WO2021258885A1 - 量子点发光面板、显示装置和制作方法 - Google Patents

量子点发光面板、显示装置和制作方法 Download PDF

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WO2021258885A1
WO2021258885A1 PCT/CN2021/093331 CN2021093331W WO2021258885A1 WO 2021258885 A1 WO2021258885 A1 WO 2021258885A1 CN 2021093331 W CN2021093331 W CN 2021093331W WO 2021258885 A1 WO2021258885 A1 WO 2021258885A1
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layer
quantum dot
emitting
light
dot light
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PCT/CN2021/093331
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English (en)
French (fr)
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张爱迪
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京东方科技集团股份有限公司
北京京东方技术开发有限公司
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Priority to US17/762,000 priority Critical patent/US20220344605A1/en
Publication of WO2021258885A1 publication Critical patent/WO2021258885A1/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
    • H10K71/20—Changing the shape of the active layer in the devices, e.g. patterning
    • H10K71/231—Changing the shape of the active layer in the devices, e.g. patterning by etching of existing layers
    • H10K71/233—Changing the shape of the active layer in the devices, e.g. patterning by etching of existing layers by photolithographic etching
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/30—Devices specially adapted for multicolour light emission
    • H10K59/35—Devices specially adapted for multicolour light emission comprising red-green-blue [RGB] subpixels
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/30—Devices specially adapted for multicolour light emission
    • H10K59/38—Devices specially adapted for multicolour light emission comprising colour filters or colour changing media [CCM]
    • 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
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • 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]
    • H10K50/18—Carrier blocking layers

Definitions

  • the present disclosure relates to the field of display technology, and in particular to a quantum dot light-emitting panel, a display device and a manufacturing method.
  • Quantum dots are an important fluorescent nanomaterial.
  • the use of quantum dots as light-emitting layer materials in the fields of flat panel lighting and optoelectronic displays has attracted more and more attention from academia and industry.
  • the external quantum efficiency (EQE) of quantum dot light emitting diodes (Quantum Dot Light Emitting Diodes, QLED) has reached more than 20%.
  • EQE quantum dot Light emitting diodes
  • QLED Quantum Dot Light Emitting Diodes
  • the patterning process of quantum dots in the light-emitting layer is a key step in determining full-color, high-resolution QLED devices.
  • there have been methods such as transfer, inkjet printing, and photolithography to realize the patterning process of quantum dots.
  • photolithography is usually used to realize the patterning of electronic materials (quantum dots).
  • Photolithography requires the help of photoresist.
  • the photoresist includes positive photoresist and negative photoresist.
  • the photoresist process forms patterned quantum dots of different colors, there is a problem that the quantum dot film layer is damaged, and the luminous efficiency of the quantum dot light-emitting panel is affected.
  • the present disclosure provides a quantum dot light-emitting panel, which includes:
  • a cathode layer, the cathode layer is located on one side of the base substrate;
  • An electron transport layer is located on the side of the cathode layer away from the base substrate;
  • a quantum dot light-emitting layer is located on a side of the electron transport layer away from the cathode layer, and has at least two light-emitting parts with different light-emitting wavelength ranges;
  • a photosensitive polymer film layer is located between the quantum dot light-emitting layer and the electron transport layer, and has a photosensitive portion corresponding to each of the light-emitting portions one-to-one, the photosensitive polymer film layer It is configured to break the molecular chain when irradiated by preset light;
  • the anode layer is located on the side of the quantum dot light-emitting layer away from the photosensitive polymer film layer.
  • the electron mobility of the photosensitive polymer film layer is lower than the electron mobility of the electron transport layer.
  • the electron transport layer and the photosensitive polymer film layer are connected by a covalent bond.
  • the electron transport layer has a hydroxyl group
  • the photosensitive polymer film layer has an amino group
  • the electron transport layer and the photosensitive polymer film layer are formed by the hydroxyl group and the amino group. The covalent bond.
  • the electron transport layer is a metal oxide.
  • the material of the metal oxide is zinc oxide, magnesium zinc oxide, or aluminum oxide zinc.
  • the photosensitive part further has one or a combination of the following covalent bonds:
  • the C-C bond, the C-O bond, the ester bond and the thioester bond are covalently broken when irradiated with the predetermined light.
  • the material of the photosensitive part is:
  • n is the number of structural units, 1 ⁇ m ⁇ 100.
  • the X functional group is one of the following:
  • the material of the photosensitive part is:
  • n is the number of structural units, 1 ⁇ n ⁇ 100.
  • the thickness of the light-emitting part is 30 nm to 60 nm.
  • a hole transport layer is further provided between the quantum dot light-emitting layer and the anode layer; a hole injection layer is further provided between the hole transport layer and the anode layer.
  • the embodiment of the present disclosure further provides a display device, which includes the quantum dot light-emitting panel provided in the embodiment of the present disclosure.
  • the embodiment of the present disclosure also provides a method for manufacturing a quantum dot light-emitting panel, including:
  • a quantum dot light-emitting layer is formed on the side of the electron transport layer away from the cathode layer, and a photosensitive polymer film layer is formed between the quantum dot light-emitting layer and the electron transport layer, wherein the quantum dots
  • the light-emitting layer has at least two light-emitting parts with different light emitting wavelength ranges
  • the photosensitive polymer film layer has a photosensitive part corresponding to each of the light-emitting parts one-to-one
  • the photosensitive polymer film layer is configured to be preset The molecular chain breaks when irradiated by light
  • An anode layer is formed on the side of the quantum dot light-emitting layer away from the photosensitive polymer film layer.
  • a quantum dot light-emitting layer is formed on the side of the electron transport layer away from the cathode layer, and a photosensitive polymer is formed between the quantum dot light-emitting layer and the electron transport layer Film layer, including:
  • the first area is blocked by a first mask, and a preset light is used to irradiate the molecular chains of the photosensitive polymer film that is not blocked by the first mask;
  • the second area is blocked by a second mask, and the preset light is used to irradiate the molecular chains of the photosensitive polymer film that are not blocked by the second mask and the first light-emitting part. Fracture, wherein the second area and the first area do not overlap each other;
  • the third area is blocked by a third mask, and the preset light is used to illuminate, so that the third mask, the first light-emitting portion and the second light-emitting portion are not blocked by The molecular chain of the photosensitive polymer film is broken, wherein the third area does not overlap with the first area and the second area;
  • the forming a photosensitive polymer film on a side of the electron transport layer away from the cathode layer includes:
  • the irradiating with preset light includes: irradiating with ultraviolet light.
  • the washing by solution includes: washing by absolute ethanol.
  • FIG. 1 is a schematic structural diagram of a quantum dot light-emitting panel provided by an embodiment of the disclosure
  • FIG. 2 is a schematic structural diagram of another quantum dot light-emitting panel provided by an embodiment of the disclosure.
  • Figure 3 is an enlarged schematic diagram of Figure 2 at position A;
  • FIG. 4 is a schematic diagram of a manufacturing process of a quantum dot light-emitting panel provided by an embodiment of the disclosure
  • FIG. 5 is a schematic diagram of the process of forming a patterned red quantum dot film according to an embodiment of the present disclosure
  • FIG. 6 is a schematic diagram of the process of forming a patterned green quantum dot film according to an embodiment of the present disclosure
  • FIG. 7 is a schematic diagram of the process of forming a patterned blue quantum dot film according to an embodiment of the disclosure.
  • the cost of negative photoresist is relatively low, but the developing solution usually uses p-xylene.
  • Organic solvents containing benzene are toxic and not conducive to environmental protection.
  • the positive photoresist has good contrast, so the generated pattern has good resolution, and the developer is an alkaline aqueous solution, which is beneficial to environmental protection, but the alkaline solution will damage the quantum dots of the light-emitting layer. Therefore, the development of a more compatible development process or a more environmentally friendly patterning process to prepare high-resolution, full-color QLEDs has become the focus and difficulty of quantum dot display technology research.
  • an embodiment of the present disclosure provides a quantum dot light-emitting panel, which includes:
  • the base substrate 1, and the base substrate 1 may specifically be a glass substrate;
  • the cathode layer 2, the cathode layer 2 is located on the side of the base substrate 1.
  • the material of the cathode layer 2 can be indium tin oxide semiconductor transparent conductive film (Indium tin oxide, ITO) or fluorine-doped SnO2 conductive glass ((SnO2:F, FTO), or indium zinc oxide (Indium Zinc Oxide, IZO), specifically, the cathode layer 2 may include a plurality of cathodes 20 spaced apart from each other;
  • the electron transport layer 3 is located on the side of the cathode layer 2 away from the base substrate 1; specifically, the electron transport layer 3 may include a plurality of electron transport parts 30 spaced apart from each other;
  • the wavelength range of the first light-emitting portion 51 may be 630 nm to 760 nm, and the light-emitting range of the second light-emitting portion 52 is 491 nm to 491 nm.
  • the wavelength range of the light emitted by the third light-emitting portion 53 is 450nm-490nm; specifically, a first light-emitting portion 51, a second light-emitting portion 52, and a third light-emitting portion 53 are arranged in sequence to form a pixel. Pixels are distributed in an array;
  • the photosensitive polymer film layer 4 the photosensitive polymer film layer 4 is located between the quantum dot light emitting layer 5 and the electron transport layer 3, has a photosensitive portion 41 corresponding to each light emitting portion 50 one-to-one, and the photosensitive polymer film layer 4 is configured as Molecular chain scission occurs when irradiated by preset light; specifically, the photosensitive polymer film layer 4 may be a polymer compound with a relative molecular mass of 20,000 to 50,000, which is formed by repeatedly connecting specific structural units through covalent bonds.
  • the photosensitive polymer film layer is a polymer compound that can break the molecular chain when irradiated by preset light (such as ultraviolet light); in addition, the photosensitive part 41 corresponds to the light-emitting part 50 one-to-one, which can be understood as each photosensitive
  • the orthographic projection of the part 41 on the base substrate 1 overlaps with the orthographic projection of a light-emitting part 50 on the base substrate 1. More specifically, the two can be overlapped in the center and have the same area.
  • the photosensitive part 41 and the light-emitting part 50 completely overlap with each other, and the two can be roughly overlapped in detail;
  • the anode layer 6 and the anode layer 6 are located on the side of the quantum dot light-emitting layer 5 away from the photosensitive polymer film layer 4.
  • a photosensitive polymer film 4 sensitive to ultraviolet light is introduced on the side of the electron transport layer 3 away from the base substrate 1, and then the quantum dot light-emitting layer 5 is introduced.
  • the mask is shielded and irradiated with preset light (such as ultraviolet light). Where the preset light is irradiated, the molecular chain of the photosensitive polymer film layer 4 is broken, which can be removed by washing with the first solution (such as ethanol solvent). Where the light is not irradiated by the preset light, the photosensitive polymer film layer 4 remains.
  • the electron mobility of the photosensitive polymer film layer 4 is lower than that of the electron transport layer 3, so that the photosensitive polymer film layer 4 can pattern the quantum dot light-emitting layer 5 at the same time. It can also function as an electron blocking layer, can effectively solve the problem of excessive injection rate of the electron transport layer (such as zinc oxide), regulate the carrier injection balance, and improve the luminous efficiency of the device.
  • the electron transport layer such as zinc oxide
  • the quantum dot light-emitting panel may further have a pixel definition layer, and the pixel definition layer includes a plurality of blocking portions 7 located between adjacent photosensitive portions 41 and between adjacent light-emitting portions 50.
  • the film layers of different light-emitting colors can be confined in different areas to form an independent structure.
  • a hole transport layer 81 between the quantum dot light-emitting layer 5 and the anode layer 6; a hole injection layer 82 is also provided between the hole transport layer 81 and the anode layer 6.
  • the material of the hole transport layer 81 may specifically be an organic material, and the material of the hole injection layer 82 may specifically be an organic material.
  • the hole transport layer 81, the hole injection layer 82, and the anode layer 6 may be a whole layer structure to simplify the process steps.
  • the electron transport layer 3 and the photosensitive polymer film layer 4 are connected by a covalent bond.
  • the electron transport layer 3 and the photosensitive polymer film layer 4 are connected by a covalent bond, which can enhance the binding force of the electron transport layer 3 and the photosensitive polymer film layer 4, and avoid the lack of molecular chains in the subsequent cleaning process. The broken photosensitive polymer film layer 4 is washed away.
  • the electron transport layer 3 has a hydroxyl group
  • the photosensitive polymer film layer 4 has an amino group
  • the electron transport layer 3 and the photosensitive polymer film layer 4 form a covalent bond through the hydroxyl group and the amino group, and the covalent bond may specifically be a hydrogen bond.
  • the electron transport layer is a metal oxide.
  • the material of the metal oxide may be zinc oxide, magnesium zinc oxide, or aluminum zinc oxide.
  • the metal oxide as the electron transport layer can have better electron transport performance, but the surface of the metal oxide is prone to form oxygen hole sites, which will quench the quantum dot light-emitting layer, and the photosensitive polymer
  • the film layer has amino groups. In addition to forming hydrogen bonds with the hydroxyl groups on the surface of the metal oxide, it has better bonding properties. The amino groups of the photosensitive polymer film layer can also eliminate oxygen vacancies on the surface of the metal oxide.
  • the electron transport layer 3 is zinc oxide.
  • the hydroxyl functional group (-OH) on the surface of the zinc oxide can form a hydrogen bond with the quaternary amino functional group on the photosensitive polymer compound, so that the electron transport layer 3 can be connected to the photosensitive polymer compound.
  • the polymer film layer 4 is more tightly bonded, which is beneficial to the adhesion of the photosensitive polymer film layer 4, wherein FIG. 3 is an enlarged schematic diagram of FIG. 2 at A.
  • the photosensitive portion 41 further has one or a combination of the following covalent bonds:
  • the material of the photosensitive portion 41 may be a polyetherimide-based compound or polyparaphenylene benzodioxazole.
  • the energy (365nm, equivalent to 3.39ev) of the preset light can be combined with the CC, CO, or the presence of the polyetherimide-based compound in the polyetheresterimide-based compound.
  • the existing ester bonds and thioester bonds and other covalent bonds have the same energy.
  • the photosensitive portion 41 may specifically be a polyetherimide-based compound, and the material of the polyetherimide-based compound may specifically be:
  • n is the number of structural units, 1 ⁇ m ⁇ 100.
  • X functional group is one of the following:
  • the photosensitive part 41 may also be a poly(p-phenylene benzodioxazole) compound, and the material of the poly(p-phenylene benzodioxazole) compound may specifically be:
  • n is the number of structural units, 1 ⁇ n ⁇ 100.
  • the thickness of the light-emitting part is 30nm-60nm. Under the condition that better light-emitting performance is satisfied, it can be used to block ultraviolet light during the patterning process of quantum dots of different colors. Specifically, for example, the patterned red quantum dot film is made first, then the patterned green quantum dot film is made, and then the blue quantum dot film is formed. For the patterned green quantum dot film, although the red quantum dot film has been formed The photosensitive part under the quantum dot film will be irradiated again, but because the thickness of the film at this stage is thicker (the thickness of the red light-emitting part is 30nm-60nm), the ultraviolet light energy reaching the photosensitive part under the red quantum dot film is higher.
  • the molecular chain of the photosensitive part under the red quantum dot film cannot be broken. Even when it is cleaned with absolute ethanol, the photosensitive part under the red quantum dot film will not be removed, and the red quantum dot film above it will not be removed. Will be removed; in the same way, when the patterned blue quantum dot film is formed, the green quantum dot film is thicker and will not be removed.
  • an embodiment of the present disclosure further provides a display device, which includes the quantum dot light-emitting panel provided by the embodiment of the present disclosure.
  • an embodiment of the present disclosure also provides a method for manufacturing a quantum dot light-emitting panel, which includes:
  • Step S100 providing a base substrate
  • Step S200 forming a cathode layer on one side of the base substrate
  • Step S300 forming an electron transport layer on the side of the cathode layer away from the base substrate;
  • Step S400 forming a quantum dot light emitting layer on the side of the electron transport layer away from the cathode layer, and forming a photosensitive polymer film layer between the quantum dot light emitting layer and the electron transport layer, wherein the quantum dot light emitting layer has at least two light emitting layers For light-emitting parts with different wavelength ranges, the photosensitive polymer film layer has a photosensitive part corresponding to each light-emitting part one-to-one, and the photosensitive polymer film layer is configured to cause molecular chain breaks when irradiated by a preset light;
  • Step S500 forming an anode layer on the side of the quantum dot light-emitting layer away from the photosensitive polymer film layer;
  • step S400 forming a quantum dot light-emitting layer on the side of the electron transport layer away from the cathode layer, and forming a photosensitive polymer film layer between the quantum dot light-emitting layer and the electron transport layer, includes:
  • the photosensitive polymer film may specifically be a polyetherimide-based compound, specifically, the polyetherimide-based compound may be dissolved in ethanol, And spin-coated on the side of the electron transport layer away from the cathode layer; heating to volatilize the solvent, thereby forming a photosensitive polymer film on the side of the electron transport layer away from the cathode layer;
  • the first quantum dot light-emitting film for example, may be a red quantum dot light-emitting film that emits red light;
  • the first area is shielded by the first mask, and a preset light is used to irradiate, so that the molecular chains of the photosensitive polymer film that are not blocked by the first mask are broken; the preset light is used for irradiation, specifically To use ultraviolet light for irradiation;
  • the photosensitive polymer film may specifically be a polyetherimide-based compound, specifically, the polyetherimide-based compound may be dissolved in ethanol, And spin-coated on the side of the electron transport layer away from the cathode layer; heating to volatilize the solvent, thereby forming a photosensitive polymer film on the side of the electron transport layer away from the cathode layer;
  • the second quantum dot light-emitting film may be a green quantum dot light-emitting film that emits green light;
  • the second area is shielded by the second mask, and a preset light is used to irradiate the molecular chains of the photosensitive polymer film that are not blocked by the second mask and the first light-emitting part.
  • the area and the first area do not overlap each other; the preset light is used for irradiation, specifically, ultraviolet light may be used for irradiation;
  • the photosensitive polymer film may specifically be a polyetherimide-based compound, specifically, the polyetherimide-based compound may be dissolved in ethanol, And spin-coated on the side of the electron transport layer away from the cathode layer; heating to volatilize the solvent, thereby forming a photosensitive polymer film on the side of the electron transport layer away from the cathode layer;
  • the third quantum dot light-emitting film may be a blue quantum dot light-emitting film that emits blue light;
  • the third area is shielded by the third mask, and preset light is used to irradiate, so that the molecular chains of the photosensitive polymer film that are not blocked by the third mask, the first light-emitting part and the second light-emitting part are broken , wherein, the third area does not overlap with the first area and the second area; the preset light is used for irradiation, specifically, ultraviolet light is used for irradiation;
  • the material of the electron transport layer may be zinc oxide nanoparticles or zinc oxide.
  • forming the electron transport layer on the side of the cathode layer away from the base substrate includes:
  • Step S301 forming a spin coating liquid including zinc oxide nanoparticles
  • Step S302 spin coating liquid on the side of the cathode layer away from the base substrate.
  • step S300 forming the electron transport layer on the side of the cathode layer away from the base substrate includes:
  • Step S303 dissolving zinc acetate or zinc nitrate in a mixed solution of ethanolamine and n-butanol to form a zinc-containing precursor fluid
  • Step S304 drop the zinc-containing precursor liquid onto the side of the cathode layer away from the base substrate for spin coating;
  • Step S305 heating to volatilize the solvent.
  • Step 1 Introduce red quantum dots in the red pixel area (first light-emitting part 51);
  • the conductive glass (the base substrate 1 on which the cathode layer 2 is formed, and the material of the cathode layer 2 can be ITO or FTO) respectively use water, isopropanol, ultrasonic cleaning, and UV UV treatment for 5 min- 10min.
  • the electron transport layer 3 can be a zinc oxide-based nanoparticle film or a zinc oxide film;
  • (a) Preparation of zinc oxide nanoparticle film for example, spin coating of zinc oxide nanoparticle, and then heat at 80°C-120°C to form a film.
  • the material of the electron transport layer 3 can also choose ion-doped zinc oxide nanoparticles, such as Mg, In, Al, Ga-doped magnesium oxide nanoparticles, etc.
  • the speed of the homogenizer is set to 500rpm-2500rpm to adjust the thickness of the film layer;
  • the photosensitive polymer film layer 4 rich in amino groups; dissolve 0.5 g of polyetherimide-based compound in 5 mL of ethanol, and add dropwise to the conductive glass, spin coating, and then place the conductive glass at 250 On a hot stage with a temperature of -300 degrees, the concurrent solvent is heated, and finally a zinc oxide film layer is introduced on the ITO glass.
  • the photosensitive polymer film layer 4 can also be selected from polyparaphenylene benzodioxazole and other ultraviolet-sensitive polymers;
  • Exposure of the mask the alignment adjustment of the mask and the conductive glass, the mask is used to block the red pixel area on the conductive glass, and the area except the red pixel area is exposed by ultraviolet rays;
  • Step 2 Introduce green quantum dots in the green pixel area (the second light-emitting part 52);
  • Mask exposure align the exposure machine and the conductive glass, and perform mask exposure on the conductive glass except for the green pixel area.
  • Step 3 Introduce blue quantum dots in the blue pixel area (third light-emitting part 53);
  • Step 4 Introduce a hole transport layer; on the above-mentioned conductive glass, a hole transport layer is spin-coated or vapor-deposited.
  • the organic material as the hole transport layer can choose TFB (poly(9,9-dioctylfluorene-co-N-(4-butylphenyl) diphenylamine)), or PVK (polyvinylcarbazole), or other commercial Chemical hole transport compounds and so on.
  • TFB spin coating film formation conditions are: 130-150 °C inert gas film formation. The thickness of the film can be adjusted according to the speed of the homogenizer;
  • Step 5 Introduce a hole injection layer; on the above-mentioned conductive glass, spin-coating or vapor-depositing the hole injection layer.
  • Organic substances can be selected as the hole injection layer PEDOT:PSS 4083 (poly 3,4-ethylenedioxythiophene/polystyrene sulfonate) or other commercial compounds suitable for the hole injection layer.
  • the spin coating film forming temperature of PEDOT is 130-150°C in air. The thickness of the film can be adjusted according to the speed of the homogenizer;
  • Step 6 introduce anode; finally, introduce anode material, such as vapor-deposited aluminum film, silver film or sputtered indium zinc oxide (IZO) film to prepare QLED devices;
  • anode material such as vapor-deposited aluminum film, silver film or sputtered indium zinc oxide (IZO) film to prepare QLED devices;
  • Step seven packaging; cover the packaging cover plate, and use ultraviolet curing glue to package the device to prepare a quantum dot light-emitting diode.
  • red, green, and blue quantum dots can be changed arbitrarily according to actual needs.
  • the thickness of the film at this stage at this position is thicker and reaches the red quantum dot
  • the ultraviolet light energy of the photosensitive part under the film is weak, so the molecular chain of the photosensitive part under the red quantum dot film cannot be broken.
  • the photosensitive part under the red quantum dot film will not be removed.
  • the red quantum dot film above it will not be removed; in the same way, the green quantum dot film will not be removed when the patterned blue quantum dot film is formed.
  • the quantum dot light-emitting panel provided by the embodiments of the present disclosure has structural feature 1:
  • the quantum dot light-emitting panel has a planar layered multi-layer superimposed structure (as shown in FIG. 2), and each functional layer from bottom to top is: a base substrate 1.
  • Cathode layer 2 electron transport layer 3 (zinc oxide), photosensitive polymer film layer 4, quantum dot light-emitting layer 5, hole transport layer 82, hole injection layer 84, anode 6; identification methods of each film layer:
  • Such a structure can be prepared by preparing cross-sectional slices of quantum dot light-emitting panels, and using high-resolution transmission electron microscopes and cross-sectional scanning electron microscopes (cross-sectional, SEM) for structure determination and composition analysis;
  • the quantum dot light-emitting panel has a typical structural feature 2: there is a specific photosensitive polymer film layer 3 (polyetherimide-based compound, or polymer pair) between the electron transport layer 3 (zinc oxide layer) and the quantum dot light-emitting layer 5 Phenylene benzobisoxazole), taking polyetherimide compound as an example, the hydroxyl functional group (-OH) on the surface of zinc oxide and the amino functional group on the molecular structure of the polyetherimide compound form a specific hydrogen bond structure , As shown in Figure 3; the thickness of the photosensitive polymer film layer 3 can be: 0.5nm-3nm; identification method: such structural features can be through Fourier infrared spectroscopy (FTIR) and secondary ion mass spectrometry (SIMS) determining structural determination and analysis, for example, the device may be a polyetherimide compound Fourier transform infrared spectroscopy (FTIR) characterized by characteristic peaks as follows: 1724cm -1 1778
  • the QLED device structure has typical structural characteristics 3: The size of the quantum dots in the quantum dot light-emitting layer 5 in the device is between 3nm-20nm; the embodiments of the present disclosure can be applied to a variety of quantum dots, specifically including: oil-soluble CdTe, CdS, CdSe, ZnSe, InP, CuInS, CuInSe, PbS, CdS/ZnS, CdSe/ZnS, CdSe/ZnSeS, CdSe/CdS, ZnSe/ZnS, InP/ZnS, CuInS/ZnS, (Zn)CuInS/ZnS, ( Mn) CuInS/ZnS, AgInS/ZnS, (Zn)AgInS/ZnS, CuInSe/ZnS, CuInSeS/ZnS, PbS/ZnS and other quantum dots; Quantum dot light-emitting layer 5 identification method: (1) The crystal
  • the quantum dot light-emitting panel provided by the embodiments of the present disclosure introduces a photosensitive polymer film sensitive to ultraviolet light on the side of the electron transport layer away from the base substrate, and then introduces the quantum dot light-emitting layer . After that, use a mask to block and irradiate with preset light (such as ultraviolet light). Where the preset light is irradiated, the molecular chain of the photosensitive polymer film is broken, and it can be washed with the first solution (such as ethanol solvent) Remove the place that is not irradiated by the preset light, and the photosensitive polymer film layer remains.
  • preset light such as ultraviolet light

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Abstract

本公开提供了一种量子点发光面板、显示装置和制作方法，所述量子点发光面板包括：衬底基板；阴极层，所述阴极层位于所述衬底基板的一侧；电子传输层，所述电子传输层位于所述阴极层的背离所述衬底基板的一侧；量子点发光层，所述量子点发光层位于所述电子传输层的背离所述阴极层的一侧，具有至少两种出光波长范围互不相同的发光部；感光高分子膜层，所述感光高分子膜层位于所述量子点发光层与所述电子传输层之间，具有与各所述发光部一一对应的感光部，所述感光高分子膜层被配置为受预设光照射时发生分子链断裂；阳极层，所述阳极层位于所述量子点发光层的背离所述感光高分子膜层的一侧。

Description

量子点发光面板、显示装置和制作方法
相关申请的交叉引用
本申请要求在2020年06月22日提交中国专利局、申请号为202010572243.8、申请名称为“量子点发光面板、显示装置和制作方法”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
本公开涉及显示技术领域，尤其涉及量子点发光面板、显示装置和制作方法。
背景技术
半导体量子点是一种重要的荧光纳米材料。将量子点作为发光层材料，应用于平板照明和光电显示领域，越来越受到学术界和工业界的关注。截止目前，在器件性能方面，量子点发光二极管(Quantum Dot Light Emitting Diodes，QLED)的外量子发光效率(External Quantum Efficiency，EQE)已经达到了20％以上。当前，发光层量子点的图形化工艺是决定全彩、高分辨QLED器件的关键步骤。目前已有转印，喷墨打印，以及光刻等方式实现量子点的图形化工艺。
在实际工业大生产角度，通常采用光刻方式实现电子材料(量子点)的图形化。光刻需要借助于光刻胶。光刻胶有正性光刻胶和负性光刻胶。但是光刻胶工艺在形成不同颜色的图案化量子点时，存在会损坏量子点膜层的问题，影响量子点发光面板的发光效率。
发明内容
本公开提供一种量子点发光面板，其中，包括：
衬底基板；
阴极层，所述阴极层位于所述衬底基板的一侧；
电子传输层，所述电子传输层位于所述阴极层的背离所述衬底基板的一侧；
量子点发光层，所述量子点发光层位于所述电子传输层的背离所述阴极层的一侧，具有至少两种出光波长范围互不相同的发光部；
感光高分子膜层，所述感光高分子膜层位于所述量子点发光层与所述电子传输层之间，具有与各所述发光部一一对应的感光部，所述感光高分子膜层被配置为受预设光照射时发生分子链断裂；
阳极层，所述阳极层位于所述量子点发光层的背离所述感光高分子膜层的一侧。
在一种可能的实施方式中，所述感光高分子膜层的电子迁移率低于所述电子传输层的电子迁移率。
在一种可能的实施方式中，各所述感光部之间均具有阻挡部。
在一种可能的实施方式中，所述电子传输层和所述感光高分子膜层通过共价键连接。
在一种可能的实施方式中，所述电子传输层具有羟基，所述感光高分子膜层具有氨基，所述电子传输层和所述感光高分子膜层通过所述羟基和所述氨基形成所述共价键。
在一种可能的实施方式中，所述电子传输层为金属氧化物。
在一种可能的实施方式中，所述金属氧化物的材料为氧化锌，氧化镁锌，或氧化铝锌。
在一种可能的实施方式中，所述感光部还具有以下共价键之一或组合：
C-C键；
C-O键；
酯键；
硫酯键；
其中，所述C-C键，所述C-O键，所述酯键以及所述硫酯键在所述预设光照射时发生共价键断裂。
在一种可能的实施方式中，所述感光部的材料为：
Figure PCTCN2021093331-appb-000001
其中，m为结构单元的个数，1<m<100。
在一种可能的实施方式中，X官能团为以下之一：
Figure PCTCN2021093331-appb-000002
在一种可能的实施方式中，所述感光部的材料为：
Figure PCTCN2021093331-appb-000003
其中，n为结构单元的个数，1<n<100。
在一种可能的实施方式中，所述发光部的厚度为30nm～60nm。
在一种可能的实施方式中，所述量子点发光层与所述阳极层之间还具有空穴传输层；所述空穴传输层与所述阳极层之间还具有空穴注入层。
本公开实施例还提供一种显示装置，其中，包括如本公开实施例提供的所述量子点发光面板。
本公开实施例还提供一种量子点发光面板的制作方法，包括：
提供一衬底基板；
在所述衬底基板的一侧形成阴极层；
在所述阴极层的背离所述衬底基板的一侧形成电子传输层；
在所述电子传输层的背离所述阴极层的一侧形成量子点发光层，以及在所述量子点发光层与所述电子传输层之间形成感光高分子膜层，其中，所述量子点发光层具有至少两种出光波长范围互不相同的发光部，所述感光高分子膜层具有与各所述发光部一一对应的感光部，所述感光高分子膜层被配置为受预设光照射时发生分子链断裂；
在所述量子点发光层的背离所述感光高分子膜层的一侧形成阳极层。
在一种可能的实施方式中，在所述电子传输层的背离所述阴极层的一侧形成量子点发光层，以及在所述量子点发光层与所述电子传输层之间形成感光高分子膜层，包括：
在所述电子传输层的背离所述阴极层的一侧形成感光高分子薄膜；
在所述感光高分子薄膜的背离所述电子传输层的一侧形成第一量子点发光薄膜；
通过第一掩膜板对第一区域遮挡，采用预设光进行照射，以使未被所述第一掩膜板遮挡的所述感光高分子薄膜的分子链断裂；
通过溶液清洗，去除分子链断裂的所述感光高分子薄膜及上方的所述第一量子点发光薄膜，形成第一发光部；
在所述电子传输层的背离所述阴极层的一侧形成感光高分子薄膜；
在所述感光高分子薄膜的背离所述电子传输层的一侧形成第二量子点发光薄膜；
通过第二掩膜板对第二区域遮挡，采用所述预设光进行照射，以使未被所述第二掩膜板以及所述第一发光部遮挡的所述感光高分子薄膜的分子链断裂，其中，所述第二区域与所述第一区域互不交叠；
通过溶液清洗，去除分子链断裂的所述感光高分子薄膜及上方的所述第二量子点发光薄膜，形成第二发光部；
在所述电子传输层的背离所述阴极层的一侧形成感光高分子薄膜；
在所述感光高分子薄膜的背离所述电子传输层的一侧形成第三量子点发光薄膜；
通过第三掩膜板对第三区域遮挡，采用所述预设光进行照射，以使未被所述第三掩膜板、所述第一发光部和所述第二发光部遮挡的所述感光高分子薄膜的分子链断裂，其中，所述第三区域与所述第一区域、所述第二区域互不交叠；
通过溶液清洗，去除分子链断裂的所述感光高分子薄膜及上方的所述第三量子点发光薄膜，形成第三发光部。
在一种可能的实施方式中，所述在所述电子传输层的背离所述阴极层的一侧形成感光高分子薄膜，包括：
将聚醚酰亚胺基化合物或聚对苯撑苯并二噁唑溶于乙醇，并旋涂于所述电子传输层的背离所述阴极层的一侧；
加热以挥发溶剂。
在一种可能的实施方式中，所述采用预设光进行照射，包括：并采用紫外光进行照射。
在一种可能的实施方式中，所述通过溶液清洗，包括：通过无水乙醇进行冲洗。
附图说明
图1为本公开实施例提供的一种量子点发光面板的结构示意图；
图2为本公开实施例提供的另一种量子点发光面板的结构示意图；
图3为图2在位置A处的放大示意图；
图4为本公开实施例提供的一种量子点发光面板的制作流程示意图；
图5为本公开实施例形成图案化的红色量子点膜时的流程示意图；
图6为本公开实施例形成图案化的绿色量子点膜时的流程示意图；
图7为本公开实施例形成图案化的蓝色量子点膜时的流程示意图。
具体实施方式
为了使得本公开实施例的目的、技术方案和优点更加清楚，下面将结合本公开实施例的附图，对本公开实施例的技术方案进行清楚、完整地描述。显然，所描述的实施例是本公开的一部分实施例，而不是全部的实施例。基于所描述的本公开的实施例，本领域普通技术人员在无需创造性劳动的前提下所获得的所有其他实施例，都属于本公开保护的范围。
除非另外定义，本公开使用的技术术语或者科学术语应当为本公开所属领域内具有一般技能的人士所理解的通常意义。本公开中使用的“第一”、“第二”以及类似的词语并不表示任何顺序、数量或者重要性，而只是用来区分不同的组成部分。“包括”或者“包含”等类似的词语意指出现该词前面的元件或者物件涵盖出现在该词后面列举的元件或者物件及其等同，而不排除其他元件或者物件。“连接”或者“相连”等类似的词语并非限定于物理的或者机械的连接，而是可以包括电性的连接，不管是直接的还是间接的。“上”、“下”、“左”、“右”等仅用于表示相对位置关系，当被描述对象的绝对位置改变后，则该相对位置关系也可能相应地改变。
为了保持本公开实施例的以下说明清楚且简明，本公开省略了已知功能和已知部件的详细说明。
采用光刻胶方式实现电子材料(量子点)的图形化时，会存在以下问题：
负性光刻胶成本较低，但是显影液通常采用对二甲苯，含苯类有机溶剂有毒，并不利于环保。正性光刻胶具有很好的对比度，所以生成的图形具有良好的分辨率，并且显影液为碱性水溶液，有利于环保，但是，碱液会破坏发光层量子点。因此，发展更加亲和的显影工艺或更环保的图案化工艺，制备高分辨、全彩QLED已经成为量子点显示工艺研究的重点和难点。
有鉴于此，参见图1，本公开实施例提供一种量子点发光面板，其中，包括：
衬底基板1，衬底基板1具体可以为玻璃衬底基板；
阴极层2，阴极层2位于衬底基板的1一侧，具体的，阴极层2的材料具 体可以为铟锡氧化物半导体透明导电膜(Indium tin oxide，ITO)，也可以为掺杂氟的SnO2导电玻璃((SnO2:F，FTO)，也可以为氧化铟锌(Indium Zinc Oxide，IZO)，具体的，阴极层2可以包括多个相互间隔的阴极20；
电子传输层3，电子传输层3位于阴极层2的背离衬底基板1的一侧；具体的，电子传输层3可以包括多个相互间隔的电子传输部30；
量子点发光层5，量子点发光层5位于电子传输层3的背离阴极层2的一侧，具有至少两种出光波长范围互不相同的发光部50；例如，具体可以包括出射红光的第一发光部51，出射绿光的第二发光部52，出射蓝光的第三发光部53，第一发光部51的出光波长范围可以为630nm～760nm，第二发光部52的出光范围为491nm～560nm、第三发光部53出射的光的波长范围为450nm～490nm；具体的，一个第一发光部51、一个第二发光部52、一个第三发光部53依次排列，可以组成一个像素，多个像素呈阵列分布；
感光高分子膜层4，感光高分子膜层4位于量子点发光层5与电子传输层3之间，具有与各发光部50一一对应的感光部41，感光高分子膜层4被配置为受预设光照射时发生分子链断裂；具体的，感光高分子膜层4具体可以为由特定的结构单元通过共价键多次重复连接而形成的相对分子质量在20000～50000的高分子化合物，且该种感光高分子膜层在受预设光(如紫外光)照射时可以发生分子链断裂的高分子化合物；另外，感光部41与发光部50一一对应，可以理解为每一感光部41在衬底基板1上的正投影与一发光部50在衬底基板1的正投影重叠，更为具体的，二者可以为中心重合，面积相等的重合关系，当然，考虑到实际的工艺误差，要求感光部41与发光部50完全重合难度较大，二者具体可以为大致重合；
阳极层6，阳极层6位于量子点发光层5的背离感光高分子膜层4的一侧。
本公开实施例提供的量子点发光面板，通过在电子传输层3的背离衬底基板1的一侧引入一层对紫外线敏感的感光高分子薄膜4，再引入量子点发光层5，之后，采用掩膜版遮挡，并进行预设光(如紫外光)照射，有预设光照射的地方，感光高分子膜层4的分子链发生断裂，可以通过第一溶液(如乙 醇溶剂)冲洗去除，未被预设光照射的地方，感光高分子膜层4保留下来，通过重复以上步骤，就可以实现多种出光范围不同的发光部50的图形化，进而可以实现全彩，高分辨率的量子点面板的制作，且形成全彩化量子点显示面板的过程中，不需要使用对量子点膜层有损害的显影液，进而可以避免实现全彩化面板的制作过程中，量子点发光层5受损，影响量子点发光面板的发光效率的问题。
在具体实施时，感光高分子膜层4的电子迁移率低于电子传输层3的电子迁移率，进而可以使感光高分子膜层4在可以实现对量子点发光层5进行图案化的同时，还可以起到电子阻挡层的作用，可以有效解决电子传输层(如氧化锌)注入速率过大的问题，调控载流子注入平衡，提升器件发光效率。
在具体实施时，参见图2所示，各感光部41之间均具有阻挡部7。本公开实施例中，量子点发光面板还可以具有像素定义层，像素定义层包括多个阻挡部7，该阻挡部7位于相邻感光部41之间，也位于相邻发光部50之间，可以将不同出光颜色的膜层限定在不同的区域内，形成一独立的结构。
在具体实施时，结合图2所示，量子点发光层5与阳极层6之间还具有空穴传输层81；空穴传输层81与阳极层6之间还具有空穴注入层82。空穴传输层81的材料具体可以为有机材料，空穴注入层82的材料具体可以为有机材料。具体的，空穴传输层81，空穴注入层82，以及阳极层6可以为一整层结构，以简化工艺步骤。
在具体实施时，电子传输层3和感光高分子膜层4通过共价键连接。本公开实施例中，电子传输层3和感光高分子膜层4通过共价键连接，可以增强电子传输层3和感光高分子膜层4的结合力，避免在后续清洗过程中，分子链没有断裂的感光高分子膜层4被清洗掉。
具体的，电子传输层3具有羟基，感光高分子膜层4具有氨基，电子传输层3和感光高分子膜层4通过羟基和氨基形成共价键，该共价键具体可以为氢键。
在具体实施时，电子传输层为金属氧化物。具体的，金属氧化物的材料 可以为氧化锌，氧化镁锌，或氧化铝锌。本公开实施例中，金属氧化物作为电子传输层，可以具有较优的电子传输性能，但金属氧化物的表面易于形成氧空穴位点，会对量子点发光层产生淬灭，而感光高分子膜层具有氨基，除可以与金属氧化物表面的羟基形成氢键，具有较佳的结合性能外，感光高分子膜层的氨基还可以对金属氧化物表面的氧空穴位点进行消除，进而可以降低金属氧化物对量子点发光层的淬灭作用，进而可以提升量子点发光面板的性能。具体的，参见图3所示，电子传输层3为氧化锌，氧化锌表面的羟基官能团(-OH)可以和感光高分子化合物上面的季氨基官能团形成氢键，可以使电子传输层3与感光高分子膜层4的结合更为紧密，有利于感光高分子膜层4的附着，其中，图3为图2在A处的放大示意图。
在具体实施时，感光部41感光部还具有以下共价键之一或组合：
C-C键；
C-O键；
酯键；
硫酯键；
其中，C-C键，C-O键，酯键以及硫酯键在预设光照射时发生共价键断裂。具体的，感光部41的材料可以为聚醚酰亚胺基化合物，或聚对苯撑苯并二噁唑。本公开实施例中，预设光(如紫外光)的能量(365nm，相当于3.39ev)可与聚醚酰亚胺基化合物中存在的C-C，C-O，或，聚醚酯亚胺基化合物中存在的酯键以及硫酯键等共价键能量相当，当这些共价键吸收特定波长的紫外辐照后将发生共价键断裂，形成大量具有强化学活性的带电高分子自由基，自由基通过重组而产生分子链断裂。断裂的感光高分子膜层在醇类溶剂的冲洗并被去除。
在具体实施时，感光部41具体可以为聚醚酰亚胺基化合物，聚醚酰亚胺基化合物的材料具体可以为：
Figure PCTCN2021093331-appb-000004
其中，m为结构单元的个数，1<m<100。具体的，X官能团为以下之一：
Figure PCTCN2021093331-appb-000005
在具体实施时，感光部41具体也可以为聚对苯撑苯并二噁唑化合物，聚对苯撑苯并二噁唑化合物的材料具体可以为：
Figure PCTCN2021093331-appb-000006
其中，n为结构单元的个数，1<n<100。
在一种可能的实施方式中，发光部的厚度为30nm～60nm，在满足较佳的发光性能的情形下，可以在对不同颜色的量子点进行图案化过程中，可以起到遮挡紫外光的作用，具体的，例如，先制作图案化的红色量子点薄膜，再制作图案化的绿色量子点薄膜，再形成蓝色量子点薄膜时，对于图案化绿色量子点薄膜时，尽管已形成的红色量子点膜下方的感光部会被再次照射，但由于该位置在该阶段的膜层厚度较厚(红色发光部的厚度为30nm～60nm)，到达红色量子点膜下方的感光部的紫外光能量较弱，因此，无法使红色量子点膜下方的感光部的分子链断裂，即使用无水乙醇清洗时，红色量子点膜下方的感光部也不会被去除，其上方的红色量子点膜也不会被去除；同理，在 形成图案化的蓝色量子点膜时，绿色量子点膜较厚也不会被去除。
基于同一发明构思，本公开实施例还提供一种显示装置，其中，包括如本公开实施例提供的量子点发光面板。
基于同一发明构思，参见图4所示，本公开实施例还提供一种量子点发光面板的制作方法，其中，包括：
步骤S100、提供一衬底基板；
步骤S200、在衬底基板的一侧形成阴极层；
步骤S300、在阴极层的背离衬底基板的一侧形成电子传输层；
步骤S400、在电子传输层的背离阴极层的一侧形成量子点发光层，以及在量子点发光层与电子传输层之间形成感光高分子膜层，其中，量子点发光层具有至少两种出光波长范围互不相同的发光部，感光高分子膜层具有与各发光部一一对应的感光部，感光高分子膜层被配置为受预设光照射时发生分子链断裂；
步骤S500、在量子点发光层的背离感光高分子膜层的一侧形成阳极层；
其中，步骤S400、在电子传输层的背离阴极层的一侧形成量子点发光层，以及在量子点发光层与电子传输层之间形成感光高分子膜层，包括：
S411、在电子传输层的背离阴极层的一侧形成感光高分子薄膜；感光高分子薄膜具体可以为聚醚酰亚胺基化合物，具体的，可以将聚醚酰亚胺基化合物溶于乙醇，并旋涂于电子传输层的背离阴极层的一侧；加热以挥发溶剂，进而实现在电子传输层的背离阴极层的一侧形成感光高分子薄膜；
S412、在感光高分子薄膜的背离电子传输层的一侧形成第一量子点发光薄膜；第一量子点发光薄膜，例如，可以为出射红光的红色量子点发光薄膜；
S413、通过第一掩膜板对第一区域遮挡，采用预设光进行照射，以使未被第一掩膜板遮挡的感光高分子薄膜的分子链断裂；采用预设光进行照射，具体可以为采用紫外光进行照射；
S414、通过溶液清洗，去除分子链断裂的感光高分子薄膜及上方的第一量子点发光薄膜，形成第一发光部；通过溶液清洗，具体可以为通过无水乙 醇进行冲洗；
S415、在电子传输层的背离阴极层的一侧形成感光高分子薄膜；感光高分子薄膜具体可以为聚醚酰亚胺基化合物，具体的，可以将聚醚酰亚胺基化合物溶于乙醇，并旋涂于电子传输层的背离阴极层的一侧；加热以挥发溶剂，进而实现在电子传输层的背离阴极层的一侧形成感光高分子薄膜；
S416、在感光高分子薄膜的背离电子传输层的一侧形成第二量子点发光薄膜；第二量子点发光薄膜，例如，可以为出射绿光的绿色量子点发光薄膜；
S417、通过第二掩膜板对第二区域遮挡，采用预设光进行照射，以使未被第二掩膜板以及第一发光部遮挡的感光高分子薄膜的分子链断裂，其中，第二区域与第一区域互不交叠；采用预设光进行照射，具体可以为采用紫外光进行照射；
S418、通过溶液清洗，去除分子链断裂的感光高分子薄膜及上方的第二量子点发光薄膜，形成第二发光部；通过溶液清洗，具体可以为通过无水乙醇进行冲洗；
S419、在电子传输层的背离阴极层的一侧形成感光高分子薄膜；感光高分子薄膜具体可以为聚醚酰亚胺基化合物，具体的，可以将聚醚酰亚胺基化合物溶于乙醇，并旋涂于电子传输层的背离阴极层的一侧；加热以挥发溶剂，进而实现在电子传输层的背离阴极层的一侧形成感光高分子薄膜；
S420、在感光高分子薄膜的背离电子传输层的一侧形成第三量子点发光薄膜；第三量子点发光薄膜，例如，可以为出射蓝光的蓝色量子点发光薄膜；
S421、通过第三掩膜板对第三区域遮挡，采用预设光进行照射，以使未被第三掩膜板、第一发光部和第二发光部遮挡的感光高分子薄膜的分子链断裂，其中，第三区域与第一区域、第二区域互不交叠；采用预设光进行照射，具体可以为采用紫外光进行照射；
S422、通过溶液清洗，去除分子链断裂的感光高分子薄膜及上方的第三量子点发光薄膜，形成第三发光部；通过溶液清洗，具体可以为通过无水乙醇进行冲洗。
在具体实施时，电子传输层的材料可以为氧化锌纳米粒子或氧化锌。
对于电子传输层的材料为氧化锌纳米粒子时，对于步骤S300、在阴极层的背离衬底基板的一侧形成电子传输层，包括：
步骤S301、形成包括氧化锌纳米粒子的旋涂液；
步骤S302、将旋涂液旋涂于阴极层的背离衬底基板的一侧。
对于电子传输层的材料为氧化锌时，对于步骤S300、在阴极层的背离衬底基板的一侧形成电子传输层，包括：
步骤S303、将醋酸锌或者硝酸锌等溶于乙醇胺和正丁醇的混合溶液中，形成含锌前驱体液；
步骤S304、将含锌前驱体液滴加到阴极层的背离衬底基板的一侧，进行旋涂；
步骤S305、加热以挥发溶剂。
以下结合图5-图7所示，对本公开实施例提供的量子点发光面板的制作方法进行进一步详细说明如下：
步骤一、红色像素区引入红色量子点(第一发光部51)；
(1)、清洗；将导电玻璃(形成有阴极层2的衬底基板1，阴极层2的材料具体可以为ITO或FTO)分别采用水，异丙醇，超声清洗，并紫外UV处理5min-10min。
(2)、引入电子传输层3；电子传输层3可以是氧化锌基纳米粒子薄膜或氧化锌薄膜；
(a)、制备氧化锌纳米粒子薄膜；例如，旋涂氧化锌纳米粒子，之后并在80℃-120℃加热成膜。电子传输层3材料还可以选择离子掺杂型氧化锌纳米粒子，如Mg，In，Al，Ga掺杂氧化镁纳米粒子等，匀胶机转速设置为500rpm-2500rpm，以调整膜层的厚度；
(b)、制备氧化锌薄膜；将2g醋酸锌(或者硝酸锌等)溶于10mL乙醇胺和正丁醇的混合溶液中，将上述导电玻璃置于匀胶机，将90μL-120μL锌的前驱体溶液滴加到导电玻璃上，旋涂。将上述导电玻璃置于250度-300 度的热台上，加热并发溶剂，在上述导电玻璃上引入聚醚酰亚胺膜层；
(3)、引入富含氨基的感光高分子膜层4；将0.5g聚醚酰亚胺基化合物溶于5mL乙醇，并滴加到上述导电玻璃，旋涂，之后将上述导电玻璃置于250度-300度的热台上，加热并发溶剂，最终在ITO玻璃上引入氧化锌膜层。此步中的感光高分子膜层4还可以选择聚对苯撑苯并二噁唑等对紫外线感光的高分子；
(4)、旋涂红色量子点；将红色量子点的低沸点溶液(氯仿、甲苯、正己烷、正辛烷、或正庚烷等)旋涂到上述基底上，并在80℃-120℃干燥成膜；
(5)、掩膜版曝光；将掩膜版和导电玻璃进行对位调整，采用掩膜版遮挡导电玻璃上的红色像素区，采用紫外线曝光除红色像素区以外的区域；
(6)、冲洗并固化成膜；采用无水乙醇冲洗上述基板，曝光区内的断裂的高分子被冲走，红色目标区的感光高分子薄膜和红色量子点薄膜则保留下来。将上述导电玻璃置于150℃-200℃的热台上，加热溶剂并固化成膜；
步骤二、绿色像素区引入绿色量子点(第二发光部52)；
(7)、再次引入富含氨基的感光高分子薄膜4；将90μL-120μL聚醚酰亚胺的乙醇溶液，并滴加到上述导电玻璃，旋涂，之后将上述导电玻璃置于250度-300度的热台上，加热并发溶剂，在上述导电玻璃上引入聚醚酰亚胺膜层；
(8)、旋涂绿色量子点；将绿色量子点的低沸点溶液(氯仿、甲苯、正己烷、正辛烷、或正庚烷等)旋涂到上述基底上，并在80℃-120℃干燥成膜；
(9)、掩膜版曝光；将曝光机和导电玻璃进行对位调整，对导电玻璃上除绿色像素区以外的区域，进行掩膜版曝光。
(10)、冲洗并固化成膜；采用无水乙醇冲洗上述基板，曝光区内断裂的高分子被冲走，绿色目标区内的感光高分子薄膜和绿色量子点薄膜则保留下来。将上述导电玻璃置于150-200℃的热台上，加热溶剂并固化成膜；
步骤三、蓝色像素区引入蓝色量子点(第三发光部53)；
(11)、再次引入富含氨基的感光高分子薄膜；将90μL-120μL聚醚酰 亚胺的乙醇溶液，并滴加到上述导电玻璃，旋涂，之后将上述导电玻璃置于250-300度的热台上，加热并发溶剂，在上述导电玻璃上引入聚醚酰亚胺膜层。
(12)、旋涂绿色量子点；将蓝色量子点的低沸点溶液(氯仿、甲苯、正己烷、正辛烷、或正庚烷等)旋涂到上述基底上，并在80℃-120℃干燥成膜。
(13)、掩膜版曝光；将曝光机和导电玻璃进行对位调整，对导电玻璃上除蓝色像素区以外的区域，进行掩膜版曝光；
(14)、冲洗并固化成膜；采用无水乙醇冲洗上述基板，曝光区内断裂的高分子被冲走，蓝色目标区内的感光高分子和蓝色量子点则保留下来。将上述导电玻璃置150℃-200℃的热台上，加热溶剂并固化成膜；
步骤四、引入空穴传输层；在上述导电玻璃上，通过旋涂或蒸镀等方式空穴传输层。有机物质做空穴传输层可以选择TFB(聚(9,9-二辛基芴-co-N-(4-丁基苯基)二苯胺))，或PVK(聚乙烯咔唑)，或者其它商业化的空穴传输化合物等。例如，TFB旋涂成膜条件为：130-150℃惰性气体中成膜。膜层厚度可以根据匀胶机转速调控；
步骤五、引入空穴注入层；在上述导电玻璃上，通过旋涂或蒸镀等方式空穴注入层。有机物质做空穴注入层可以选择PEDOT:PSS 4083(聚3，4-乙烯二氧噻吩/聚苯乙烯磺酸盐)或者其它商业化的适用于空穴注入层的化合物。例如，PEDOT的旋涂成膜温度为空气130-150℃等。膜层厚度可以根据匀胶机转速调控；
步骤六、引入阳极；最后引入阳极材料，例如蒸镀铝膜，银膜或溅射铟锌氧化物(IZO)膜制备QLED器件；
步骤七、封装；加盖封装盖板，采用紫外固化胶对器件进行封装，制备量子点发光二极管。
需要说明的是：红色、绿色、蓝色量子点的图形化顺序，可以根据实际需要，任意更换。另外，可以理解的是，对于图案化绿色量子点薄膜时，尽管已形成的红色量子点膜下方的感光部会被再次照射，但由于该位置在该阶段的膜层厚度较厚，到达红色量子点膜下方的感光部的紫外光能量较弱，因 此，无法使红色量子点膜下方的感光部的分子链断裂，即使用无水乙醇清洗时，红色量子点膜下方的感光部也不会被去除，其上方的红色量子点膜也不会被去除；同理，在形成图案化的蓝色量子点膜时，绿色量子点膜也不会被去除。
本公开实施例提供的量子点发光面板具有结构特征1：该量子点发光面板具有平面层状多膜层叠加结构(结合图2所示)，各功能层从下到上分别为：衬底基板1、阴极层2、电子传输层3(氧化锌)、感光高分子薄膜层4、量子点发光层5、空穴传输层82、空穴注入层84、阳极6；各个膜层的鉴别方法：这样的结构可以通过制备量子点发光面板的截面切片，借助高分辨透射电子显微镜以及截面扫描电子显微镜(cross-sectional，SEM)进行结构确定和组成分析；
该量子点发光面板具有典型结构特征2：在电子传输层3(氧化锌层)和量子点发光层5之间存在特定的感光高分子膜层3(聚醚酰亚胺基化合物，或者聚对苯撑苯并二噁唑)，以聚醚酰亚胺基化合物为例，氧化锌表面的羟基官能团(-OH)和聚醚酰亚胺基化合物分子结构上的氨基官能团形成特定的氢键结构，如图3所示；感光高分子膜层3的厚度可以为：0.5nm-3nm之间；鉴别方法：这样的结构特征可以通过傅里叶红外光谱(FTIR)以及二次离子质谱(SIMS)确定进行结构确定和分析，例如，器件中的聚醚酰亚胺基化合物可以用傅里叶红外光谱(FTIR)表征，特征峰如下：1724cm -1和1778cm -1处的双峰为酰亚胺环中的羰基吸收峰；1362cm -1，1237cm -1和1275cm -1处的吸收带归属于芳醚C-O-C的伸缩振动峰；1446cm -1～1630cm -1处的峰为苯环骨架的伸缩振动峰。
该QLED器件结构具有典型结构特征3：器件中量子点发光层5中的量子点尺寸大小在3nm-20nm之间；本公开实施例可以适用于多种量子点，具体包括：油溶性的CdTe、CdS、CdSe、ZnSe、InP、CuInS、CuInSe、PbS、CdS/ZnS、CdSe/ZnS、CdSe/ZnSeS、CdSe/CdS、ZnSe/ZnS、InP/ZnS、CuInS/ZnS、(Zn)CuInS/ZnS、(Mn)CuInS/ZnS、AgInS/ZnS、(Zn)AgInS/ZnS、CuInSe/ZnS、 CuInSeS/ZnS、PbS/ZnS等量子点；量子点发光层5鉴别方法：(1)量子点的晶体结构特征，可以通过高分辨透射电子显微镜(HRTEM)和X-射线衍射仪(XRD)进行判断；(2)量子点的元素组成特征，可以采用能谱仪(EDS)进行判断；(3)量子点的表面配体特征，表面配体的官能团可以采用傅立叶红外光谱(FTIR)，紫外可见吸收光谱(UV-Vis)以及核磁共振光谱(HNMR)进行定性和定量分析；(4)量子点的光谱学特征，例如荧光发射窄，吸收光谱宽等特征，可以用紫外可见吸收光谱(UV-Vis)和荧光光谱(PL)确定。
本发明实施例有益效果如下：本公开实施例提供的量子点发光面板，通过在电子传输层的背离衬底基板的一侧引入一层对紫外线敏感的感光高分子薄膜，再引入量子点发光层。之后，采用掩膜版遮挡，并进行预设光(如紫外光)照射，有预设光照射的地方，感光高分子膜层的分子链发生断裂，可以通过第一溶液(如乙醇溶剂)冲洗去除，未被预设光照射的地方，感光高分子膜层保留下来，通过重复以上步骤，就可以实现多种出光范围不同的发光部的图形化，进而可以实现全彩，高分辨率的量子点面板的制作，且形成全彩化量子点显示面板的过程中，不需要使用对量子点膜层有损害的显影液，进而可以避免实现全彩化面板的制作过程中，量子点膜层受损，影响量子点发光面板的发光效率的问题。
显然，本领域的技术人员可以对本发明进行各种改动和变型而不脱离本发明的精神和范围。这样，倘若本发明的这些修改和变型属于本发明权利要求及其等同技术的范围之内，则本发明也意图包含这些改动和变型在内。

Claims (19)

  1. 一种量子点发光面板，其中，包括：
    衬底基板；
    阴极层，所述阴极层位于所述衬底基板的一侧；
    电子传输层，所述电子传输层位于所述阴极层的背离所述衬底基板的一侧；
    量子点发光层，所述量子点发光层位于所述电子传输层的背离所述阴极层的一侧，具有至少两种出光波长范围互不相同的发光部；
    感光高分子膜层，所述感光高分子膜层位于所述量子点发光层与所述电子传输层之间，具有与各所述发光部一一对应的感光部，所述感光高分子膜层被配置为受预设光照射时发生分子链断裂；
    阳极层，所述阳极层位于所述量子点发光层的背离所述感光高分子膜层的一侧。
  2. 如权利要求1所述的量子点发光面板，其中，所述感光高分子膜层的电子迁移率低于所述电子传输层的电子迁移率。
  3. 如权利要求1或2所述的量子点发光面板，其中，各所述感光部之间均具有阻挡部。
  4. 如权利要求1所述的量子点发光面板，其中，所述电子传输层和所述感光高分子膜层通过共价键连接。
  5. 如权利要求4所述的量子点发光面板，其中，所述电子传输层具有羟基，所述感光高分子膜层具有氨基，所述电子传输层和所述感光高分子膜层通过所述羟基和所述氨基形成所述共价键。
  6. 如权利要求5所述的量子点发光面板，其中，所述电子传输层为金属氧化物。
  7. 如权利要求6所述的量子点发光面板，其中，所述金属氧化物的材料为氧化锌，氧化镁锌，或氧化铝锌。
  8. 如权利要求7所述的量子点发光面板，其中，所述感光部还具有以下共价键之一或组合：
    C-C键；
    C-O键；
    酯键；
    硫酯键；
    其中，所述C-C键，所述C-O键，所述酯键以及所述硫酯键在所述预设光照射时发生共价键断裂。
  9. 如权利要求8所述的量子点发光面板，其中，所述感光部的材料为：
    Figure PCTCN2021093331-appb-100001
    其中，m为结构单元的个数，1<m<100。
  10. 如权利要求9所述的量子点发光面板，其中，X官能团为以下之一：
    Figure PCTCN2021093331-appb-100002
  11. 如权利要求8所述的量子点发光面板，其中，所述感光部的材料为：
    Figure PCTCN2021093331-appb-100003
    其中，n为结构单元的个数，1<n<100。
  12. 如权利要求1所述的量子点发光面板，其中，所述发光部的厚度为30nm～60nm。
  13. 如权利要求1所述的量子点发光面板，其中，所述量子点发光层与所述阳极层之间还具有空穴传输层；所述空穴传输层与所述阳极层之间还具有空穴注入层。
  14. 一种显示装置，其中，包括如权利要求1-13任一项所述的量子点发光面板。
  15. 一种量子点发光面板的制作方法，其中，包括：
    提供一衬底基板；
    在所述衬底基板的一侧形成阴极层；
    在所述阴极层的背离所述衬底基板的一侧形成电子传输层；
    在所述电子传输层的背离所述阴极层的一侧形成量子点发光层，以及在所述量子点发光层与所述电子传输层之间形成感光高分子膜层，其中，所述量子点发光层具有至少两种出光波长范围互不相同的发光部，所述感光高分子膜层具有与各所述发光部一一对应的感光部，所述感光高分子膜层被配置为受预设光照射时发生分子链断裂；
    在所述量子点发光层的背离所述感光高分子膜层的一侧形成阳极层。
  16. 如权利要求15所述的制作方法，其中，在所述电子传输层的背离所述阴极层的一侧形成量子点发光层，以及在所述量子点发光层与所述电子传输层之间形成感光高分子膜层，包括：
    在所述电子传输层的背离所述阴极层的一侧形成感光高分子薄膜；
    在所述感光高分子薄膜的背离所述电子传输层的一侧形成第一量子点发光薄膜；
    通过第一掩膜板对第一区域遮挡，采用预设光进行照射，以使未被所述第一掩膜板遮挡的所述感光高分子薄膜的分子链断裂；
    通过溶液清洗，去除分子链断裂的所述感光高分子薄膜及上方的所述第一量子点发光薄膜，形成第一发光部。
  17. 如权利要求16所述的制作方法，其中，所述在所述电子传输层的背离所述阴极层的一侧形成感光高分子薄膜，包括：
    将聚醚酰亚胺基化合物或聚对苯撑苯并二噁唑溶于乙醇，并旋涂于所述电子传输层的背离所述阴极层的一侧；
    加热以挥发溶剂。
  18. 如权利要求17所述的制作方法，其中，所述采用预设光进行照射，包括：并采用紫外光进行照射。
  19. 如权利要求18所述的制作方法，其中，所述通过溶液清洗，包括：通过无水乙醇进行冲洗。
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