导致量子点的电荷注入能力和传输能力仍然有待提高。而短链配体可有效提高电子和空穴的注入和传输能力，但容易导致量子点聚集沉降。
 技术问题
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，旨在解决量子点难以兼顾良好的分散性和电荷注入传输能力的问题。
 技术解决方案
为解决上述技术问题，本申请实施例采用的技术方案是：
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：
提供底电极基板，在所述底电极基板的底电极表面形成第一纳米柱结构；
在所述第一纳米柱结构表面结合含有初始配体的量子点，提供目标配体与所述量子点表面的初始配体进行交换，制备得到结合有目标配体的量子点薄膜；
其中，量子点的直径标记为d，相邻的第一纳米柱之间的间距标记为l 1，第一纳米柱的高度标记为h，第一纳米柱的最大径向尺寸标记为s 1，相邻的三个所述第一纳米柱的共同外接圆的半径标记为r 1。
第二方面，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，以及设置在所述阳极和所述阴极之间的量子点薄膜，其中，所述阳极或所述阴极的表面设置第一纳米柱结构，且所述量子点薄膜与所述第一纳米柱结构接触的表面与所述第一纳米柱结构互补，所述量子点薄膜的另一表面为平整表面；其中，将量子点的直径标记为d，相邻的第一纳米柱之间的间距标记为l 1，第一纳米柱的高度标记为h，第一纳米柱的最大径向尺寸标记为s 1，相邻的三个所述第一纳米柱的共同外接圆的半径标记为r 1。
有益效果
本申请提供的量子点发光二极管的制备方法，先在底电极基板的底电极表面形成第一纳米柱结构；然后在所述第一纳米柱结构表面结合含有初始配体的量子点，结合有初始配体的量子点进入第一纳米柱结构的孔隙中，通过控制第一纳米柱结构之间的间距宽度和纳米柱的尺寸，使得至少量子点能够以单颗粒的形式排列，可以减少量子点聚集沉降，提高了量子点的分散性能和稳定性；最后，采用目标配体对表面结合有初始配体的量子点进行配体交换，在量子点表面结合能够提高电荷注入能力和传输能力的目标配体，最终得到能够兼具良好的分散性和电荷注入传输能力的量子点薄膜。此外，该方法操作简单，成本低廉。
本申请提供的量子点发光二极管，将量子点设置在基板的纳米柱结构中，从而可以通过控制纳米柱结构之间的间距宽度和纳米柱的尺寸，至少使得量子点以单颗粒的形式排列，可以避免量子点之间聚集沉降，提高了量子点的分散性能和稳定性。进一步的，单分散量子点提高了表面配体选择的灵活性，使得在避免团聚的前提下，短链配体在量子点表面的结合变得容易，从而提高空穴和电子的注入和传输能力，改善QLED器件性能。
 附图说明
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。
图1是本申请实施例提供的量子点发光二极管的制备工艺流程图；
图2是本申请实施例1提供的ITO层表面制备的单层聚苯乙烯纳米球薄膜的剖视图；
图3是本申请实施例1提供的ITO层表面制备的单层聚苯乙烯纳米球薄膜的俯视图；
图4是本申请实施例1提供的ITO层表面形成聚苯乙烯纳米球掩膜后的剖视图；
图5是本申请实施例1采用ITO刻蚀液对覆盖聚苯乙烯纳米球掩模的ITO进行刻蚀，在ITO表面形成第一纳米柱结构的示意图；
图6是本申请实施例1提供的刻蚀后在ITO表面形成第一纳米柱结构的示意图；
图7是本申请实施例1提供的在ITO纳米柱上制备空穴注入层、空穴传输层后的结构图；
图8是本申请实施例1提供的沉积表面配体为油酸的量子点后的结构示意图；
图9是本申请实施例1提供的量子点进行配体交换后的示意图；
图10是本申请实施例1提供的乙基硫醇配体与油酸进行配体交换的反应示意图；
图11是本申请实施例1制备得到的量子点发光二极管的结构示意图。
 本发明的实施方式
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。
在本申请的描述中，需要理解的是，术语“第一”、“第二”仅用于描述目的，而不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量。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。
本申请实施例说明书中所提到的相关成分的重量不仅仅可以指代各组分的具体含量，也可以表示各组分间重量的比例关系，因此，只要是按照本申请实施例说明书相关组分的含量按比例放大或缩小均在本申请实施例说明书公开的范围之内。具体地，本申请实施例说明书中所述的重量可以是µg、mg、g、kg等化工领域公知的质量单位。
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的制备方法，包括以下步骤：
S01. 提供底电极基板，在底电极基板的底电极表面形成第一纳米柱结构；；
S02. 在第一纳米柱结构表面结合含有初始配体的量子点，提供目标配体与量子点表面的初始配体进行交换，制备得到结合有目标配体的量子点薄膜。
本申请实施例提供的量子点发光二极管的制备方法，先在底电极基板的底电极表面形成第一纳米柱结构；然后在第一纳米柱结构表面结合含有初始配体的量子点，结合有初始配体的量子点进入第一纳米柱结构的孔隙中，通过控制第一纳米柱结构之间的间距宽度和纳米柱的尺寸，使得至少量子点能够以单颗粒的形式排列，可以减少量子点聚集沉降，提高了量子点的分散性能和稳定性；最后，采用目标配体对表面结合有初始配体的量子点进行配体交换，在量子点表面结合能够提高电荷注入能力和传输能力的目标配体，最终得到能够兼具良好的分散性和电荷注入传输能力的量子点薄膜。此外，该方法操作简单，成本低廉。
具体的，上述步骤S01中，提供底电极基板，底电极基板包括衬底，以及在衬底上设置的底电极。其中，衬底可以为刚性衬底，也可以为柔性衬底。底电极可以为阳极，也可以为阴极。在一些实施例中，底电极为ITO电极。在衬底上制备底电极的方式没有严格限定，可以采用常规的溅射、蒸镀等工艺，在沉底上制备底电极。
在一些实施例中，在底电极基板的底电极表面形成第一纳米柱结构的方法为：对底电极基板上的底电极进行刻蚀处理。对底电极基板上的底电极进行刻蚀处理后，使底电极背离衬底的表面凸设形成若干纳米柱，得到第一纳米柱结构。
在一些实施例中，对底电极基板上的底电极进行刻蚀处理的步骤，包括：
E11. 在底电极基板的底电极上制备单层聚苯乙烯纳米球薄膜；
E12. 对单层聚苯乙烯纳米球薄膜中的聚苯乙烯纳米球进行RIE刻蚀处理，在聚苯乙烯纳米球之间形成间隙；
E13. 以聚苯乙烯纳米球作为掩膜，对底电极进行刻蚀处理，去除聚苯乙烯纳米球，制备得到具有第一纳米柱结构的底电极。
具体的，上述步骤E11中，在底电极基板的底电极上制备单层聚苯乙烯纳米球薄膜，单层聚苯乙烯纳米球薄膜用于制作第一纳米柱结构的刻蚀模板。
在一些实施例中，通过溶液加工法在底电极基板的底电极上制备单层聚苯乙烯纳米球薄膜，包括但不限于自组织法和旋涂法。该方法中，包括配置聚苯乙烯纳米球混悬液的步骤。聚苯乙烯纳米球混悬液的配置方法为：将聚苯乙烯纳米球分散在溶剂中，得到聚苯乙烯纳米球混悬液。在一些实施例中，配置聚苯乙烯纳米球的质量百分浓度为0.1%~10%的聚苯乙烯纳米球的混悬液，且混悬液中的溶剂为去离子水和乙醇的混合溶剂。在这种情况下，聚苯乙烯纳米球的含量合适，且以去离子水和乙醇的混合溶剂作为分散体系，得到的聚苯乙烯纳米球混悬液具有自组装特性，从而有利于聚苯乙烯在底电极的表面形成单层聚苯乙烯纳米球薄膜。
在一些实施例中，采用单一尺寸的聚苯乙烯纳米球制备单层聚苯乙烯纳米球薄膜，此时在底电极表面形成六角密堆积、且周期有序排列的单层聚苯乙烯纳米球薄膜；在一些实施例中，采用不同尺寸的聚苯乙烯纳米球制备单层聚苯乙烯纳米球薄膜，此时在底电极表面形成单层无序的聚苯乙烯纳米球薄膜。
在一些实施例中，单层聚苯乙烯纳米球薄膜中，聚苯乙烯纳米球的直径为10nm~1000nm。聚苯乙烯纳米球的直径在此范围内时，可以通过后续RIE刻蚀处理，调控聚苯乙烯纳米球的尺寸和相邻聚苯乙烯纳米球的间距，从而以刻蚀后的聚苯乙烯纳米球为模板，得到合适的第一纳米柱结构的尺寸和相邻第一纳米柱之间的间距。值得注意的是，当量子点发光层直接设置在底电极上时，量子点在第一纳米柱的间隙和第一纳米柱表面直接沉积，这种情况下，选择的聚苯乙烯纳米球的直径通常小于100nm。当底电极表面沉积第一功能层，量子点发光层设置在第一功能层上时，由于在底电极的第一纳米柱结构表现会形成至少一层膜层，因此，随着膜层厚度的增加，纳米柱之间的间隙变小，纳米柱的最大径向尺寸逐渐增加，这种情况下，选择的聚苯乙烯纳米球的直径通常大于60nm。
上述步骤E12中，对单层聚苯乙烯纳米球薄膜中的聚苯乙烯纳米球进行RIE刻蚀处理，减小聚苯乙烯纳米球的尺寸，并增加相邻聚苯乙烯纳米球之间的间距。对单层聚苯乙烯纳米球薄膜中的聚苯乙烯纳米球进行RIE刻蚀（反应离子刻蚀）处理的步骤中，刻蚀参数可以根据聚苯乙烯纳米球的初始尺寸、以及刻蚀后的预期尺寸进行调控。在一些实施例中，刻蚀气氛可为氧气、四氟化碳中的一种或两种以上形成的混合气体，流速可为1sccm~200sccm，刻蚀功率可为0.1W~100W，刻蚀时间可为1s~500s。
对聚苯乙烯纳米球的刻蚀，结合下文第一纳米柱结构中相邻第一纳米柱结构的间距以及第一纳米柱结构的最大径向尺寸进行调节。
上述步骤E13中，以刻蚀后的聚苯乙烯纳米球作为掩膜，对底电极进行刻蚀处理。在一些实施例中，采用可与底电极反应，但是对聚苯乙烯纳米球无腐蚀活性或腐蚀效果微弱的刻蚀液对覆盖有聚苯乙烯纳米球的底电极进行刻蚀处理。在一些实施例中，对底电极进行刻蚀处理的步骤中，采用无机酸刻蚀液对底电极进行刻蚀处理。无机酸刻蚀液对聚苯乙烯纳米球无腐蚀活性或腐蚀效果微弱，因此，采用聚苯乙烯纳米球作为掩膜时，由于聚苯乙烯纳米球的阻挡，无机酸刻蚀液对覆盖聚苯乙烯纳米球的底电极区域没有刻蚀作用，而对没有覆盖聚苯乙烯纳米球的区域进行反应刻蚀，最终在没有覆盖聚苯乙烯纳米球的底电极区域形成凹陷，相应的，覆盖聚苯乙烯纳米球的区域则形成纳米柱。在一些实施例中，无机酸刻蚀液选自氢氟酸、硝酸、磷酸、硫酸、盐酸、醋酸中的一种或多种形成的混合溶液。当采用上述无机酸刻蚀液时，调控无机酸刻蚀液的质量浓度为0.1%~20%，从而合理控制刻蚀速度，以防止刻蚀反应过于剧烈导致底电极过刻蚀，不能形成第一纳米柱结构。刻蚀过程中，刻蚀温度和刻蚀时间可根据刻蚀液的选择进行调节，在一些实施例中，刻蚀温度为20℃~100℃，刻蚀时间为1s~5h。
在一些实施例中，用无机酸刻蚀液对底电极进行刻蚀处理时，无机酸刻蚀液中，添加有铁盐、亚铁盐和丙酮中的至少一种。通过添加铁盐、亚铁盐和丙酮中的至少一种，有利于经刻蚀液刻蚀形成的凹陷壁面更光滑平整，即纳米柱的壁面更光滑平整，从而有利于提高量子点的填充均匀性。
刻蚀完成后，采用溶液法、烧灼等方法去除残留的聚苯乙烯纳米球，从而得到与PS纳米球掩模板周期、大小一致的第一纳米柱。
在一些实施例中，对底电极基板上的底电极进行刻蚀处理的步骤，包括：
E21.提供具有与第一纳米柱结构互补的微纳结构的压印模板；
E22.在底电极上形成光刻胶，并采用压印模板对光刻胶进行压印处理，得到表面形成微纳结构的光刻胶层；
E23.对具有纳米柱结构的光刻胶层进行刻蚀，将纳米柱结构转移至底电极表面，制备得到具有第一纳米柱结构的底电极。
具体的，上述步骤E21中，本申请实施例中，压印模板为具有与第一纳米柱结构互补的微纳结构，该微纳结构作为压印模板，通过压印处理转移到待处理的膜层上。因此，压印模板的基材需具有较大的硬度，使得在压印得以进行，且在压印过程中能够保持微纳结构的形状。可选的，压印模具为具有微纳结构的石英压印模具。
在一些实施例中，石英压印模具可以通过下述方法制备获得：选用对紫外光线透明性能良好的石英玻璃作为压印模板的基材；用酒精、丙酮、酒精溶液，依次对石英基片进行超声清洗，烘干待用；在石英玻璃表面蒸镀一层5nm~50 nm 的金属Cr薄膜，在金属Cr薄膜上沉积电子束光刻胶层；利用电子束直写技术进行光刻胶直写曝光、显影，在光刻胶层上形成微纳结构；以具有微纳结构的光刻胶为阻挡层，对金属Cr薄膜进行干法刻蚀；再以金属Cr薄膜为阻挡层对石英基片进行干法刻蚀，从而得到石英衬底上光子晶体微结构的石英压印模板。
上述步骤E22中，在底电极上形成光刻胶，在底电极上形成光刻胶层的方式没有严格限定，可以采用常规方法制备。采用压印模板对光刻胶进行压印处理，得到表面形成微纳结构的光刻胶层。
在一些实施例中，采用上述的石英压印模具对光刻胶进行压印处理。具体的，采用石英压印模具，设置模板厚度、基片厚度、光刻胶厚度、真空压力、曝光时间等参数，进行压印处理；石英压印模板压入光刻胶后，进行紫外固化，随后进行脱模处理，从而实现纳米压印模具的图形转移。
上述步骤E23中，对具有微纳结构的光刻胶层进行刻蚀，将光刻胶上的微结构图案转移到底电极表面，从而获得第一纳米柱结构。在一些实施例中，采用RIE刻蚀方法，将光刻胶上的微结构图案转移到底电极表面，从而获得第一纳米柱结构。
并采用压印模板对光刻胶进行压印处理，在光刻胶层表面形成纳米柱结构。在一些实施例中，采用上述的压印模板，设置模板厚度、
本申请实施例中，经过刻蚀处理得到的第一纳米柱之间存在间隙，间隙用于直接容纳表面结合有初始配体的量子点；或在沉积第一功能层后，容纳表面结合有初始配体的量子点。
为了方便下文中各量度关系的描述，作出如下标记：将量子点的直径标记为d，相邻的第一纳米柱之间的间距标记为l 1，第一纳米柱的高度标记为h，第一纳米柱的最大径向尺寸标记为s 1，相邻的三个第一纳米柱的共同外接圆的半径标记为r 1。其中，第一纳米柱的最大径向尺寸是指第一纳米柱在垂直于轴向方向上的最大宽度，相邻的第一纳米柱之间的间距为相邻的两个第一纳米柱之间的最小距离。
本申请实施例中，d、l 1、s 1、h、r 1之间的关系及其可选情形，根据量子点沉积的位置差异而异。
在一种实施方式中，直接在底电极的第一纳米柱结构上沉积量子点，即第一纳米柱结构之间的空隙直接用于容纳量子点。此时，为了使得沉积在第一纳米柱间隙中的量子点具有较好的分散性和稳定性，即便在下述步骤S02配体交换过程中、以及配体交换后也不发生团聚，本申请实施例中，d、l 1满足：d≤l 1＜2d；或d、l 1满足：l 1＜d，且r 1、d满足：d≤2r 1＜2d。在这种情况下，第一纳米柱结构之间的空隙在径向平面能且只能容量一个量子点，从而可以使得量子点有序排列，即便在配体交换后结合短链配体，也不会出现团聚现象。在一些实施例中，l 1约为一个量子点的直径大小，即l 1为2nm~20nm。
在一些实施例中，第一纳米柱结构中，h、d满足：d≤h≤5d。即量子点在第一纳米柱结构之间的空隙中的沉积厚度为1个量子点至5个量子点的厚度。若量子点的厚度过厚，则会产生较高的电压，影响量子点的发光性能。在一些实施例中，第一纳米柱结构中，h、d的关系满足：3d≤h≤4d。即量子点在第一纳米柱结构之间的空隙中的沉积厚度为3个量子点至4个量子点的厚度。
在一些实施例中，第一纳米柱结构中，s 1、d满足：s 1≤d，即第一纳米柱结构中第一纳米柱的最大径向尺寸小于等于量子点的直径，使得第一纳米柱的上表面最多容纳一个量子点，以避免量子点在配体交换过程中、以及配体交换后发生团聚。
上述步骤S02中，在第一纳米柱结构表面结合含有初始配体的量子点，量子点落入第一纳米柱之间的空隙之间的空隙中，有序排列。
在另一种实施方式中，量子点发光二极管的制备方法，还包括：在第一纳米柱结构表面制备第一功能层，且第一功能层具有与第一纳米柱结构对应的第二纳米柱结构；在第二纳米柱结构表面结合含有初始配体的量子点，提供目标配体与量子点表面的初始配体进行交换，制备得到结合有目标配体的量子点薄膜；其中，相邻的第二纳米柱之间的间距标记为l 2，第二纳米柱的最大径向尺寸标记为s 2，相邻的三个第二纳米柱的共同外接圆的半径标记为r 2。第一功能层根据底电极的类型，为电子功能层、空穴功能层的一种：当底电极为阳极时，第一功能层为空穴功能层；当底电极为阴极时，第一功能层为电子功能层。其中，电子功能层包括电子注入层、电子传输层中的至少一层；空穴功能层包括空穴注入层、空穴传输层中的至少一层。
在这种实施方式下，第一纳米柱结构并不用于直接结合量子点并规范量子点的排布，而是为第一功能层表面形成与第一纳米柱结构对应的第二纳米柱结构提供结构基础。相当于在第一纳米柱结构的表面，再形成一层厚度均一的第一功能层，得到第二纳米柱结构，第二纳米柱结构之间的空隙用于容纳量子点。此时，相较于第一纳米柱，第二纳米柱之间的间隙更小，但第二纳米柱的最大径向尺寸增加，具体的，l 1、l 2满足：l 2＜l 1；同时，s 1、s 2满足：s 1＜s 2。
为了使得沉积在第二纳米柱间隙中的量子点具有较好的分散性和稳定性，即便在下述步骤S02配体交换过程中、以及配体交换后也不发生团聚，本申请实施例中，d、l 2满足：d≤l 2＜2d；或d、l 2满足：l 2＜d，且r 2、d满足：d≤2r 2＜2d。在这种情况下，第二纳米柱结构之间的空隙在径向平面能且只能容量一个量子点，从而可以使得量子点有序排列，即便在配体交换后结合短链配体，也不会出现团聚现象。在一些实施例中，l 2约为一个量子点的直径大小，即l 2为2nm~20nm。
在一些实施例中，第二纳米柱结构中，h、d满足：d≤h≤5d。即量子点在第二纳米柱结构之间的空隙中的沉积厚度为1个量子点至5个量子点的厚度。若量子点的厚度过厚，则会产生较高的电压，影响量子点的发光性能。在一些实施例中，第二纳米柱结构中，h、d的关系满足：3d≤h≤4d。即量子点在第二纳米柱结构之间的空隙中的沉积厚度为3个量子点至4个量子点的厚度。
在一些实施例中，第二纳米柱结构中，s2、d满足：s2≤d，即第二纳米柱结构中第二纳米柱的最大径向尺寸小于等于量子点的直径，使得第二纳米柱的上表面最多容纳一个量子点，以避免量子点在配体交换过程中、以及配体交换后发生团聚。
在上述实施例的基础上，在第一纳米柱结构表面结合含有初始配体的量子点，量子点落入第一纳米柱之间的空隙或第二纳米柱之间的空隙中，有序排列。为了避免沉积的量子点发生团聚，初始配体为长链配体。长链配体的类型没有严格的限定，为量子点选择能够阻止其团聚的常规配体，尤其为碳原子数大于等于10的配体。
在一些实施例中，在第一纳米柱结构表面结合含有初始配体的量子点，第一纳米柱结构的顶表面上，量子点的厚度为1d-2d，即第一纳米柱结构的顶表面最多形成两个量子点高度的量子点。在一些实施例中，在第一纳米柱结构表面制备第一功能层，使第一功能层具有与第一纳米柱结构对应的第二纳米柱结构；在第一功能层的表面沉积表面结合有初始配体的量子点，且第二纳米柱结构的顶表面上，量子点的厚度为1d-2d。此时，在纳米柱表面的量子点的层数较少，加之纳米柱最大径向尺寸较小，因此，可以降低甚至减缓纳米柱表面上的量子点的团聚，提高整体分散性能。本申请实施例中，提供目标配体与量子点表面的初始配体进行交换，得到结合有目标配体的量子点薄膜。原则上，目标配体的选择没有限定，但是为了提高量子点中空穴和电子的注入和传输能力，待引入量子点上的目标配体，选自短链配体，即初始配体中的碳原子数大于目标配体中的碳原子数。
在一些实施例中，采用目标配体溶液对结合有初始配体的量子点进行冲洗，利用不同配体与量子点结合力的差异，实现目标配体和初始配体之间的配体交换。具体的，长链配体如油酸配体与量子点结合力f 1较弱，短链配体如硫醇配体与量子点结合力f 2较强，因此在结合有初始配体的量子点冲洗目标配体溶液时，与量子点结合力较强的短链配体将与量子点结合能力弱的长链配体置换下来。应当理解的是，目标配体溶液的溶剂为不可溶量子点的溶剂，如乙腈。
在一些实施例中，在量子点发光薄膜表面制备顶电极，顶电极为与底电极相对的电极。当底电极为阳极时，顶电极为阴极；当底电极为阴极时，顶电极为阳极。
在一些实施例中，在量子点发光薄膜表面制备顶电极之前，还包括：在量子点薄膜背离底电极的表面，制备顶电极；或在量子点薄膜背离底电极的表面，制备第二功能层，在第二功能层背离量子点薄膜的表面制备顶电极。其中，第二功能层为与第一功能层相对的功能层。当第一功能层为电子功能层时，顶电极为空穴功能层；当第一功能层为空穴功能层时，顶电极为电子功能层。
本申请实施例第二方面提供一种量子点发光二极管，包括相对设置的阳极和阴极，以及设置在阳极和阴极之间的量子点薄膜，其中，阳极或阴极的表面设置第一纳米柱结构，且量子点薄膜与第一纳米柱结构接触的表面与第一纳米柱结构互补，量子点薄膜的另一表面为平整表面。
本申请实施例提供的量子点发光二极管，将量子点设置在基板的纳米柱结构中，从而可以通过控制纳米柱结构之间的间距宽度和纳米柱的尺寸，至少使得量子点以单颗粒的形式排列，可以避免量子点之间聚集沉降，提高了量子点的分散性能和稳定性。进一步的，单分散量子点提高了表面配体选择的灵活性，使得在避免团聚的前提下，短链配体在量子点表面的结合变得容易，从而提高空穴和电子的注入和传输能力，改善QLED器件性能。
本申请实施例中，为了方便下文中各量度关系的描述，作出如下标记：将量子点的直径标记为d，相邻的第一纳米柱之间的间距标记为l 1，第一纳米柱的高度标记为h，第一纳米柱的最大径向尺寸标记为s 1，相邻的三个第一纳米柱的共同外接圆的半径标记为r 1。
本申请实施例中，d、l 1、s 1、h之间的关系及其可选情形，根据量子点薄膜设置的位置差异而异。
在一种实施方式中，量子点薄膜直接设置在底电极的第一纳米柱结构上，即第一纳米柱结构之间的空隙直接用于容纳量子点。此时，为了使得第一纳米柱间隙中的量子点具有较好的分散性和稳定性，避免量子点团聚发生团聚，本申请实施例中，d、l 1满足：d≤l 1＜2d；或d、l 1满足：l 1＜d，且r 1、d满足：d≤2r 1＜2d。在这种情况下，第一纳米柱结构之间的空隙在径向平面能且只能容量一个量子点，从而可以使得量子点有序排列，即便在配体交换后结合短链配体，也不会出现团聚现象。在一些实施例中，l 1约为一个量子点的直径大小，即l 1为2nm~20nm。
在一些实施例中，第一纳米柱结构中，h、d满足：d≤h≤5d。即量子点在第一纳米柱结构之间的空隙中的沉积厚度为1个量子点至5个量子点的厚度。若量子点的厚度过厚，则会产生较高的电压，影响量子点的发光性能。在一些实施例中，第一纳米柱结构中，h、d的关系满足：3d≤h≤4d。即量子点在第一纳米柱结构之间的空隙中的沉积厚度为3个量子点至4个量子点的厚度。
在一些实施例中，第一纳米柱结构中，s 1、d满足：s 1≤d，即第一纳米柱结构中第一纳米柱的最大径向尺寸小于等于量子点的直径，使得第一纳米柱的上表面最多容纳一个量子点，以避免量子点表面的配体为短链配体时量子点之间发生团聚现象。
在另一种实施方式中，在阳极和量子点薄膜之间设置空穴功能层，且当阳极设置第一纳米柱结构时，空穴功能层设置有与第一纳米柱结构对应的第二纳米柱结构；相邻的第二纳米柱之间的间距标记为l 2，第二纳米柱的最大径向尺寸标记为s 2，相邻的三个第二纳米柱的共同外接圆的半径标记为r 2，l 1、l 2满足：l 2＜l 1；s 1、s 2满足：s 1＜s 2；或者
在阴极和量子点薄膜之间设置电子功能层，且当阴极设置第一纳米柱结构时，电子功能层设置有与第一纳米柱结构对应的第二纳米柱结构；相邻的第二纳米柱之间的间距标记为l 2，第二纳米柱的最大径向尺寸标记为s 2，l 1、l 2满足：l 2＜l 1；s 1、s 2满足：s 1＜s 2。
其中，电子功能层包括电子注入层、电子传输层中的至少一层；空穴功能层包括空穴注入层、空穴传输层中的至少一层。
在这种实施方式下，第一纳米柱结构并不用于直接结合量子点并规范量子点的排布，而是为第一功能层表面形成与第一纳米柱结构对应的第二纳米柱结构提供结构基础。相当于在第一纳米柱结构的表面，再形成厚度均一的电子功能层或空穴功能层后，得到第二纳米柱结构，第二纳米柱结构之间的空隙用于容纳量子点。此时，相较于第一纳米柱，第二纳米柱之间的间隙更小，但第二纳米柱的最大径向尺寸增加，具体的，l 1、l 2满足：l 2＜l 1；同时，s 1、s 2满足：s 1＜s 2。
为了使得沉积在第二纳米柱间隙中的量子点具有较好的分散性和稳定性，避免量子点团聚发生团聚，本申请实施例中，d、l 2满足：d≤l 2＜2d；或d、l 2满足：l 2＜d，且r 2、d满足：d≤2r 2＜2d。在这种情况下，第二纳米柱结构之间的空隙在径向平面能且只能容量一个量子点，从而可以使得量子点有序排列，即便在配体交换后结合短链配体，也不会出现团聚现象。在一些实施例中，l 2约为一个量子点的直径大小，即l 2为2nm~20nm。
在一些实施例中，第二纳米柱结构中，h、d满足：d≤h≤5d。即量子点在第二纳米柱结构之间的空隙中的沉积厚度为1个量子点至5个量子点的厚度。若量子点的厚度过厚，则会产生较高的电压，影响量子点的发光性能。在一些实施例中，第二纳米柱结构中，h、d的关系满足：3d≤h≤4d。即量子点在第二纳米柱结构之间的空隙中的沉积厚度为3个量子点至4个量子点的厚度。
在一些实施例中，第二纳米柱结构中，s 2、d满足：s 2≤d，即第二纳米柱结构中第二纳米柱的最大径向尺寸小于等于量子点的直径，使得第二纳米柱的上表面最多容纳一个量子点，以避免量子点在配体交换过程中、以及配体交换后发生团聚。
在一些实施例中，在底电极上沉积表面结合有初始配体的量子点，第一纳米柱结构的顶表面上，量子点的厚度为1d-2d。在一些实施例中，在底电极表面制备第一功能层，使第一功能层具有与第一纳米柱结构对应的第二纳米柱结构；在第一功能层的表面沉积表面结合有初始配体的量子点，且第二纳米柱结构的顶表面上，量子点的厚度为1d-2d。此时，在纳米柱表面的量子点的层数较少，加之纳米柱最大径向尺寸较小，因此，可以降低甚至减缓纳米柱表面上的量子点的团聚，提高整体分散性能。
本申请实施例中，量子点薄膜中的量子点的表面配体，为短链配体，尤其为碳原子数不多于6的短链配体，从而使得量子点在具有较好分散性和稳定性的同时，兼具良好的电子和空穴的注入和传输能力，进而改善量子点发光二极管的性能。
下面结合具体实施例进行说明。 实施例 1
如图2-11所示，一种量子点发光二极管的制备方法，包括以下步骤：
在透明衬底上制备ITO电极；
配置聚苯乙烯质量百分浓度为0.1%~10%的聚苯乙烯去离子水/乙醇混合液，采用自组织法在ITO电极的ITO表面制备单层周期有序/无序的PS纳米球掩薄膜，ITO层表面制备的单层聚苯乙烯纳米球薄膜的剖视图如图2所示，ITO层表面制备的单层聚苯乙烯纳米球薄膜的俯视图如图3所示。对所制备的单层周期有序/无序的聚苯乙烯纳米球薄膜进行RIE刻蚀，增加聚苯乙烯纳米球之间的间隙，得到聚苯乙烯纳米球掩膜，ITO层表面形成聚苯乙烯纳米球掩膜后的剖视图如图4所示。如图5所示，采用ITO刻蚀液对覆盖聚苯乙烯纳米球掩模的ITO进行刻蚀，得到与聚苯乙烯纳米球掩模板周期、大小一致的ITO纳米柱，在ITO表面形成第一纳米柱结构。刻蚀完成后，采用溶液法、烧灼等方法去除残留的聚苯乙烯纳米球，从而得到与PS纳米球掩模板周期、大小一致的ITO纳米柱，如图6所示。
如图7所示，在ITO纳米柱上制备空穴注入层、空穴传输层，且使得空穴注入层、空穴传输层保持纳米柱结构，形成第二纳米柱结构，并控制第二纳米柱的间隙与量子点的尺寸适配；
如图8所示，在第二纳米柱结构上制备表面结合油酸配体的量子点发光薄膜，量子点落入第二纳米柱间隙；如图9、图10所示，用乙基硫醇配体溶液对量子点薄膜进行冲洗，完成配体交换过程，得到表面结合有乙基硫醇配体的量子点薄膜。
在量子点薄膜表面完成电子传输层、电子注入层、阴极的制备，得到量子点发光二极管，如图11所示。 实施例 2
一种量子点发光二极管的制备方法，包括以下步骤：
在透明衬底上制备ITO电极；
选用对紫外光线透明性能良好的石英玻璃作为压印模板的基材；用酒精、丙酮、酒精溶液，依次对石英基片进行超声清洗，烘干待用；在石英玻璃表面蒸镀一层40 nm 的金属Cr薄膜，在金属Cr薄膜上沉积电子束光刻胶层；利用电子束直写技术进行光刻胶直写曝光、显影，在光刻胶层上形成微纳结构；以具有微纳结构的光刻胶为阻挡层，对金属Cr薄膜进行干法刻蚀；再以金属Cr薄膜为阻挡层对石英基片进行干法刻蚀，从而得到石英衬底上光子晶体微结构的石英压印模板。
在ITO电极上形成光刻胶，设置模板厚度、基片厚度、光刻胶厚度、真空压力、曝光时间等参数，采用石英压印模板对光刻胶进行压印处理，得到表面形成微纳结构的光刻胶层；对具有微纳结构的光刻胶层进行RIE刻蚀，将光刻胶上的微结构图案转移到ITO电极表面，从而获得纳米柱结构；
在ITO纳米柱上制备空穴注入层、空穴传输层，且使得空穴注入层、空穴传输层保持纳米柱结构，形成第二纳米柱结构，并控制第二纳米柱的间隙与量子点的尺寸适配；
在第二纳米柱结构上制备表面结合油酸配体的量子点发光薄膜，量子点落入第二纳米柱间隙；用乙基硫醇配体溶液对量子点薄膜进行冲洗，完成配体交换过程，得到表面结合有乙基硫醇配体的量子点薄膜。
在量子点薄膜表面完成电子传输层、电子注入层、阴极的制备，得到量子点发光二极管。
对比例1
一种量子点发光二极管的制备方法，包括以下步骤：
在透明衬底上制备ITO电极；
在ITO电极上制备表面结合油酸配体的量子点发光薄膜；
在量子点薄膜表面完成电子传输层、电子注入层、阴极的制备，得到量子点发光二极管。
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 (30)

  1. 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：
    提供底电极基板，在所述底电极基板的底电极表面形成第一纳米柱结构；
    在所述第一纳米柱结构表面结合含有初始配体的量子点，提供目标配体与所述量子点表面的初始配体进行交换，制备得到结合有目标配体的量子点薄膜；
    其中，量子点的直径标记为d，相邻的第一纳米柱之间的间距标记为l 1，第一纳米柱的高度标记为h，第一纳米柱的最大径向尺寸标记为s 1，相邻的三个所述第一纳米柱的共同外接圆的半径标记为r 1。
  2. 如权利要求1所述的量子点发光二极管的制备方法，其特征在于，所述d、l 1满足：d≤l 1＜2d；或
    所述d、l 1满足：l 1＜d，且所述r 1、d满足：d≤2r 1＜2d。
  3. 如权利要求2所述的量子点发光二极管的制备方法，其特征在于，所述l 1为2nm~20nm。
  4. 如权利要求1所述的量子点发光二极管的制备方法，其特征在于，所述第一纳米柱结构中，h、d满足：d≤h≤5d。
  5. 如权利要求4所述的量子点发光二极管的制备方法，其特征在于，所述h、d的关系满足：3d≤h≤4d。
  6. 如权利要求1所述的量子点发光二极管的制备方法，其特征在于，所述第一纳米柱结构中，s 1、d满足：s 1≤d。
  7. 如权利要求1所述的量子点发光二极管的制备方法，其特征在于，所述第一纳米柱结构的顶表面上，量子点的厚度为1d-2d。
  8. 如权利要求1所述的量子点发光二极管的制备方法，其特征在于，所述方法还包括：
    在所述第一纳米柱结构表面制备第一功能层，且所述第一功能层具有与所述第一纳米柱结构对应的第二纳米柱结构；
    在所述第二纳米柱结构表面结合含有初始配体的量子点，提供目标配体与所述量子点表面的初始配体进行交换，制备得到结合有目标配体的量子点薄膜；
    其中，相邻的第二纳米柱之间的间距标记为l 2，第二纳米柱的最大径向尺寸标记为s 2，相邻的三个所述第二纳米柱的共同外接圆的半径标记为r 2，所述l 1、l 2满足：l 2＜l 1；所述s 1、s 2满足：s 1＜s 2。
  9. 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d、l 2满足：d≤l 2＜2d，或
    所述d、l 2满足：l 2＜d，且所述r 2、d满足：d≤2r 2＜2d。
  10. 如权利要求9所述的量子点发光二极管的制备方法，其特征在于，所述第二纳米柱结构的顶表面上，量子点的厚度为1d-2d；
    所述第二纳米柱结构中，s 2、d满足：s 2≤d。
  11. 如权利要求9所述的量子点发光二极管的制备方法，其特征在于，所述l 2为2nm~20nm。
  12. 如权利要求1至11任一项所述的量子点发光二极管的制备方法，其特征在于，在所述底电极基板的底电极表面形成第一纳米柱结构的方法：对所述底电极基板上的底电极进行刻蚀处理。
  13. 如权利要求12所述的量子点发光二极管的制备方法，其特征在于，对所述底电极基板上的底电极进行刻蚀处理的步骤，包括：
    在所述底电极基板的底电极上制备单层聚苯乙烯纳米球薄膜；
    对所述单层聚苯乙烯纳米球薄膜中的聚苯乙烯纳米球进行RIE刻蚀处理，在聚苯乙烯纳米球之间形成间隙；
    以聚苯乙烯纳米球作为掩膜，对底电极进行刻蚀处理，去除所述聚苯乙烯纳米球，制备得到具有第一纳米柱结构的底电极。
  14. 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，在所述底电极基板的底电极上制备单层聚苯乙烯纳米球薄膜的步骤包括：配置聚苯乙烯纳米球的质量百分浓度为0.1%~10%的聚苯乙烯纳米球的混悬液，且所述混悬液中的溶剂为去离子水和乙醇的混合溶剂。
  15. 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，所述单层聚苯乙烯纳米球薄膜中，聚苯乙烯纳米球的直径为100nm~1000nm。
  16. 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，对底电极进行刻蚀处理的步骤中，采用无机酸刻蚀液对底电极进行刻蚀处理。
  17. 如权利要求16所述的量子点发光二极管的制备方法，其特征在于，所述无机酸刻蚀液中，添加有铁盐、亚铁盐和丙酮中的至少一种。
  18. 如权利要求12所述的量子点发光二极管的制备方法，其特征在于，对所述底电极基板上的底电极进行刻蚀处理的步骤，包括：
    提供具有与所述第一纳米柱结构互补的微纳结构的压印模板；
    在所述底电极上形成光刻胶，并采用所述压印模板对所述光刻胶进行压印处理，得到表面形成微纳结构的光刻胶层；
    对具有纳米柱结构的光刻胶层进行刻蚀，将纳米柱结构转移至所述底电极表面，制备得到具有第一纳米柱结构的底电极。
  19. 如权利要求1至11、13至18任一项所述的量子点发光二极管的制备方法，其特征在于，所述初始配体中的碳原子数大于所述目标配体中的碳原子数。
  20. 如权利要求1至11、13至18任一项所述的量子点发光二极管的制备方法，其特征在于，所述制备方法还包括：在量子点薄膜背离所述底电极的表面，制备顶电极；或在量子点薄膜背离所述底电极的表面，制备第二功能层，在第二功能层背离所述量子点薄膜的表面制备顶电极。
  21. 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，以及设置在所述阳极和所述阴极之间的量子点薄膜，其中，所述阳极或所述阴极的表面设置第一纳米柱结构，且所述量子点薄膜与所述第一纳米柱结构接触的表面与所述第一纳米柱结构互补，所述量子点薄膜的另一表面为平整表面其中，量子点的直径标记为d，相邻的第一纳米柱之间的间距标记为l 1，第一纳米柱的高度标记为h，第一纳米柱的最大径向尺寸标记为s 1，相邻的三个所述第一纳米柱的共同外接圆的半径标记为r 1。
  22. 如权利要求21所述的量子点发光二极管，其特征在于，所述d、l 1满足：d≤l 1＜2d；或
    所述d、l 1满足：l 1＜d，且所述r 1、d满足：d≤2r 1＜2d。
  23. 如权利要求21所述的量子点发光二极管，其特征在于，所述l 1为2nm~20nm。
  24. 如权利要求21至23任一项所述的量子点发光二极管，其特征在于，所述第一纳米柱结构中，h、d满足：d≤h≤5d。
  25. 如权利要求24所述的量子点发光二极管，其特征在于，所述h、d的关系满足：3d≤h≤4d。
  26. 如权利要求21至23任一项所述的量子点发光二极管，其特征在于，所述第一纳米柱结构中，s 1、d满足：s 1≤d。
  27. 如权利要求21至23任一项所述的量子点发光二极管，其特征在于，所述第一纳米柱结构的顶表面上，量子点的厚度为1d-2d。
  28. 如权利要求21所述的量子点发光二极管，其特征在于，在所述阳极和所述量子点薄膜之间设置空穴功能层，且当所述阳极设置第一纳米柱结构时，所述空穴功能层设置有与所述第一纳米柱结构对应的第二纳米柱结构；相邻的第二纳米柱之间的间距标记为l 2，第二纳米柱的最大径向尺寸标记为s 2，相邻的三个所述第二纳米柱的共同外接圆的半径标记为r 2，所述l 1、l 2满足：l 2＜l 1；所述s 1、s 2满足：s 1＜s 2；或
    在所述阴极和所述量子点薄膜之间设置电子功能层，且当所述阴极设置第一纳米柱结构时，所述电子功能层设置有与所述第一纳米柱结构对应的第二纳米柱结构；相邻的第二纳米柱之间的间距标记为l 2，第二纳米柱的最大径向尺寸标记为s 2，所述l 1、l 2满足：l 2＜l 1；所述s 1、s 2满足：s 1＜s 2。
  29. 如权利要求28所述的量子点发光二极管，其特征在于，所述d、l 2满足：d≤l 2＜2d；或
    所述d、l 2满足：l 2＜d，且所述r 2、d满足：d≤2r 2＜2d。
  30. 如权利要求29所述的量子点发光二极管，其特征在于，所述l 2为2nm~20nm；和/或
    所述第二纳米柱结构的顶表面上，量子点的厚度为1d-2d；和/或
    所述第二纳米柱结构中，s 2、d满足：s 2≤d。
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105845791A (zh) * 2016-05-30 2016-08-10 广东技术师范学院 一种高效率纳米结构led及其设计和制备方法
CN106206972A (zh) * 2016-09-05 2016-12-07 Tcl集团股份有限公司 量子点发光层制备方法、量子点发光二极管及制备方法
CN108463744A (zh) * 2015-12-31 2018-08-28 沙特基础工业全球技术公司 用于提高oled照明的提取效率的多功能分级纳米和微透镜

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007098451A1 (en) * 2006-02-17 2007-08-30 Solexant Corporation Nanostructured electroluminescent device and display
CN101830430B (zh) * 2010-05-24 2013-03-27 山东大学 一种大面积、高度均匀有序量子点阵列制造方法
KR20120057298A (ko) * 2010-11-26 2012-06-05 서울옵토디바이스주식회사 발광 소자 및 그 제조 방법
CN102280545A (zh) * 2011-08-17 2011-12-14 中国科学院苏州纳米技术与纳米仿生研究所 硅基光发射器件及其制备方法
CN109427978B (zh) * 2017-08-22 2020-05-26 Tcl科技集团股份有限公司 一种qled器件及其制备方法
CN107565065A (zh) * 2017-08-24 2018-01-09 深圳市华星光电半导体显示技术有限公司 倒置型量子点发光二极管及其制作方法
CA2985254A1 (en) * 2017-11-14 2019-05-14 Vuereal Inc Integration and bonding of micro-devices into system substrate
CN109980052B (zh) * 2017-12-27 2020-11-17 Tcl科技集团股份有限公司 一种qled器件及其制备方法
CN108899430A (zh) * 2018-07-03 2018-11-27 京东方科技集团股份有限公司 一种量子点发光二极管及其制备方法、显示面板
CN110429096B (zh) * 2018-09-18 2021-11-12 广东聚华印刷显示技术有限公司 显示器件

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108463744A (zh) * 2015-12-31 2018-08-28 沙特基础工业全球技术公司 用于提高oled照明的提取效率的多功能分级纳米和微透镜
CN105845791A (zh) * 2016-05-30 2016-08-10 广东技术师范学院 一种高效率纳米结构led及其设计和制备方法
CN106206972A (zh) * 2016-09-05 2016-12-07 Tcl集团股份有限公司 量子点发光层制备方法、量子点发光二极管及制备方法

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