WO2023028757A1 - 量子点材料、量子点发光器件及其制备方法 - Google Patents

量子点材料、量子点发光器件及其制备方法 Download PDF

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WO2023028757A1
WO2023028757A1 PCT/CN2021/115327 CN2021115327W WO2023028757A1 WO 2023028757 A1 WO2023028757 A1 WO 2023028757A1 CN 2021115327 W CN2021115327 W CN 2021115327W WO 2023028757 A1 WO2023028757 A1 WO 2023028757A1
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quantum dot
group
light
dot material
polar
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PCT/CN2021/115327
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French (fr)
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梅文海
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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 PCT/CN2021/115327 priority Critical patent/WO2023028757A1/zh
Priority to CN202180002354.8A priority patent/CN116420439A/zh
Priority to US17/796,310 priority patent/US20240209255A1/en
Publication of WO2023028757A1 publication Critical patent/WO2023028757A1/zh

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    • C—CHEMISTRY; METALLURGY
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/54—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing zinc or cadmium
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/56—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing sulfur
    • C—CHEMISTRY; METALLURGY
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
    • C09K11/881—Chalcogenides
    • C09K11/883—Chalcogenides with zinc or cadmium
    • 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
    • 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

Definitions

  • the disclosure belongs to the field of display technology, and in particular relates to a quantum dot material, a quantum dot light-emitting device and a preparation method thereof.
  • Quantum Dots Light Emitting Doide Display is a new type of display technology developed on the basis of Organic Light-Emitting Diode (OLED).
  • OLED Organic Light-Emitting Diode
  • the light-emitting layer of QLED devices is a quantum dot layer, in which electrons/holes are injected into the quantum dot layer through the electron/hole transport layer, and electrons and holes recombine in the quantum dot layer to emit light.
  • QLED has the advantages of narrow luminous peak, high color saturation, and wide color gamut. With the deepening of QLED research and the continuous improvement of quantum efficiency, it has become a future trend to further adopt new processes and technologies to realize its industrialization.
  • photolithography is generally used to pattern quantum dots to prepare high-resolution QLED or QD-LCD.
  • it is easy to form residues after the development process, which is easy to cause full-color quantum dots.
  • the color mixing in point display affects the display effect.
  • the present disclosure aims to solve at least one of the technical problems existing in the prior art, and provides a quantum dot material, a quantum dot light-emitting device and a preparation method thereof.
  • an embodiment of the present disclosure provides a quantum dot material, wherein the quantum dot material includes: a quantum dot body and a quantum dot ligand that forms a coordination effect with the quantum dot body; the quantum dot ligand Satisfy the first general formula;
  • the first general formula includes:
  • A is a coordination group
  • B is the first linking group
  • C1 is the first polar group
  • C2 is the second polar group
  • D1 is the second linking group
  • D2 is the third linking group
  • E is an end group
  • m is an integer greater than or equal to 1
  • i is an integer greater than or equal to 1
  • the first linking group includes: -(CH 2 ) n -
  • the third linking groups all include: -(CH 2 ) n -, At least one of; n is an integer greater than or equal to 0.
  • both the first polar group and the second polar group include: at least one of -O-.
  • the end group includes: at least one of the
  • the segment where the first polar group is located is the first main chain
  • the segment where the second polar group is located is the second main chain
  • the segment where the coordination group is located is for branch chain
  • the sum of the number of atoms in the first main chain and the second main chain and the number of atoms in the branch chain is greater than or equal to 5 and less than or equal to 12.
  • the number of carbon atoms spaced between two adjacent first polar groups or two adjacent second polar groups is less than or equal to 2.
  • the number of the first polar group and the number of the second linking group are multiple, and the multiple first polar groups are different, multiple The second linking group is different;
  • the number of the second polar group and the third linking group are multiple, and the multiple second polar groups are different, and the multiple third The linking groups are different.
  • the first polar group is different from the second polar group.
  • the chemical formula of the quantum dot ligand is:
  • the quantum dot ligand also includes: a photosensitive group
  • the photosensitive group is connected with the first polar group or the second polar group.
  • the first polar group or the second polar group is a photosensitive group.
  • the quantum dots include: CdS, CdSe, ZnSe, InP, PbS, CsPbCl 3 , CsPbBr 3 , CsPhI 3 , CdS/ZnS, CdSe/ZnS, ZnSe, InP/ZnS, PbS/ZnS, CsPbCl 3 / At least one of ZnS, CsPbBr3/ZnS, and CsPhI3 /ZnS.
  • an embodiment of the present disclosure provides a quantum dot light emitting device, wherein the quantum dot light emitting device includes: a first electrode layer and a second electrode layer oppositely arranged, and the first electrode layer and the second electrode layer A light-emitting layer between the two electrode layers; the light-emitting layer includes the quantum dot material provided above.
  • the luminescent layer further includes: quantum dot products formed after being illuminated.
  • the chemical formula of the quantum dot material is:
  • an embodiment of the present disclosure provides a method for preparing a quantum dot light-emitting device, wherein the method for preparing the quantum dot light-emitting device includes:
  • the quantum dot material layer includes the quantum dot material provided above;
  • a second electrode layer is formed on the light emitting layer.
  • forming a quantum dot material layer on the first electrode layer, and performing photolithography on the quantum dot material layer to form a light-emitting layer including:
  • a photoacid generator is added to the quantum dot material, so that the quantum dot material and the photoacid generator react to form a light-emitting layer.
  • FIG. 1 is a schematic diagram of the solvent properties of quantum dot materials provided by embodiments of the present disclosure in polar solvents;
  • Fig. 2 is a schematic flowchart of a method for manufacturing a quantum dot light-emitting device provided by an embodiment of the present disclosure.
  • photolithography is generally used to pattern quantum dots to prepare high-resolution QLED or QD-LCD.
  • it is easy to form residues after the development process, which is easy to cause full-color quantum dots.
  • the color mixing in point display affects the display effect.
  • embodiments of the present disclosure provide a quantum dot material, a quantum dot light-emitting device, a display substrate and a preparation method thereof. , a quantum dot light-emitting device, a display substrate and a preparation method thereof are further described in detail.
  • the quantum dot material includes: a quantum dot body and a quantum dot ligand that forms a coordination effect with the quantum dot body; the quantum dot ligand satisfies the first general formula; the first general formula includes :
  • A is a coordination group
  • B is the first linking group
  • C1 is the first polar group
  • C2 is the second polar group
  • D1 is the second linking group
  • D2 is the third linking group
  • E is an end group
  • m is an integer greater than or equal to 1
  • i is an integer greater than or equal to 1
  • the first linking group includes: -(CH 2 ) n -
  • the second linking group and the third linking group Groups include: -(CH 2 ) n -, At least one of; n is an integer greater than or equal to 0.
  • the coordination group can form a coordination bond with the surface of the quantum dot body, so that the quantum dot ligand can be connected with the quantum dot body to form a quantum dot material with the quantum dot ligand, and can reduce defects on the surface of the quantum dot.
  • the first linking group can connect the coordinating group with other groups, so that the coordinating bond and other groups together form a quantum dot ligand.
  • Both the first polar group and the second polar group have polarity, and they can be compatible with polar solvents, so as to improve the solubility of the quantum dot ligands in polar solvents.
  • the second linking group and the third linking group can respectively link the first polar group and the second polar group with other groups to form quantum dot ligands with strong solubility.
  • the terminal group can be formed at the end of each chain segment in the quantum dot ligand, which can improve the stability of the quantum dot ligand.
  • group can be formed with one or more second polar groups, or only have the first polar group without the second polar group, and its specific chemical structure can be set according to actual needs, and will not be described here limited.
  • n is an integer greater than or equal to 0. When n is 0, it means that the number of the first linking group, the second linking group and the third linking group in the quantum dot material is 0,
  • the polar group can be directly connected to the terminal terminal, the coordination group and the polar group. In the embodiment of the present disclosure, there is no need for a linking group to connect between the two groups.
  • the quantum dot ligand is connected to the surface of the quantum dot, wherein the quantum dot ligand can have a branched structure as shown in the first general formula above, and the quantum dot ligand can be Formed with a first polar group and/or a second polar group, since both the first polar group and the second polar group can improve the solubility of the quantum dot ligand in a polar solvent, it can Improve the solubility of the overall quantum dot material in polar solvents.
  • polar solvents can be used to dissolve and completely remove excess quantum dot materials, thereby avoiding excess
  • the residual quantum dot material causes the mixing of quantum dot materials of different colors, thereby avoiding color mixing in full-color quantum dot display to improve the display effect.
  • the coordinating group includes: at least one of mercapto, amino, carboxyl, and phosphooxy.
  • Mercapto (-SH), amino (-NH2), carboxyl Phosphorus Both have a strong coordination ability with the atoms on the surface of the quantum dot, which can form a stable connection between the quantum dot body and the quantum dot ligand, so as to improve the stability of the quantum dot material.
  • the coordinating group in the embodiment of the present disclosure is a mercapto group (-SH), which has stronger coordinating ability than other coordinating groups.
  • both the first polar group and the second polar group include: at least one of -O-.
  • a polar group refers to a group whose positive and negative charge centers do not overlap. Specifically, it can be considered that the atoms at both ends of a chemical bond have different electronegativity, and the positive and negative charge centers will not overlap.
  • both the first polar group and the second polar group in the embodiments of the present disclosure may include ester groups Amide group Ether bonds (-O-), all of which have strong polarity, have strong solvent properties in polar solvents. Therefore, the solubility of the overall quantum dot material in the solvent can be improved.
  • the excess quantum dot material can be dissolved and completely removed with a polar solvent, thereby avoiding The excess quantum dot material residue causes quantum dot materials of different colors to mix, thereby avoiding color mixing in full-color quantum dot display and improving the display effect.
  • the terminal group can specifically be at least one of the
  • the end group The ends of the individual chain segments in the quantum dot ligand can be formed, which can improve the stability of the quantum dot ligand.
  • the segment where the first polar group is located is the first main chain
  • the segment where the second polar group is located is the second main chain
  • the segment where the coordination group is located is a branched chain;
  • the sum of the number of atoms in the first main chain and the second main chain and the number of atoms in the branch chain is greater than or equal to 5 and less than or equal to 12.
  • the sum of the number of atoms in the first main chain and the second main chain and the number of atoms in the branch chain is greater than or equal to 5, which can ensure that the quantum dot material has good solubility in polar solvents and avoid quantum dots.
  • the material coagulates in the solvent, resulting in the residue of redundant quantum dot materials in the photolithography process, and the sum of the number of atoms in the first main chain and the second main chain and the number of atoms in the branch chain is less than Or is equal to 12, which can ensure the transport performance of the quantum dot material to the carrier, so as to improve the luminous brightness of the quantum dot light-emitting device, so as to ensure the display effect of the display substrate.
  • the number of carbon atoms separated between two adjacent first polar groups or two adjacent second polar groups is less than or equal to 2.
  • the adjacent first polar groups can be connected by the second linking group, and the adjacent second polar groups
  • the groups can be connected by a third linking group, and the number of carbon atoms spaced between two adjacent first polar groups or two adjacent second polar groups is less than or equal to 2, which can be in While ensuring the connection, it can avoid that the longer chain segments affect the stability of the overall quantum dot material.
  • the number of the first polar group and the second linking group are multiple, and the multiple first polar groups are different, and the multiple second linking groups different groups; when i is greater than or equal to 2, the number of the second polar groups and the third linking groups are multiple, and the multiple second polar groups are different, and the multiple third linking groups are different.
  • the multiple first polarities may be different, and the multiple second polar groups may also be different.
  • some of the first polar groups in the plurality of first polar groups can be ester groups Another part of the first polar group can be an amide group
  • Some of the second polar groups in the plurality of second polar groups can be amide groups
  • Another part of the second polar group can be an ether bond (-O-).
  • each first polar group can also be the same, and each second polar group can also be the same. It can be formed according to actual needs.
  • Quantum dot ligands with polar groups to improve the solubility of the overall quantum dot material in solvents.
  • polar solvents can be used to remove excess quantum dot materials. Dissolving and completely removing, thereby avoiding the mixing of quantum dot materials of different colors caused by excess quantum dot material residue, thereby avoiding color mixing in full-color quantum dot display, so as to improve the display effect.
  • the first polar group and the second polar group are different.
  • the first polar group and the second polar group may be different groups.
  • the first polar group can be an ester group
  • the second polar group can be an ether bond (-O-).
  • the first polar group and the second group can also be the same group, and a multipolar group can be formed according to actual needs.
  • Quantum dot ligands to improve the solubility of the overall quantum dot material in the solvent when using photoresisting technology to pattern quantum dot materials, polar solvents can be used to dissolve and completely remove excess quantum dot materials , so as to avoid the mixing of quantum dot materials of different colors caused by redundant quantum dot material residues, thereby avoiding color mixing in full-color quantum dot display, so as to improve the display effect.
  • the chemical formula of the quantum dot ligand is:
  • the quantum dot ligand has a plurality of polar groups, all of which have strong polarity, and have strong solvability in polar solvents. Therefore, the solubility of the overall quantum dot material in the solvent can be improved, and when the quantum dot material is patterned by the photoresisting process, a polar solvent can be used to dissolve and completely remove the excess quantum dot material, thereby avoiding The excess quantum dot material residue causes quantum dot materials of different colors to mix, thereby avoiding color mixing in full-color quantum dot display and improving the display effect.
  • the quantum dot ligand further includes: a photosensitive group; the photosensitive group is connected to the first polar group or the second polar group.
  • the photosensitive group can undergo a chemical reaction under the condition of light, so that the chemical bond formed by the photosensitive group breaks.
  • the quantum dot material can be irradiated with light such as ultraviolet light to irradiate the quantum dot material. Patterning is performed so that excess quantum dot materials can be removed to form patterns of quantum dot materials of different colors.
  • the polar groups in quantum dot ligands can also be photosensitive groups, which can not only facilitate the patterning of quantum dot materials, but also improve the solubility of quantum dot materials in polar solvents to Avoid the mixing of quantum dot materials of different colors caused by redundant quantum dot material residues.
  • the quantum dots include: CdS, CdSe, ZnSe, InP, PbS, CsPbCl 3 , CsPbBr 3 , CsPhI 3 , CdS/ZnS, CdSe/ZnS, ZnSe, InP/ZnS, PbS/ZnS, CsPbCl 3 / At least one of ZnS, CsPbBr3/ZnS, and CsPhI3 /ZnS.
  • the quantum dots can be CdS, CdSe, ZnSe, InP, PbS, CsPbCl 3 , CsPbBr 3 , CsPhI 3 , CdS/ZnS, CdSe/ZnS, ZnSe, InP/ZnS, PbS/ZnS, CsPbCl 3 At least one of /ZnS, CsPbBr3/ZnS, and CsPhI3 /ZnS, the specific type of quantum dots can be reasonably selected according to actual needs, which is not limited here.
  • the chemical formula of the quantum dot ligand X in the first quantum dot material is:
  • the chemical formula of the quantum dot ligand Y in the second quantum material is:
  • red light quantum dot materials containing ligand X and ligand Y can be prepared by ligand exchange respectively.
  • Two quantum dot material solutions of the same concentration were spin-coated on a sol-gel zinc oxide substrate to form a film, and developed with chloroform, and the developed film was subjected to an emission spectrum test (as shown in Figure 1), and oxidized in the test curve After the emission peak of zinc is normalized, it can be seen from the figure that the number of photons at the red emission peak of the thin film using ligand X is about 1.6 times the number of photons at the corresponding emission peak of the thin film of ligand Y.
  • Y's red light quantum dot material can effectively reduce the quantum dot material residue by about 40%.
  • An embodiment of the present disclosure also provides a quantum dot light-emitting device.
  • the quantum dot light-emitting device includes: a first electrode layer and a second electrode layer oppositely arranged, and a light-emitting layer between the first electrode layer and the second electrode layer;
  • the layer comprises a quantum dot material as provided in any of the above embodiments.
  • the light-emitting layer includes: the quantum dot material provided in any one of the above-mentioned embodiments.
  • the light-emitting layer may also include quantum dot products formed by quantum dot materials after being irradiated.
  • the chemical formula of the quantum dot material can be:
  • the chemical formula of the quantum dot product can be:
  • the light-emitting layer in the quantum dot light-emitting device provided by the embodiments of the present disclosure is made of the above-mentioned quantum dot material and the quantum dot product formed by the quantum dot material after being illuminated.
  • the quantum dot ligands in the quantum dot material are connected to the quantum dots.
  • Surface, wherein the quantum dot ligand can be a branched structure as shown in the first general formula above, and the first polar group and/or the second polar group can be formed in the quantum dot ligand, because Both the first polar group and the second polar group can improve the solubility of the quantum dot ligand in polar solvents, so the solubility of the overall quantum dot material in the solvent can be improved.
  • polar solvents can be used to dissolve and completely remove excess quantum dot materials, thereby avoiding the mixing of quantum dot materials of different colors caused by excess quantum dot material residues, thereby avoiding full-color quantum dots. Click the color mixing in the display to improve the display effect.
  • An embodiment of the present disclosure also provides a display device, which includes the quantum dot light emitting device provided in any one of the above embodiments.
  • the display device can be a terminal device with a display function such as a mobile phone, a television, a tablet computer, and a vehicle recorder, and its realization principle and beneficial effects are the same as those of the quantum dot material described above, and will not be repeated here.
  • FIG. 2 is a schematic flowchart of the method for preparing a display substrate provided by an embodiment of the present disclosure. As shown in FIG. 2 , the method for preparing a display substrate includes the following steps:
  • the quantum dot material layer includes the above-mentioned quantum dot material, and the quantum dot material includes: a quantum dot body and a quantum dot ligand that forms a coordination effect with the quantum dot body; the quantum dot ligand satisfies the first general formula;
  • a formula includes:
  • A is a coordination group
  • B is the first linking group
  • C1 is the first polar group
  • C2 is the second polar group
  • D1 is the second linking group
  • D2 is the third linking group
  • E is an end group
  • m is an integer greater than or equal to 1
  • i is an integer greater than or equal to 1
  • the first linking group includes: -(CH 2 ) n -
  • the second linking group and the third linking group Groups include: -(CH 2 ) n -, At least one of; n is an integer greater than or equal to 0.
  • a quantum dot material layer is formed on the first electrode layer, and photolithography is performed on the quantum dot material layer to form a light-emitting layer, including: A photoacid generator is added to the photoacid generator, so that the quantum dot material and the photoacid generator react to form a light-emitting layer.
  • the photosensitive groups in the quantum dot material can be broken to form quantum dot products, and the polar groups are destroyed, so that the quantum dot products can be dissolved in polar solvents.
  • the solvent in the solvent is much smaller than the solubility of the original quantum dot material in polar solvents, so polar solvents can be used to remove excess quantum dot materials to avoid residual quantum dot materials.
  • the quantum dot light-emitting device is an inverted bottom-emitting light-emitting device, and the manufacturing process of the inverted bottom-emitting light-emitting device is as follows.
  • the quantum dot material is a cadmium selenide/zinc sulfide core-shell structure, the original ligand is pyridine, and the concentration is 20mg/ml.
  • the original ligand is pyridine
  • the concentration is 20mg/ml.
  • the quantum dot light-emitting device is an upright bottom-emitting light-emitting device, and the preparation process of the upright bottom-emission light-emitting device is as follows.
  • the quantum dot light-emitting device is a positive top-emitting light-emitting device
  • the preparation process of the positive top-emitting light-emitting device is as follows.
  • the quantum dot material is a cadmium selenide/zinc sulfide core-shell structure, the original ligand is pyridine, and the concentration is 20mg/ml.
  • the original ligand is pyridine
  • the concentration is 20mg/ml.

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Abstract

一种量子点材料、量子点发光器件及其制备方法，属于显示技术领域，其可解决现有的量子点材料的溶解性较差，在光刻过程中容易发生残留，容易造成混色的问题。量子点材料包括：量子点主体及与量子点主体形成配位作用的量子点配体；量子点配体满足第一通式；第一通式包括： (I) 其中，A为配位基团，B为第一连接基团，C1为第一极性基团，C2为第二极性基团，D1为第二连接基团，D2为第三连接基团，E为末端基团；m为大于或等于1的整数；i为大于或等于1的整数；第一连接基团包括：-(CH2)n-；第二连接基团和第三连接基团均包括：-(CH2)n-、(II) 中的至少一种；n为大于或等于0的整数。

Description

量子点材料、量子点发光器件及其制备方法 技术领域
本公开属于显示技术领域，具体涉及一种量子点材料、量子点发光器件及其制备方法。
背景技术
量子点发光二极管显示(Quantum Dots Light Emitting Doide Display，QLED)是基于有机发光二极管显示(Organic Light-Emitting Diode，OLED)的基础上发展起来的一种新型显示技术。与OLED技术的不同之处在于，QLED器件的发光层为量子点层，其中，电子/空穴通过电子/空穴传输层注入到量子点层，电子和空穴在量子点层中复合发光。与有OLED技术相比，QLED具有发光峰窄，色彩饱和度高，色域宽等优点。随着QLED研究日益深入，量子效率不断提升，需要进一步采用新的工艺和技术来实现其产业化已成为未来的趋势。
目前，一般利用光刻工艺对量子点进行图案化达到制备高分辨率QLED或者QD-LCD，然而，目前量子点进行直接图案化的工艺中很容易在显影过程后形成残留，容易造成全彩量子点显示中的混色，影响显示效果。
发明内容
本公开旨在至少解决现有技术中存在的技术问题之一，提供一种量子点材料、量子点发光器件及其制备方法。
第一方面，本公开实施例提供一种量子点材料，其中，所述量子点材料包括：量子点主体及与所述量子点主体形成配位作用的量子点配体；所述量子点配体满足第一通式；所述第一通式包括：
Figure PCTCN2021115327-appb-000001
其中，A为配位基团，B为第一连接基团，C1为第一极性基团，C2为第二极性基团，D1为第二连接基团，D2为第三连接基团，E为末端基团；m为大于或等于1的整数；i为大于或等于1的整数；所述第一连接基团包括：-(CH 2) n-；所述第二连接基团和所述第三连接基团均包括：-(CH 2) n-、
Figure PCTCN2021115327-appb-000002
中的至少一种；n为大于或等于0的整数。
可选地，所述第一极性基团和所述第二极性基团均包括：
Figure PCTCN2021115327-appb-000003
-O-中的至少一种。
可选地，所述末端基团包括：
Figure PCTCN2021115327-appb-000004
中的至少一种。
可选地，所述第一极性基团所在的链段为第一主链，所述第二极性基团所在的链段为第二主链，所述配位基团所在的链段为支链；
所述第一主链和所述第二主链中原子数较多的一者与所述支链的原子数之和大于或等于5，且小于或等于12。
可选地，相邻的两个所述第一极性基团或相邻的两个所述第二极性基团之间间隔的碳原子数量小于或等于2。
可选地，当m大于或等于2时，所述第一极性基团和所述第二连接基团的数量均为多个，且多个所述第一极性基团不同，多个所述第二连接基团不同；
当i大于或等于2时，所述第二极性基团和所述第三连接基团的数量均为多个，且多个所述第二极性基团不同，多个所述第三连接基团不同。
可选地，所述第一极性基团与所述第二极性基团不同。
可选地，所述量子点配体的化学式为：
Figure PCTCN2021115327-appb-000005
可选地，所述量子点配体还包括：光敏基团；
所述光敏基团与所述第一极性基团或所述第二极性基团连接。
可选地，所述第一极性基团或所述第二极性基团为光敏基团。
可选地，所述量子点包括：CdS、CdSe、ZnSe、InP、PbS、CsPbCl 3、CsPbBr 3、CsPhI 3、CdS/ZnS、CdSe/ZnS、ZnSe、InP/ZnS、PbS/ZnS、CsPbCl 3/ZnS、CsPbBr3/ZnS、CsPhI 3/ZnS中的至少一种。
第二方面，本公开实施例提供一种量子点发光器件，其中，所述量子点发光器件包括：相对设置的第一电极层和第二电极层、及所述第一电极层和所述第二电极层之间的发光层；所述发光层包括如上述提供的量子点材料。
可选地，所述发光层还包括：经过光照后所形成的量子点生成物。
可选地，所述量子点材料的化学式为：
Figure PCTCN2021115327-appb-000006
所述量子点生成物的化学式为：
Figure PCTCN2021115327-appb-000007
第三方面，本公开实施例提供一种量子点发光器件的制备方法，其中，所述量子点发光器件的制备方法包括：
在基底上形成第一电极层；
在所述第一电极层上形成量子点材料层，并对所述量子点材料层进行光刻，以形成发光层；其中，所述量子点材料层包括如上述提供的量子点材料；
在所述发光层上形成第二电极层。
可选地，在所述第一电极层上形成量子点材料层，并对所述量子点材料层进行光刻，以形成发光层，包括：
在光照条件下，在量子点材料中加入光致生酸剂，使得所述量子点材料和所述光致生酸剂反应，以形成发光层。
附图说明
图1为本公开实施例提供的量子点材料在极性溶剂中的溶剂性示意图；
图2为本公开实施例提供的量子点发光器件的制备方法的流程示意图。
具体实施方式
为使本领域技术人员更好地理解本公开的技术方案，下面结合附图和具体实施方式对本公开作进一步详细描述。
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。同样，“一个”、“一”或者“该”等类似词语也不表示数量限制，而是表示存在至少一个。“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。
目前，一般利用光刻工艺对量子点进行图案化达到制备高分辨率QLED或者QD-LCD，然而，目前量子点进行直接图案化的工艺中很容易在显影过程后形成残留，容易造成全彩量子点显示中的混色，影响显示效果。
为了至少解决上述的技术问题之一，本公开实施例提供了一种量子点材料、量子点发光器件、显示基板及其制备方法，下面将结合附图及具体实施方式对本公开提供的量子点材料、量子点发光器件、显示基板及其制备方法进行进一步详细说明。
本公开实施例提供了一种量子点材料，量子点材料包括：量子点主体及与量子点主体形成配位作用的量子点配体；量子点配体满足第一通式；第一通式包括：
Figure PCTCN2021115327-appb-000008
其中，A为配位基团，B为第一连接基团，C1为第一极性基团，C2为第二极性基团，D1为第二连接基团，D2为第三连接基团，E为末端基团；m为大于或等于1的整数；i为大于或等于1的整数；第一连接基团包括： -(CH 2) n-；第二连接基团和第三连接基团均包括：-(CH 2) n-、
Figure PCTCN2021115327-appb-000009
中的至少一种；n为大于或等于0的整数。
配位基团可以与量子点主体表面形成配位键，使得量子点配体与量子点主体可以连接，以形成具有量子点配体的量子点材料，并且可以减少量子点表面的缺陷。第一连接基团可以将配位基团与其他基团连接，以使得配位键与其他基团共同形成量子点配体。第一极性基团和第二极性基团均具有极性，其可以与极性溶剂相溶，以提高量子点配体在极性溶剂中的溶解性。第二连接基团和第三连接基团可以分别将第一极性基团和第二极性基团与其他基团连接，以形成溶解性较强的量子点配体。末端基团可以形成在量子点配体中各个链段的末端，可以提高量子点配体的稳定性。
在此需说明的是，在上述第一通式中，m为大于或等于1的整数；i为大于或等于1的整数表示在量子点配体中可以形成有一个或多个第一极性基团，可以形成有一个或多个第二极性基团，也可以仅具有第一极性基团无第二极性基团，其具体化学结构可以根据实际需要进行设置，在此不进行限定。进一步需要说明的是，n为大于或等于0的整数，当n为0时，即表示在量子点材料中第一连接基团、第二连接基团和第三连接基团的数量为0，极性基团与末端极端、配位基团及极性基团之间可以直接进行连接，在本公开实施例中，两个基团之间并不是必须具有连接基团连接的。
本公开实施例提供的量子点材料，量子点配体连接于量子点的表面，其中的量子点配体可以为如上述第一通式所示的支化结构，并且在量子点配体中可以形成有第一极性基团和/或第二极性基团，由于第一极性基团和第二极性基团均可以提高量子点配体在极性溶剂中的溶解性，因此可以提高整体的量子点材料在极性溶剂中的溶解性，在利用光可以工艺对量子点材料进行图案化时，可以采用极性溶剂将多余的量子点材料进行溶解并完全去除，从而可以避免多余的量子点材料残留造成不同颜色的量子点材料混合，进而可以 避免全彩量子点显示中的混色，以提高显示效果。
在一些实施例中，配位基团包括：巯基、氨基、羧基、磷氧基中的至少一种。巯基(-SH)、氨基(-NH2)、羧基
Figure PCTCN2021115327-appb-000010
磷氧基
Figure PCTCN2021115327-appb-000011
均与量子点表面的原子具有较强的配位能力，可以使得量子点主体与量子点配体之间形成稳定连接，以提高量子点材料的稳定性。优选地，在本公开实施例中配位基团为巯基(-SH)，其较其他配位基团具有更强的配位能力。
在一些实施例中，第一极性基团和第二极性基团均包括：
Figure PCTCN2021115327-appb-000012
-O-中的至少一种。
在此需要说明的是，极性基团是指正负电荷中心不重合的基团，具体可以认为一个化学键的两端的原子电负性不同，正负电荷的中心就不会重合。具体地，本公开实施例中的第一极性基团和第二极性基团均可以包括酯基
Figure PCTCN2021115327-appb-000013
酰胺基
Figure PCTCN2021115327-appb-000014
醚键(-O-)，其均具有较强的极性，在极性溶剂中具有较强的溶剂性。因此可以提高整体的量子点材料在进行溶剂中的溶解性，在利用光可以工艺对量子点材料进行图案化时，可以采用极性溶剂将多余的量子点材料进行溶解并完全去除，从而可以避免多余的量子点材料残留造成不同颜色的量子点材料混合，进而可以避免全彩量子点显示中的混色，以提高显示效果。
在一些实施例中，末端基团具体可以为
Figure PCTCN2021115327-appb-000015
中的至少一种。
需要说明的是，末端基团
Figure PCTCN2021115327-appb-000016
可以形成在量子点配体中各个链段的末端，其可以提高量子点配体的稳定性。
在一些实施例中，第一极性基团所在的链段为第一主链，第二极性基团所在的链段为第二主链，配位基团所在的链段为支链；第一主链和第二主链中原子数较多的一者与支链的原子数之和大于或等于5，且小于或等于12。
第一主链和第二主链中原子数较多的一者与支链的原子数之和大于或 等于5，这样可以保证量子点材料在极性溶剂中具有良好的溶解性，避免量子点材料在溶剂中发生聚沉，造成在光刻过程中多余的量子点材料的残留，并且，第一主链和第二主链中原子数较多的一者与支链的原子数之和小于或等于12，可以保证量子点材料对载流子的传输性能，以提高量子点发光器件的发光亮度，从而可以保证显示基板的显示效果。
在一些实施例中，相邻的两个第一极性基团或相邻的两个第二极性基团之间间隔的碳原子数量小于或等于2。
量子点配体中具有多个第一极性基团或多个第二极性基团时，相邻的第一极性基团可以通过第二连接基团连接，相邻的第二极性基团之间可以通过第三连接基团连接，相邻的两个第一极性基团或相邻的两个第二极性基团之间间隔的碳原子数量小于或等于2，可以在保证连接的同时，可以避免较长的链段影响整体的量子点材料的稳定性。
在一些实施例中，当m大于或等于2时，第一极性基团和第二连接基团的数量均为多个，且多个第一极性基团不同，多个第二连接基团不同；当i大于或等于2时，第二极性基团和第三连接基团的数量均为多个，且多个第二极性基团不同，多个第三连接基团不同。
在实际应用中，第一极性基团和第二极性基团的数量为多个时，多个第一极性可以不同，以及多个第二极性基团也可以不同。例如，多个第一极性基团中部分第一极性基团可以为酯基
Figure PCTCN2021115327-appb-000017
另一部分第一极性基团可以为酰胺基
Figure PCTCN2021115327-appb-000018
多个第二极性基团中部分第二极性基团可以为酰胺基
Figure PCTCN2021115327-appb-000019
另一部分第二极性基团可以为醚键(-O-)，当然，各个第一极性基团也可以相同，各个第二极性基团也可以相同，可以根据实际需要形成具有多个极性基团的量子点配体，以提高整体的量子点材料在进行溶剂中的溶解性，在利用光可以工艺对量子点材料进行图案化时，可以采用极性溶剂 将多余的量子点材料进行溶解并完全去除，从而可以避免多余的量子点材料残留造成不同颜色的量子点材料混合，进而可以避免全彩量子点显示中的混色，以提高显示效果。
在一些实施例中，第一极性基团和第二极性基团不同。
在实际应用中，第一极性基团和第二极性基团可以为不同的基团。例如，第一极性基团可以为酯基
Figure PCTCN2021115327-appb-000020
第二极性基团可以为醚键(-O-)，当然，第一极性基团和第二基团也可以为相同的基团，可以根据实际需要形成具有多个极性基团的量子点配体，以提高整体的量子点材料在进行溶剂中的溶解性，在利用光可以工艺对量子点材料进行图案化时，可以采用极性溶剂将多余的量子点材料进行溶解并完全去除，从而可以避免多余的量子点材料残留造成不同颜色的量子点材料混合，进而可以避免全彩量子点显示中的混色，以提高显示效果。
具体地，量子点配体的化学式为：
Figure PCTCN2021115327-appb-000021
由上述的化学式可以看出，该量子点配体具有多个极性基团，其均具有较强的极性，在极性溶剂中具有较强的溶剂性。因此可以提高整体的量子点材料在进行溶剂中的溶解性，在利用光可以工艺对量子点材料进行图案化时，可以采用极性溶剂将多余的量子点材料进行溶解并完全去除，从而可以避免多余的量子点材料残留造成不同颜色的量子点材料混合，进而可以避免全彩量子点显示中的混色，以提高显示效果。
在一些实施例中，量子点配体还包括：光敏基团；光敏基团与第一极性基团或第二极性基团连接。
光敏基团可以在光照的条件下发生化学反应，使得其中的光敏基团形成的化学键发生断裂，在光刻工艺中，可以利用紫外光等光线，对量子点材料 进行照射，以对量子点材料进行图案化，从而可以形成将多余的量子点材料去除，进而形成不同颜色的量子点材料的图案。在实际应用中，量子点配体中的极性基团也可以为光敏基团，其不仅可以有利于量子点材料的图案化，还可以提高量子点材料在极性溶剂中的溶解性，以避免多余的量子点材料残留造成不同颜色的量子点材料混合。
在一些实施例中，量子点包括：CdS、CdSe、ZnSe、InP、PbS、CsPbCl 3、CsPbBr 3、CsPhI 3、CdS/ZnS、CdSe/ZnS、ZnSe、InP/ZnS、PbS/ZnS、CsPbCl 3/ZnS、CsPbBr3/ZnS、CsPhI 3/ZnS中的至少一种。
在此需要说明的是，量子点可以为CdS、CdSe、ZnSe、InP、PbS、CsPbCl 3、CsPbBr 3、CsPhI 3、CdS/ZnS、CdSe/ZnS、ZnSe、InP/ZnS、PbS/ZnS、CsPbCl 3/ZnS、CsPbBr3/ZnS、CsPhI 3/ZnS中的至少一种，可以根据实际需要合理选择量子点的具体类型，在此不在进行限定。
下面将以两种不同的量子点材料为例对本公开实施例提供的量子点材料在有机溶剂中的溶解性进行进一步详细描述。
第一种量子点材料中量子点配体X的化学式为：
Figure PCTCN2021115327-appb-000022
第二种量子材料中量子点配体Y的化学式为：
Figure PCTCN2021115327-appb-000023
在实际应用中，可以分别通过配体交换制备了含有配体X和配体Y的红光量子点材料。将相同浓度的两种量子点材料溶液在sol-gel氧化锌基底上旋涂成膜，并使用氯仿进行显影，将显影过后的薄膜进行发射光谱测试(如图1)，在对测试曲线中氧化锌的发射峰进行归一化处理后，从图中可以看到，使用配体X的薄膜红光发射峰处的光子数是配体Y薄膜对应发射峰光子数的大约1.6倍，含有配体Y的红光量子点材料可以有效降低约40％的量子点材料残留。
本公开实施例还提供了一种量子点发光器件，量子点发光器件包括：相对设置的第一电极层和第二电极层、及第一电极层和第二电极层之间的发光层；发光层包括如上述任一实施例提供的量子点材料。发光层包括：如上述任一实施例所提供的量子点材料。
可选地，发光层还可以包括量子点材料经过光照后所形成的量子点生成物。
在一些实施例中，量子点材料的化学式可以为：
Figure PCTCN2021115327-appb-000024
量子点生成物的化学式可以为：
Figure PCTCN2021115327-appb-000025
具体地，在光刻过程中量子点材料的化学反应式如下：
Figure PCTCN2021115327-appb-000026
本公开实施例提供的量子点发光器件中发光层采用上述的量子点材料以及量子点材料经过光照后所形成的量子点生成物制成，量子点材料中的量子点配体连接于量子点的表面，其中的量子点配体可以为如上述第一通式所示的支化结构，并且在量子点配体中可以形成有第一极性基团和/或第二极性基团，由于第一极性基团和第二极性基团均可以提高量子点配体在极性溶剂中的溶解性，因此可以提高整体的量子点材料在进行溶剂中的溶解性，在利用光可以工艺对量子点材料进行图案化时，可以采用极性溶剂将多余的量子点材料进行溶解并完全去除，从而可以避免多余的量子点材料残留造成不同颜色的量子点材料混合，进而可以避免全彩量子点显示中的混色，以提高显示效果。
本公开实施例还提供了一种显示装置，该显示装置包括如上述任一实施例提供的量子点发光器件。该显示装置可以为手机、电视、平板电脑、车载记录仪等具有显示功能的终端设备，其实现原理及有益效果与上述地量子点材料的实现原理及有益效果相同，在此不在赘述。
本公开实施例还提供了一种显示基板的制备方法，图2为本公开实施例提供的显示基板的制备方法的流程示意图，如图2所示，该显示基板的制备方法包括如下步骤：
S201，在基底上形成第一电极层；
S202，在第一电极层上形成量子点材料层，并对量子点材料层进行光刻，以形成发光层。
在步骤S202中，量子点材料层包括上述的量子点材料，量子点材料包括：量子点主体及与量子点主体形成配位作用的量子点配体；量子点配体满足第一通式；第一通式包括：
Figure PCTCN2021115327-appb-000027
其中，A为配位基团，B为第一连接基团，C1为第一极性基团，C2为第二极性基团，D1为第二连接基团，D2为第三连接基团，E为末端基团；m为大于或等于1的整数；i为大于或等于1的整数；第一连接基团包括：-(CH 2) n-；第二连接基团和第三连接基团均包括：-(CH 2) n-、
Figure PCTCN2021115327-appb-000028
中的至少一种；n为大于或等于0的整数。
S203，在发光层上形成第二电极层。
在一些实施例中，上述的步骤S202中，在第一电极层上形成量子点材料层，并对量子点材料层进行光刻，以形成发光层，包括：在光照条件下，在量子点材料中加入光致生酸剂，使得量子点材料和光致生酸剂反应，以形成发光层。
量子点材料在光照的条件下，在光致生酸剂的作用下，其中的光敏基团可以发生断裂，生成量子点生成物，极性基团被破坏，使得量子点生成物在极性溶剂中的溶剂性远远小于原来的量子点材料在极性溶剂中的溶解性，因此可以采用极性溶剂将多余的量子点材料去除，避免量子点材料残留。
具体地，在光刻过程中量子点材料的化学反应式如下：
Figure PCTCN2021115327-appb-000029
下面结合具体量子点发光器件的结构，对本公开实施例提供的量子点发 光器件的制备过程进行进一步详细说明。
第一种实现方式，量子点发光器件为倒置底发射型发光器件，如下为倒置底发射型发光器件制备过程。
量子点材料为硒化镉/硫化锌核壳结构，原始配体为吡啶，浓度为20mg/ml。取1ml量子点溶液并向其中加入0.33mlY配体，室温下搅拌4小时完成配体交换，之后使用8ml甲醇将量子点进行沉淀，离心后弃去上清液；使用1ml氯仿溶解量子点，使用8ml甲醇进行沉淀，离心后丢弃上清液，80度真空抽干后将量子点粉末重新溶于甲苯中形成20mg/ml的溶液。
在ITO基板上氮气中旋涂氧化镍纳米粒子(2000rpm,30s，25mg/ml),120度退火20分钟；在空气中旋涂Y配体红光量子点溶液(3000rpm,30s)，其中加入5％wt的2,4-双(三氯甲基)-6-对甲氧基苯乙烯基-S-三嗪作为光致生酸剂，完成旋涂后UV曝光150mj，曝光完后使用氯仿对膜层进行显影，显影完成后120度退火20分钟形成图案化的红光量子点发光层。
在空气中旋涂Y配体绿光量子点溶液(3000rpm,30s)，其中加入3％wt的2,4-双(三氯甲基)-6-对甲氧基苯乙烯基-S-三嗪作为光致生酸剂，完成旋涂后UV曝光300mj，曝光完后使用氯仿对膜层进行显影，显影完成后120度退火20分钟形成图案化的绿光量子点发光层。
在空气中旋涂Y配体蓝光量子点溶液(3000rpm,30s)，其中加入2％wt的2,4-双(三氯甲基)-6-对甲氧基苯乙烯基-S-三嗪作为光致生酸剂，完成旋涂后UV曝光300mj，曝光完后使用氯仿对膜层进行显影，显影完成后120度退火20分钟形成图案化的蓝光量子点发光层。
继续旋涂氧化锌纳米粒子(3000rpm，30s，30mg/ml)，120度退火20分钟；蒸镀铝电极120nm，封装后完成倒置底发射型发光器件制备。
第二种实现方式，量子点发光器件为正置底发射型发光器件，如下为正置底发射型发光器件制备过程。
在ITO基板上氮气中旋涂氧化镍纳米粒子(2000rpm,30s，25mg/ml),120度退火20分钟；在空气中旋涂Y配体红光量子点溶液(3000rpm,30s)，其中加入5％wt的2,4-双(三氯甲基)-6-对甲氧基苯乙烯基-S-三嗪作为光致生酸剂，完成旋涂后UV曝光150mj，曝光完后使用氯仿对膜层进行显影，显影完成后120度退火20分钟形成图案化的红光量子点发光层。
在空气中旋涂Y配体绿光量子点溶液(3000rpm,30s)，其中加入3％wt的2,4-双(三氯甲基)-6-对甲氧基苯乙烯基-S-三嗪作为光致生酸剂，完成旋涂后UV曝光300mj，曝光完后使用氯仿对膜层进行显影，显影完成后120度退火20分钟形成图案化的绿光量子点发光层。
在空气中旋涂Y配体蓝光量子点溶液(3000rpm,30s)，其中加入2％wt的2,4-双(三氯甲基)-6-对甲氧基苯乙烯基-S-三嗪作为光致生酸剂，完成旋涂后UV曝光300mj，曝光完后使用氯仿对膜层进行显影，显影完成后120度退火20分钟形成图案化的蓝光量子点发光层。
继续旋涂氧化锌纳米粒子(3000rpm，30s，30mg/ml)，120度退火20分钟；蒸镀铝电极120nm，封装后完成正置底发射型发光器件制备。
第三种实现方式，量子点发光器件为正置顶发射型发光器，如下为正置顶发射型发光器件的制备过程。
量子点材料为硒化镉/硫化锌核壳结构，原始配体为吡啶，浓度为20mg/ml。取1ml量子点溶液并向其中加入0.33ml Y配体，室温下搅拌4小时完成配体交换，之后使用8ml甲醇将量子点进行沉淀，离心后弃去上清液；使用1ml氯仿溶解量子点，使用8ml甲醇进行沉淀，离心后丢弃上清液，80度真空抽干后将量子点粉末重新溶于甲苯中形成20mg/ml的溶液。
在ITO/Ag/ITO基板上氮气中旋涂氧化镍纳米粒子(2000rpm,30s，25mg/ml),120度退火20分钟；；在空气中旋涂Y配体红光量子点溶液(3000rpm,30s)，其中加入5％wt的2,4-双(三氯甲基)-6-对甲氧基苯乙烯基-S- 三嗪作为光致生酸剂，完成旋涂后UV曝光150mj，曝光完后使用氯仿对膜层进行显影，显影完成后120度退火20分钟形成图案化的红光量子点发光层。
在空气中旋涂Y配体绿光量子点溶液(3000rpm,30s)，其中加入3％wt的2,4-双(三氯甲基)-6-对甲氧基苯乙烯基-S-三嗪作为光致生酸剂，完成旋涂后UV曝光300mj，曝光完后使用氯仿对膜层进行显影，显影完成后120度退火20分钟形成图案化的绿光量子点发光层。
在空气中旋涂Y配体蓝光量子点溶液(3000rpm,30s)，其中加入2％wt的2,4-双(三氯甲基)-6-对甲氧基苯乙烯基-S-三嗪作为光致生酸剂，完成旋涂后UV曝光300mj，曝光完后使用氯仿对膜层进行显影，显影完成后120度退火20分钟形成图案化的蓝光量子点发光层。
继续旋涂氧化锌纳米粒子(3000rpm，30s，30mg/ml)，120度退火20分钟；溅射氧化铟镓锌(IGZO)电极50nm，封装后完成正置顶发射型发光器件制备。
可以理解的是，以上实施方式仅仅是为了说明本公开的原理而采用的示例性实施方式，然而本公开并不局限于此。对于本领域内的普通技术人员而言，在不脱离本公开的精神和实质的情况下，可以做出各种变型和改进，这些变型和改进也视为本公开的保护范围。

Claims (16)

  1. 一种量子点材料，其中，所述量子点材料包括：量子点主体及与所述量子点主体形成配位作用的量子点配体；所述量子点配体满足第一通式；所述第一通式包括：
    Figure PCTCN2021115327-appb-100001
    其中，A为配位基团，B为第一连接基团，C1为第一极性基团，C2为第二极性基团，D1为第二连接基团，D2为第三连接基团，E为末端基团；m为大于或等于1的整数；i为大于或等于1的整数；所述第一连接基团包括：-(CH 2) n-；所述第二连接基团和所述第三连接基团均包括：-(CH 2) n-、
    Figure PCTCN2021115327-appb-100002
    中的至少一种；n为大于或等于0的整数。
  2. 根据权利要求1所述的量子点材料，其中，所述第一极性基团和所述第二极性基团均包括：
    Figure PCTCN2021115327-appb-100003
    -O-中的至少一种。
  3. 根据权利要求1所述的量子点材料，其中，所述末端基团包括：-、
    Figure PCTCN2021115327-appb-100004
    中的至少一种。
  4. 根据权利要求1所述的量子点材料，其中，所述第一极性基团所在的链段为第一主链，所述第二极性基团所在的链段为第二主链，所述配位基团所在的链段为支链；
    所述第一主链和所述第二主链中原子数较多的一者与所述支链的原子数之和大于或等于5，且小于或等于12。
  5. 根据权利要求1所述的量子点材料，其中，相邻的两个所述第一极性基团或相邻的两个所述第二极性基团之间间隔的碳原子数量小于或等于2。
  6. 根据权利要求1所述的量子点材料，其中，当m大于或等于2时，所述第一极性基团和所述第二连接基团的数量均为多个，且多个所述第一极性基团不同，多个所述第二连接基团不同；
    当i大于或等于2时，所述第二极性基团和所述第三连接基团的数量均为多个，且多个所述第二极性基团不同，多个所述第三连接基团不同。
  7. 根据权利要求6所述的量子点材料，其中，所述第一极性基团与所述第二极性基团不同。
  8. 根据权利要求1所述的量子点材料，其中，所述量子点配体的化学式为：
    Figure PCTCN2021115327-appb-100005
  9. 根据权利要求1所述的量子点材料，其中，所述量子点配体还包括：光敏基团；
    所述光敏基团与所述第一极性基团或所述第二极性基团连接。
  10. 根据权利要求1所述的量子点材料，其中，所述第一极性基团或所述第二极性基团为光敏基团。
  11. 根据权利要求1所述的量子点材料，其中，所述量子点包括：CdS、CdSe、ZnSe、InP、PbS、CsPbCl 3、CsPbBr 3、CsPhI 3、CdS/ZnS、CdSe/ZnS、ZnSe、InP/ZnS、PbS/ZnS、CsPbCl 3/ZnS、CsPbBr3/ZnS、CsPhI 3/ZnS中的至少一种。
  12. 一种量子点发光器件，其中，所述量子点发光器件包括：相对设置的第一电极层和第二电极层、及所述第一电极层和所述第二电极层之间的发光层；所述发光层包括如权利要求1-11任一项所述的量子点材料。
  13. 根据权利要求12所述的量子点发光器件，其中，所述发光层还包括：所述量子点材料经过光照后所形成的量子点生成物。
  14. 根据权利要求13所述的量子点发光器件，其中，所述量子点材料 的化学式为：
    Figure PCTCN2021115327-appb-100006
    所述量子点生成物的化学式为：
    Figure PCTCN2021115327-appb-100007
  15. 一种量子点发光器件的制备方法，其中，所述量子点发光器件的制备方法包括：
    在基底上形成第一电极层；
    在所述第一电极层上形成量子点材料层，并对所述量子点材料层进行光刻，以形成发光层；其中，所述量子点材料层包括如权利要求1-11任一项所述的量子点材料；
    在所述发光层上形成第二电极层。
  16. 根据权利要求15所述的量子点发光器件的制备方法，其中，在所述第一电极层上形成量子点材料层，并对所述量子点材料层进行光刻，以形成发光层，包括：
    在光照条件下，在量子点材料中加入光致生酸剂，使得所述量子点材料和所述光致生酸剂反应，以形成发光层。
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