WO2023050214A1 - 量子点配体、量子点-配体体系及量子点材料 - Google Patents

量子点配体、量子点-配体体系及量子点材料 Download PDF

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WO2023050214A1
WO2023050214A1 PCT/CN2021/121925 CN2021121925W WO2023050214A1 WO 2023050214 A1 WO2023050214 A1 WO 2023050214A1 CN 2021121925 W CN2021121925 W CN 2021121925W WO 2023050214 A1 WO2023050214 A1 WO 2023050214A1
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quantum dot
group
ligand
linking
solution
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PCT/CN2021/121925
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French (fr)
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陈卓
梅文海
李卓
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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 CN202180002751.5A priority Critical patent/CN116210361A/zh
Priority to PCT/CN2021/121925 priority patent/WO2023050214A1/zh
Publication of WO2023050214A1 publication Critical patent/WO2023050214A1/zh

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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
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/50—Wavelength conversion elements

Definitions

  • the present disclosure relates to the field of display technology, in particular to a quantum dot ligand, a quantum dot-ligand system and a quantum dot material.
  • quantum dot preparation technology With the in-depth development of quantum dot preparation technology, the stability and luminous efficiency of quantum dots continue to improve, the research on quantum dot electroluminescent diodes (Quantum Dot Light Emitting Diodes, QLED) continues to deepen, and the application prospects of QLED in the display field are increasingly bright . However, the efficiency of QLEDs has not yet reached mass production levels. One of the important reasons is that the high-resolution patterning technology of QLED has not yet achieved a breakthrough.
  • the inorganic nanoparticle characteristics of quantum dots make it impossible to form a film and pattern by evaporation; it is difficult to achieve high resolution by inkjet printing.
  • the purpose of the present disclosure is to provide a quantum dot ligand, a quantum dot-ligand system and a quantum dot material.
  • the quantum dot ligand provides a basis for the quantum dot film layer to be formed by photolithography.
  • a quantum dot ligand includes an X group, a Y group and a Z group,
  • the Y group is used to provide at least two connection sites, wherein at least one connection site is used to connect to X, and the remaining connection sites are used to connect to the Z group;
  • the X group is a coordination group, which is used to form a coordination bond with the surface of the quantum dot;
  • the Z group is a saturated 3-5 membered heterocyclic group containing O or S.
  • the Z group in the quantum dot ligand is used to open a ring and undergo a cross-linking reaction with the adjacent quantum dot ligand under external influence.
  • the Y group includes at least one linking group, the linking group provides at least two linking sites, and one of the linking sites of the linking group
  • the linking site is used for linking with the Z group, and the linking group is selected from an alkylene group with 2-12 carbon atoms.
  • the Y group further includes a carrier transport regulating group, and the carrier transport regulating group is connected between the linking group and the Z group between.
  • the carrier transport regulating group is selected from aniline structure, triphenylamine structure or carbazole structure.
  • the Y group further includes a dissolving group, the dissolving group is connected between the linking group and the Z group, and the dissolving group is selected from self contained Structure.
  • the coordinating group is selected from an amino group, a carboxylic acid group, a mercapto group, a phosphino group, a phosphinoxy group or a saturated heterocyclic group containing a disulfide bond.
  • the Z group is selected from epoxy groups.
  • the quantum dot ligand is selected from the group consisting of the following structures:
  • R 1 , R 2 , R 3 and R 4 are each independently selected from amino, carboxylate, mercapto, phosphino, phosphinoxy or
  • Ar 1 is selected from the group containing aniline, carbazolyl or The structure, R 5 is selected from
  • n1, n2 and n3 are each independently selected from any integer of 2-8.
  • the quantum dot ligand is selected from the group consisting of the following structures:
  • R is selected from
  • n1, n2, and n3 are each independently selected from any integer of 2-8.
  • a quantum dot-ligand system including quantum dots, a photoacid generator and the quantum dot ligand described in the first aspect.
  • the photoacid generator is selected from sulfonium salts, triazines, sulfonate esters or diazonium salts.
  • a quantum dot-ligand material comprising at least two quantum dot-ligand units, the quantum dot-ligand units including quantum dots and the quantum dots described in the first aspect Ligands, the quantum dot-ligand units are bonded and cross-linked to each other through the ring opening of the Z group to form a network structure.
  • a method for preparing a quantum dot film layer including:
  • the quantum dot-ligand solution is a mixed solution comprising quantum dots, photoacid generators and quantum dot ligands as described in the first aspect;
  • Developing treatment is carried out to form the quantum dot film layer.
  • a quantum dot light-emitting device including an anode, a cathode, and a functional layer disposed between the anode and the cathode, the functional layer includes a quantum dot light-emitting layer, and the quantum dot
  • the dot light-emitting layer includes the quantum dot-ligand material as described in the third aspect.
  • the functional layer further includes a hole injection layer, a hole transport layer, an electron transport layer and an electron injection layer.
  • a method for preparing a quantum dot light-emitting device including:
  • a green quantum dot-ligand solution is provided, the green quantum dot-ligand solution is a mixed solution comprising green quantum dots, photoacid generators and quantum dot ligands as described in the first aspect;
  • a blue quantum dot-ligand solution is provided, the blue quantum dot-ligand solution is a mixed solution comprising blue quantum dots, photoacid generators and quantum dot ligands as described in the first aspect;
  • red quantum dot-ligand solution is provided, the red quantum dot-ligand solution is a mixed solution comprising red quantum dots, photoacid generators and quantum dot ligands as described in the first aspect;
  • the red quantum dot-ligand solution is coated on the substrate, exposed and developed to form red sub-pixels.
  • a display device including the quantum dot light emitting device as described in the fifth aspect.
  • the quantum dot ligand provided in the present disclosure contains a coordination group and a saturated 3-5 membered heterocyclic group containing O or S. Coordinating groups can form coordination bonds with quantum dots, thereby forming quantum dot-ligand units.
  • the saturated 3-5-membered heterocyclic group containing O or S can undergo a ring-opening reaction with the assistance of photoacid generators, so that cross-linking occurs between quantum dots and ligand units, thereby providing energy for the quantum dot film.
  • the provided base is formed using a photolithographic process.
  • FIG. 1 is a schematic diagram of the structure of a green-quantum dot ligand solution coated on a substrate in an exemplary embodiment of the present disclosure
  • FIG. 2 is a schematic diagram of the structure of green light sub-pixels in an exemplary embodiment of the present disclosure
  • FIG. 3 is a schematic diagram of the structure of a blue-quantum dot ligand solution coated on a substrate in an exemplary embodiment of the present disclosure
  • FIG. 4 is a schematic diagram of a blue light sub-pixel structure in an exemplary embodiment of the present disclosure
  • Fig. 5 is a schematic diagram of the structure of a red-quantum dot ligand solution coated on a substrate in an exemplary embodiment of the present disclosure
  • FIG. 6 is a schematic diagram of a red light sub-pixel structure in an exemplary embodiment of the present disclosure.
  • Example embodiments will now be described more fully with reference to the accompanying drawings.
  • Example embodiments may, however, be embodied in many forms and should not be construed as limited to the examples set forth herein; rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the concept of example embodiments to those skilled in the art.
  • the described features, structures, or characteristics may be combined in any suitable manner in one or more embodiments. In the following description, numerous specific details are provided in order to give a thorough understanding of embodiments of the present disclosure.
  • a structure When a structure is "on" another structure, it may mean that a structure is integrally formed on another structure, or that a structure is “directly” placed on another structure, or that a structure is “indirectly” placed on another structure through another structure. other structures.
  • Quantum dots are composed of zinc, cadmium, selenium and sulfur atoms. They are nanomaterials with crystal diameters between 2-10nm. It emits pure monochromatic light of various colors and can change the color of light from the light source.
  • quantum dots cannot achieve the same vapor deposition method as self-luminous OLEDs due to their shortcomings of being easily affected by heat and moisture.
  • they can only be printed by inkjet.
  • it is difficult to achieve high resolution by inkjet printing.
  • the disclosure provides a quantum dot ligand and a quantum dot-ligand system containing the quantum dot ligand.
  • the system has photosensitive properties and can directly form red, green, and blue sub-pixels through a photolithography process, avoiding similar Due to the technical difficulty of improving the resolution of inkjet printing, such as the need for higher-precision printing nozzles, etc.
  • the quantum dot ligand provided by the present disclosure is helpful to realize the production of high-resolution QLED products, facilitates the preparation of the process, improves the process yield, and can greatly improve the utilization rate of quantum dot materials, thereby providing a large-scale QLED. Industrialization provides the basis.
  • the disclosure provides a quantum dot ligand, the quantum dot ligand includes an X group, a Y group and a Z group,
  • the Y group is used to provide at least two connection sites, wherein at least one connection site is used for connecting with X, and the remaining connection sites are used for connecting with Z group;
  • the X group is a coordination group, which is used to form a coordination bond with the surface of the quantum dot;
  • the Z group is a saturated 3-5 membered heterocyclic group containing O or S.
  • the quantum dot ligand provided in the present disclosure contains a coordination group and a saturated 3-5 membered heterocyclic group containing O or S. Coordinating groups can form coordination bonds with quantum dots, thereby forming quantum dot-ligand units.
  • the saturated 3-5-membered heterocyclic group containing O or S can undergo a ring-opening reaction with the assistance of photoacid generators, so that cross-linking occurs between quantum dots and ligand units, thereby providing energy for the quantum dot film.
  • the basis is formed by photolithography.
  • Quantum dots are inorganic semiconductor nanoparticles synthesized by a solution method with a size between 1-10 nm, which is close to or smaller than the exciton Bohr radius of the particle. Due to their small size and large specific surface area, quantum dots are prone to agglomeration, and the surface of quantum dots has many surface defects. Therefore, the surface of quantum dots is usually covered with organic surface ligands during application. The protective effect makes the quantum dots have better solubility in the solution.
  • the migration of carriers (electrons and holes) in quantum dots is confined inside the quantum dots, which makes quantum dots have unique optical and electrical properties. Due to the unique size-dependent properties, the light-absorbing and light-emitting properties of quantum dots can be easily tuned by controlling particle size, shape, or surface structure.
  • the surface of quantum dots is usually coated with a layer of organic ligands. These surface ligands not only determine the solubility and surface chemical functionality of quantum dots, but also largely affect the fluorescence quantum yield and electrical properties of quantum dots. .
  • a site of attachment means that certain groups provide a chemical bond that can be used to attach to other groups.
  • the Y group can have two or more linking sites, and different linking sites can be linked to different groups.
  • the Y group is used to provide at least two attachment sites, at least one of which is for attachment to the X group and the remaining attachment sites are for attachment to the Z group.
  • the connection point is used to connect with the X group or the Z group, specifically the connection point can be directly connected with the X group or the Z group, and can also be indirectly connected with the X group or the Z group through an intermediate group. group connection.
  • the number of X groups in the quantum dot ligand structure is multiple.
  • the quantum dot ligand The number of Z groups in the structure is multiple.
  • the X group and the Z group are the terminal groups of the quantum dot ligand structure.
  • the coordinating group is connected to the surface of the quantum dot through a coordination bond, thereby introducing the quantum dot ligand of the present disclosure onto the quantum dot.
  • the Z group is a saturated 3-5 membered heterocyclic group containing O or S. Specifically, it may be a saturated 3-membered heterocyclic group, a saturated 4-membered heterocyclic group or a saturated 5-membered heterocyclic group.
  • the Z group is a photosensitive group
  • the Z group in the quantum dot ligand is used for ring opening and cross-linking reaction with the adjacent quantum dot ligand under external influence.
  • the Y group includes at least one linking group, the linking group provides at least two linking sites, and among the linking sites of the linking group, one linking site is used to link with the Z group,
  • the linking group is selected from alkylene groups with 2-12 carbon atoms.
  • the Y group may include one or more linking groups.
  • the linking group has two linking sites, one of which is used to link with the coordinating group, that is, the X group, and the other linking site is used to link with the Z group connect.
  • the multiple linking groups may be the same or different.
  • One of the linking sites in these linking groups is used to link to the Z group, and the remaining linking sites are used to link to the X group or other linking groups, and at least one of the linking groups has at least one of the linking groups
  • the attachment site is for attachment to the X group.
  • one of the linking groups can be used as a parent chain, and the other linking groups can be used as branch chains.
  • the parent chain linking group has a plurality of linking sites, wherein at least one linking site of the parent chain linking group is used to link with the X group, at least one linking site is used to link with the Z group, and the remaining linking sites For connecting with branched linking groups.
  • the branch linking group may have two linking sites, wherein one linking site of the branching linking group is used for linking with the parent chain linking group, and the other linking site is used for linking with the Z group.
  • the Y group formed by connecting multiple linking groups behaves as a branched dendritic molecule.
  • the linking group is selected from alkylene groups with 2-12 carbon atoms. Specifically, the number of carbon atoms in the alkylene group may be 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12.
  • the alkylene group may be straight chain or branched chain. Such as ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, etc.
  • the Y group further includes a carrier transport regulating group, and the carrier transport regulating group is connected between the linking group and the Z group.
  • the carrier transport regulating group is set in the quantum dot ligand so as to subsequently form a quantum dot-ligand material with strong carrier transport capability.
  • the carrier transport regulating group is selected from aniline structure, triphenylamine structure or carbazole structure. Among them, triphenylamine structure and carbazole structure are beneficial to hole transport.
  • the Y group further includes a dissolving group, the dissolving group is connected between the linking group and the Z group, and the dissolving group is selected from the group consisting of of the structure.
  • the dissolving group can be connected between the linking group and the carrier transport regulating group, or can be connected to the carrier transport regulating group and the Z group ( between photosensitive groups). Setting the dissolving group in the quantum dot ligand of the present disclosure, on the one hand, helps the synthesis of the quantum dot ligand, and on the other hand, also helps to increase the solubility of the quantum dot ligand.
  • the coordinating group is selected from an amino group, a carboxylic acid group, a mercapto group, a phosphino group, a phosphinoxy group or a saturated heterocyclic group containing a disulfide bond.
  • the saturated heterocyclic group containing a disulfide bond may be a saturated five-membered ring or a six-membered ring.
  • the S atom in the mercapto forms a coordination bond with the surface of the ZnSe/CdSe quantum dot.
  • the coordination group When the coordination group is selected from the amino group, the N atom in the amino group forms a coordination bond with the surface of the ZnSe/CdSe quantum dot.
  • the coordination group When the coordination group is selected from a saturated heterocyclic group containing a disulfide bond, the disulfide bond is broken, and the S atom in it forms a coordination bond with the surface of the ZnSe/CdSe quantum dot.
  • the Z group is preferably an epoxy group.
  • the epoxy group is a three-membered ring, and the three-membered ring is easier to synthesize and has a faster rate of ring-opening polymerization, and does not require heating.
  • the quantum dot ligand is selected from the group consisting of the following structures:
  • R 1 , R 2 , R 3 and R 4 are each independently selected from amino, carboxylate, mercapto, phosphino, phosphinoxy or
  • Ar 1 is selected from the group containing aniline, carbazolyl or The structure, R 5 is selected from
  • n1, n2 and n3 are each independently selected from any integer of 2-8.
  • triphenylamine group has very strong rigidity, causes its solubility difference, and R5 group has stronger solubility, and R5 is connected with triphenylamine group, helps to improve triphenylamine Solubility of the structure.
  • the description method used is "independently selected from” in a broad sense, which can mean that in different groups, the specific options expressed by the same symbols do not affect each other, or it can mean that In the same group, the specific options expressed by the same symbols do not affect each other.
  • the quantum dot ligand is selected from the group consisting of the following structures:
  • R is selected from
  • n1, n2, and n3 are each independently selected from any integer of 2-8.
  • the epoxy group has sufficient solubility in PGMEA (propylene glycol methyl ether acetate) and other medium-polarity to high-polarity solvents. Therefore, the epoxy group in the present disclosure can be used as a photosensitive group, Can also be used as a solubilizing group, which contains The structural connection of the quantum dot ligands can jointly enhance the solubility of the quantum dot ligands while ensuring that the quantum dot ligands of the present disclosure have photosensitive properties.
  • PGMEA propylene glycol methyl ether acetate
  • the present disclosure also provides a quantum dot-ligand system, including quantum dots, a photoacid generator and the aforementioned quantum dot ligands.
  • the inorganic portion of quantum dots in this disclosure includes, but is not limited to, CdS, CdSe, ZnSe, InP, PbS, CsPbCl 3 , CsPbBr 3 , CsPhI 3 , CdS/ZnS, CdSe/ZnS, ZnSe, InP/ZnS, PbS/ZnS, CsPbCl 3 /ZnS, CsPbBr 3 /ZnS, CsPhI 3 /ZnS, ZnSe, ZnTeSe/ZnSe and other quantum dots; also include ZnO, ZnMgO, ZnAlO, ZnLiO and other nano particle materials.
  • a photoacid generator is a light-sensitive compound that decomposes under light to produce acid (H + ).
  • the photoacid generator is selected from sulfonium salts, triazines, sulfonate esters or diazonium salts.
  • the photoacid generator is selected from triphenylsulfonium hexafluoroantimonate, (4,6)-bis(trichloromethyl)-1,3,5 triazine derivatives, N-p-toluenesulfonium Acyloxyphthalimide, Diazofluoroborate.
  • quantum dots and quantum dot ligands can be connected by coordination bonds to form quantum dot-ligand units, and photoacid generators can be decomposed under light to generate acid (H + ), which promotes
  • acid H +
  • the saturated heterocyclic group containing O or S in the dot-ligand unit is ring-opened, and the quantum dot-ligand unit is cross-linked.
  • the present disclosure also provides a quantum dot-ligand material, including at least two quantum dot-ligand units, the quantum dot-ligand units include quantum dots and the above-mentioned quantum dot ligands, and the quantum dot-ligand units pass through The Z groups are ring-opened and bonded to each other to form a network structure.
  • the present disclosure also provides a method for preparing a quantum dot film layer, including:
  • the quantum dot-ligand solution is a mixed solution including quantum dots, photoacid generators and the above-mentioned quantum dot ligands;
  • Developing treatment is carried out to form a quantum dot film layer.
  • the present disclosure also provides a quantum dot light-emitting device, including an anode, a cathode, and a functional layer disposed between the anode and the cathode, the functional layer includes a quantum dot light-emitting layer, and the quantum dot light-emitting layer includes the above-mentioned quantum dot-ligand material.
  • the functional layer also includes a hole injection layer, a hole transport layer, an electron transport layer and an electron injection layer.
  • the quantum dot light-emitting device may include an anode, a hole transport layer, a quantum dot light-emitting layer, an electron transport layer and a cathode which are sequentially stacked.
  • the anode includes an anode material, preferably a material with a large work function that facilitates hole injection into the functional layer.
  • anode materials include: metals such as nickel, platinum, vanadium, chromium, copper, zinc and gold or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO) and indium zinc oxide (IZO). It preferably comprises a transparent electrode comprising indium tin oxide (ITO) as an anode.
  • the hole transport layer may include one or more hole transport materials, and the hole transport materials may be selected from carbazole polymers, carbazole-linked triarylamine compounds, or other types of compounds. No special restrictions are made.
  • the electron transport layer can be a single-layer structure or a multilayer structure, which can include one or more electron transport materials, and the electron transport material can be selected from benzimidazole derivatives, oxadiazole derivatives, quinoxaline derivatives material or other electron transport materials, the present disclosure makes no special limitation on this.
  • the cathode includes a cathode material that is a material with a small work function that facilitates injection of electrons into the functional layer.
  • cathode materials include: metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead or alloys thereof; or multilayer materials such as LiF/Al, Liq/ Al, LiO 2 /Al, LiF/Ca, LiF/Al, and BaF 2 /Ca, but not limited thereto.
  • a hole injection layer may also be provided between the anode and the hole transport layer to enhance the ability to inject holes into the hole transport layer.
  • An electron injection layer may also be provided between the cathode and the electron transport layer to enhance the ability to inject electrons into the electron transport layer.
  • the present disclosure also provides a method for preparing a quantum dot light-emitting device, including the following steps:
  • the green quantum dot-ligand solution is a mixed solution including green quantum dots, photoacid generators and the above-mentioned quantum dot ligands;
  • the blue quantum dot-ligand solution is a mixed solution including blue quantum dots, photoacid generators and the above-mentioned quantum dot ligands;
  • red quantum dot-ligand solution is provided, and the red quantum dot-ligand solution is a mixed solution including red quantum dots, photoacid generators and the above-mentioned quantum dot ligands;
  • the red quantum dot-ligand solution is coated on the substrate, exposed and developed to form red sub-pixels.
  • the present disclosure also provides a display device, including the above-mentioned quantum dot light-emitting device.
  • the display device of the present disclosure may be electronic equipment such as a mobile phone, a tablet computer, and a television, which will not be listed here.
  • Lipoic acid thioctic acid, CAS 62-46-4; 20.6g, 100mmol
  • allyl alcohol prop-2-en-1-ol, CAS 107-18-6; 5.81g, 100mmol
  • 4-dimethyl Aminopyridine 4-dimethylaminopyridine, DMAP, CAS 1122-58-3; 1.22 g, 10 mmol
  • the synthesis formula and synthesis method of the quantum dot ligand described above are only illustrative examples of the synthesis method of the quantum dot coordination in the present disclosure, and those skilled in the art can refer to the above method to synthesize other quantum dot ligands protected in the present disclosure.
  • Photolithography process forms quantum dot film layer
  • Quantum dot-ligand solution is provided, and the quantum dot-ligand solution is a mixed solution comprising quantum dots, photoacid generators and quantum dot ligands, and the specific steps are as follows:
  • Dissolve the quantum dot CdSe/ZnSe of the oleic acid ligand in toluene solution add the quantum dot ligand provided by the present disclosure, such as the ligand shown in Table 1, stir for 4-12 hours, use ethyl acetate/toluene to precipitate/ After dissolving for 3 times, use ethyl acetate to precipitate, dry, and dissolve in toluene to obtain quantum dots with quantum dot ligands in the present disclosure, as shown in Table 2.
  • a green quantum dot-ligand solution a blue quantum dot-ligand solution, and a red quantum dot-ligand solution can be prepared respectively by controlling the size of the quantum dots.
  • Quantum dots with quantum dot ligands of the present disclosure are as follows:
  • the green quantum dot-ligand solution is coated on the substrate 1 to form a green quantum dot film layer 21, and the first patterning (Photo Mask) process is added, and the whole is exposed to ultraviolet light.
  • the substrate After exposure, heat the substrate at 90°C for 120s (to promote complete Boc deprotection reaction); then use one or more mixtures of chloroform, toluene, chlorobenzene, tetrahydrofuran, n-hexane, n-heptane, n-octane
  • the solvent is used as a developer for rinsing and development; after development, the substrate is heated again in an environment of 90° C. for 120 s to remove the developer to form green sub-pixels 211 .
  • the blue quantum dot-ligand solution is coated to form a blue quantum dot film layer 22, and the second Photo Mask is added to expose the whole with ultraviolet light, and then developed and fixed to form a blue light matte layer.
  • the red quantum dot-ligand solution is finally coated to form a red quantum dot film layer 23, and the third Photo Mask is added to expose the whole with ultraviolet light, and then developed and fixed to form a red light matte layer. 231 pixels.
  • the changes of the quantum dots after exposure of other ligands can refer to the above content.
  • the display panel includes a quantum dot light-emitting device, and the quantum dot light-emitting device includes an anode, a hole injection layer, a hole transport layer, a quantum dot light-emitting layer, an electron transport layer, an electron injection layer and a cathode that are sequentially stacked.
  • the display panel preparation method specifically includes the following steps:
  • the transparent substrate is cleaned by standard methods, and then the gate metal Mo 200nm is sequentially deposited and patterned; the gate dielectric SiO 2 is 150nm; the active layer IGZO is 40nm and patterned; the source and drain metal Mo 200nm is patterned; The SiO 2 layer is 300nm, and patterned; the pixel electrode ITO is 40nm, and patterned; finally, the acrylic material is deposited by spin coating, photolithography, and curing to form a pixel definition layer, about 1.5um, to form a TFT backplane;
  • the surface of the TFT backplane is treated with plasma.
  • the hole injection layer and the hole transport layer are prepared by spin coating, such as spin coating PEDOT (poly 3,4-ethylenedioxythiophene): PSS (polystyrene sulfonic acid) and TFB, etc.; the overall thickness is 50- 100nm.
  • PEDOT poly 3,4-ethylenedioxythiophene
  • PSS polystyrene sulfonic acid
  • TFB hole transport layer
  • the quantum dot film layer is formed by using the above photolithography process, which specifically includes coating the green quantum dot-ligand solution, adding the first Photo Mask, exposing the whole with ultraviolet light, and then developing and fixing to form green light sub-pixels; and then coating Cloth the blue quantum dot-ligand solution, add the second Photo Mask, expose the whole with ultraviolet light, then develop and fix to form blue light sub-pixels; finally apply the red quantum dot-ligand solution, add the third Photo Mask , using ultraviolet light to expose the whole, and then developing and fixing to form red light sub-pixels.
  • the cathode can use Al layer, etc., about 500-1000nm, after the evaporation is completed, package and cut to complete the preparation of the entire display panel.
  • the light output mode of the AMQLED device can be bottom light output, the minimum sub-pixel area that can be prepared is 10-30 microns, and the display panel is about 300-800ppi.

Abstract

一种量子点配体、量子点-配体体系及量子点材料，属于显示技术领域。该量子点配体包括X基团、Y基团和Z基团，其中，所述Y基团用于提供至少两个连接位点，其中至少一个连接位点用于与X连接，剩余连接位点用于与所述Z基团连接；所述X基团为配位基团，用于与量子点表面形成配位键；所述Z基团为含O或S的饱和3-5元杂环基团。含O或S的饱和3-5元杂环基团可在光致生酸剂的辅助作用下，进行开环反应，使量子点-配体单元间发生交联，从而为量子点膜层能采用光刻工艺形成提供的基础。

Description

量子点配体、量子点-配体体系及量子点材料 技术领域
本公开涉及显示技术领域，尤其涉及一种量子点配体、量子点-配体体系及量子点材料。
背景技术
随着量子点制备技术的深入发展，量子点的稳定性以及发光效率不断提升，量子点电致发光二极管(Quantum Dot Light Emitting Diodes，QLED)的研究不断深入，QLED在显示领域的应用前景日渐光明。然而，QLED的效率还没有达到量产水平。其中一个重要原因是QLED的高分辨率图案化技术还没有取得突破。
量子点的无机纳米粒子特征使其无法通过蒸镀成膜并图案化；通过喷墨打印法很难达到较高的分辨率。
所述背景技术部分公开的上述信息仅用于加强对本公开的背景的理解，因此它可以包括不构成对本领域普通技术人员已知的现有技术的信息。
公开内容
本公开的目的在于提供一种量子点配体、量子点-配体体系及量子点材料，该量子点配体为量子点膜层能采用光刻工艺形成提供了基础。
为实现上述发明目的，本公开采用如下技术方案：
根据本公开的第一个方面，提供一种量子点配体，所述量子点配体包括X基团、Y基团和Z基团，
其中，所述Y基团用于提供至少两个连接位点，其中至少一个连接位点用于与X连接，剩余连接位点用于与所述Z基团连接；
所述X基团为配位基团，用于与量子点表面形成配位键；
所述Z基团为含O或S的饱和3-5元杂环基团。
在本公开的一种示例性实施例中，所述量子点配体中的所述Z基团用于在外界作用下开环与相邻所述量子点配体发生交联反应。
在本公开的一种示例性实施例中，所述Y基团包括至少一个连接基团，所述连接基团提供至少两个连接位点，所述连接基团的连接位点中，其中一个连接位点用于与所述Z基团连接，所述连接基团选自碳原子数为2-12的亚烷基。
在本公开的一种示例性实施例中，所述Y基团还包括载流子传输调节基团，所述载流子传输调节基团连接于所述连接基团和所述Z基团之间。
在本公开的一种示例性实施例中，所述载流子传输调节基团选自苯胺结构、三苯胺类结构或咔唑类结构。
在本公开的一种示例性实施例中，所述Y基团还包括溶解基团，所述溶解基团连接于所述连接基团和所述Z基团之间，所述溶解基团选自包含
Figure PCTCN2021121925-appb-000001
的结构。
在本公开的一种示例性实施例中，所述配位基团选自氨基，羧酸基，巯基，膦基，膦氧基或含双硫键的饱和杂环基。
在本公开的一种示例性实施例中，所述Z基团选自环氧基。
在本公开的一种示例性实施例中，所述量子点配体选自如下结构所组成的组：
Figure PCTCN2021121925-appb-000002
其中，R 1、R 2、R 3和R 4各自独立地选自氨基，羧酸基，巯基，膦基，膦氧基或
Figure PCTCN2021121925-appb-000003
Ar 1选自含亚苯胺基、亚咔唑基或
Figure PCTCN2021121925-appb-000004
的结构，R 5选自
Figure PCTCN2021121925-appb-000005
n1、n2和n3各自独立地选自2-8的任意整数。
在本公开的一种示例性实施例中，所述量子点配体选自如下结构所组成的组：
Figure PCTCN2021121925-appb-000006
其中，R选自
Figure PCTCN2021121925-appb-000007
n1、n2、n3各自独立地选自2-8的任意整数。
根据本公开的第二个方面，提供一种量子点-配体体系，包括量子点、光致生酸剂和第一方面所述的量子点配体。
在本公开的一种示例性实施例中，所述光致生酸剂选自硫鎓盐类、三嗪类，磺酸酯类或重氮盐类。
根据本公开的第三个方面，提供一种量子点-配体材料，包括至少两 个量子点-配体单元，所述量子点-配体单元包括量子点和第一方面所述的量子点配体，所述量子点-配体单元之间通过所述Z基团开环相互键合交联形成网状结构。
根据本公开的第四个方面，提供一种量子点膜层的制备方法，包括：
提供量子点-配体溶液，所述量子点-配体溶液为包括量子点、光致生酸剂和如第一方面所述的量子点配体的混合溶液；
于基底上涂布所述量子点-配体溶液，进行曝光处理，使得光致生酸剂产生氢离子，并催化所述Z基团开环发生交联反应；
进行显影处理，形成所述量子点膜层。
根据本公开的第五个方面，提供一种量子点发光器件，包括阳极、阴极和设置于所述阳极和所述阴极之间的功能层，所述功能层包括量子点发光层，所述量子点发光层包括如第三方面所述的量子点-配体材料。
在本公开的一种示例性实施例中，所述功能层还包括空穴注入层、空穴传输层、电子传输层和电子注入层。
根据本公开的第六个方面，提供一种量子点发光器件的制备方法，包括：
提供绿色量子点-配体溶液，所述绿色量子点-配体溶液为包括绿色量子点、光致生酸剂和如第一方面所述的量子点配体的混合溶液；
提供蓝色量子点-配体溶液，所述蓝色量子点-配体溶液为包括蓝色量子点、光致生酸剂和如第一方面所述的量子点配体的混合溶液；
提供红色量子点-配体溶液，所述红色量子点-配体溶液为包括红色量子点、光致生酸剂和如第一方面所述的量子点配体的混合溶液；
于基底上涂布所述绿色量子点-配体溶液，进行曝光显影，形成绿色子像素；
于基底上涂布所述蓝色量子点-配体溶液，进行曝光显影，形成蓝色子像素；
于基底上涂布所述红色量子点-配体溶液，进行曝光显影，形成红色子像素。
根据本公开的第七个方面，提供一种显示装置，包括如第五方面所述的量子点发光器件。
本公开提供的量子点配体中包含有配位基团和含O或S的饱和3-5元杂环基团。配位基团可以与量子点之间形成配位键，从而形成量子点-配体单元。含O或S的饱和3-5元杂环基团可在光致生酸剂的辅助作用下，进行开环反应，使量子点-配体单元间发生交联，从而为量子点膜层能采用光刻工艺形成提供的基础。
附图说明
通过参照附图详细描述其示例实施方式，本公开的上述和其它特征及优点将变得更加明显。
图1是本公开示例性实施例中在基底上涂布绿色-量子点配体溶液结构示意图；
图2是本公开示例性实施例中形成绿光亚像素结构示意图；
图3是本公开示例性实施例中在基底上涂布蓝色-量子点配体溶液结构示意图；
图4是本公开示例性实施例中形成蓝光亚像素结构示意图；
图5是本公开示例性实施例中在基底上涂布红色-量子点配体溶液结构示意图；
图6是本公开示例性实施例中形成红光亚像素结构示意图。
图中主要元件附图标记说明如下：
1-基底；21-绿色量子点膜层；211-绿光亚像素；22-蓝色量子点膜层；221-蓝光亚像素；23-红色量子点膜层；231-红光亚像素。
具体实施方式
现在将参考附图更全面地描述示例实施例。然而，示例实施例能够以多种形式实施，且不应被理解为限于在此阐述的范例；相反，提供这些实施例使得本公开将更加全面和完整，并将示例实施例的构思全面地传达给本领域的技术人员。所描述的特征、结构或特性可以以任何合适的方式结合在一个或更多实施例中。在下面的描述中，提供许多具体细节从而给出对本公开的实施例的充分理解。
在图中，为了清晰，可能夸大了区域和层的厚度。在图中相同的附图标记表示相同或类似的结构，因而将省略它们的详细描述。
所描述的特征、结构或特性可以以任何合适的方式结合在一个或更多实施例中。在下面的描述中，提供许多具体细节从而给出对本公开的实施例的充分理解。然而，本领域技术人员将意识到，可以实践本公开的技术方案而没有所述特定细节中的一个或更多，或者可以采用其它的方法、组元、材料等。在其它情况下，不详细示出或描述公知结构、材料或者操作以避免模糊本公开的主要技术创意。
当某结构在其它结构“上”时，有可能是指某结构一体形成于其它结构上，或指某结构“直接”设置在其它结构上，或指某结构通过另一结构“间接”设置在其它结构上。
用语“一个”、“一”、“所述”用以表示存在一个或多个要素/组成部分/等；用语“包括”和“具有”用以表示开放式的包括在内的意思并且是指除了列出的要素/组成部分/等之外还可存在另外的要素/组成部分/等。用语“第一”和“第二”等仅作为标记使用，不是对其对象的数量限制。
量子点(Quantum Dots，QD)由锌、镉、硒和硫原子构成，是晶体直径在2-10nm之间的纳米材料，其光电特性独特，受到光电刺激后，会根据量子点的直径大小，发出各种不同颜色的纯正单色光，能够改变光源光线的颜色。
相关技术中，量子点因其容易受热量和水分影响的缺点，无法实现与自发光OLED相同的蒸镀方式，目前只能喷墨印刷。然而，通过喷墨打印很难达到较高的分辨率。
本公开提供一种量子点配体，及包含该量子点配体的量子点-配体体系，该体系具有光敏特性，可通过光刻工艺直接形成红、绿、蓝亚像素，避开了类似于喷墨打印提升分辨率的技术难度，如需要更高精度的打印喷头等。本公开提供的量子点配体有助于实现高分辨率的QLED产品生产，方便了工艺方面的制备，提升了工艺良率，能够大幅提升量子点材料的使用率，从而为大规模的QLED的产业化提供了基础。
本公开提供一种量子点配体，量子点配体包括X基团、Y基团和Z基团，
其中，Y基团用于提供至少两个连接位点，其中至少一个连接位点用于与X连接，剩余连接位点用于与Z基团连接；
X基团为配位基团，用于与量子点表面形成配位键；
Z基团为含O或S的饱和3-5元杂环基团。
本公开提供的量子点配体中包含有配位基团和含O或S的饱和3-5元杂环基团。配位基团可以与量子点之间形成配位键，从而形成量子点-配体单元。含O或S的饱和3-5元杂环基团可在光致生酸剂的辅助作用下，进行开环反应，使量子点-配体单元间发生交联，从而为量子点膜层能采用光刻工艺形成提供基础。
量子点(QDs)是一种通过溶液法合成且尺寸介于1-10nm的无机半导体纳米颗粒，该尺寸近似或小于粒子的激子波尔半径。量子点由于尺寸很小、比表面积大，容易发生团聚，并且量子点的表面缺陷较多，因此在应用时量子点的表面通常还包覆着有机表面配体，该有机表面配体既起到保护作用又使量子点在溶液中有较好的溶解性。量子点中载流子(电子和空穴)的迁移被限制在量子点的内部，这样使得量子点具有独特的光学和电学性质。由于独特的尺寸依赖性质，量子点的吸光性能和发光性能可以很容易地通过控制颗粒尺寸、形状或表面结构来调节。
量子点的表面通常会包覆一层有机配体，这些表面配体不仅决定着量子点的溶解性、表面化学功能性，还在很大程度上影响到量子点的荧光量子产率、电学性质。
在本公开中，连接位点是指某些基团提供化学键，该化学键可用于与其他基团连接。Y基团可以有两个或多个连接位点，不同的连接位点可与不同的基团连接。
Y基团用于提供至少两个连接位点，其中至少一个连接位点用于与X基团连接，剩余连接位点用于与Z基团连接。在该表述中，连接位点用于与X基团或Z基团连接，具体该连接位点可直接与X基团或Z基团连接，也可以通过中间基团间接与X基团或Z基团连接。当有多个连接位点与X基团连接时，量子点配体结构中X基团的数量为多个，同理，当有多个连接位点与Z基团连接时，量子点配体结构中Z基团的数量为多个。X基团和Z基团为量子点配体结构的末端基团。
配位基团通过配位键与量子点的表面连接，从而将本公开的量子点配体引入到量子点上。
Z基团为含O或S的饱和3-5元杂环基团。具体可以为饱和3元杂环基团、饱和4元杂环基团或饱和5元杂环基团。
在本公开一些实施例中，Z基团为光敏基团，量子点配体中的Z基团用于在外界作用下开环与相邻量子点配体发生交联反应。
在本公开一些实施例中，Y基团包括至少一个连接基团，连接基团提供至少两个连接位点，连接基团的连接位点中，一个连接位点用于与Z基团连接，所述连接基团选自碳原子数为2-12的亚烷基。
Y基团可以包括一个或多个连接基团。当Y基团只包含一个连接基团时，该连接基团具有两个连接位点，其中一个用于与配位基团，即X基团连接，另一个连接位点用于与Z基团连接。
当Y基团包含多个连接基团时，多个连接基团间可相同或不同。这些连接基团中的一个连接位点用于与Z基团连接，其余连接位点用于与X基团或其他连接基团连接，且连接基团中至少有一个连接基团中的至少一个连接位点用于与X基团连接。举例而言，当Y基团包含多个连接基团时，可以以其中一个连接基团为母链，其他连接基团为支链。母链连接基团具有多个连接位点，其中，母链连接基团的至少一个连接位点用于与X基团连接，至少一个连接位点用于与Z基团连接，剩余连接位点用于与支链连接基团连接。支链连接基团可具有两个连接位点，其中，支链连接基团的一个连接位点用于与母链连接基团连接，另一个连接位点用于与Z基团连接。此时，多个连接基团连接形成的Y基团表现为具有分支的树枝状分子。
连接基团选自碳原子数为2-12的亚烷基。具体地，亚烷基的碳原子数可以为2、3、4、5、6、7、8、9、10、11或12。亚烷基可以为直链亚烷基或支链亚烷基。如乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、戊基、己基、庚基、辛基等。
在本公开一些实施例中，Y基团还包括载流子传输调节基团，载流子传输调节基团连接于连接基团和Z基团之间。将载流子传输调节基团设置在该量子点配体中，以便后续形成具有强载流子传输能力的量子点-配体材料。
载流子传输调节基团选自苯胺结构、三苯胺类结构或咔唑类结构。 其中，三苯胺类结构、咔唑类结构有利于空穴传输。
在本公开一些实施例中，Y基团还包括溶解基团，溶解基团连接于连接基团和Z基团之间，溶解基团选自包含
Figure PCTCN2021121925-appb-000008
的的结构。
当Y基团包括载流子传输调节基团时，溶解基团可连接于连接基团与载流子传输调节基团之间，也可以连接于载流子传输调节基团和Z基团(光敏基团)之间。将溶解基团设置在本公开量子点配体中，一方面有助于量子点配体的合成，另一方面也有助于增加量子点配体的溶解性。
在本公开一些实施例中，配位基团选自氨基，羧酸基，巯基，膦基，膦氧基或含双硫键的饱和杂环基。其中，含双硫键的饱和杂环基可以为饱和的五元环或六元环。举例而言，当配位基团选自巯基时，巯基中的S原子与ZnSe/CdSe量子点的表面形成配位键。当配位基团选自氨基时，氨基中的N原子与ZnSe/CdSe量子点的表面形成配位键。当配位基团选自含双硫键的饱和杂环基时，双硫键断开，其中的S原子与ZnSe/CdSe量子点的表面形成配位键。
在本公开一些实施例中，Z基团优选为环氧基。环氧基为三元环，三元环较易合成且开环聚合速率较快，且不需要加热。
在本公开一些实施例中，量子点配体选自如下结构所组成的组：
Figure PCTCN2021121925-appb-000009
其中，R 1、R 2、R 3和R 4各自独立地选自氨基，羧酸基，巯基，膦基， 膦氧基或
Figure PCTCN2021121925-appb-000010
Ar 1选自含亚苯胺基、亚咔唑基或
Figure PCTCN2021121925-appb-000011
的结构，R 5选自
Figure PCTCN2021121925-appb-000012
n1、n2和n3各自独立地选自2-8的任意整数。
在该实施例中，三苯胺基团因具有很强的刚性，导致其溶解性差，而R 5基团具有较强的溶解性，将R 5与三苯胺基团连接，有助于改善三苯胺结构的溶解性。
在本公开中，所采用的描述方式“各自独立地选自”做广义理解，其既可以是指在不同基团中，相同符号之间所表达的具体选项之间互相不影响，也可以表示在相同的基团中，相同符号之间所表达的具体选项之间互相不影响。
在本公开一些实施例中，量子点配体选自如下结构所组成的组：
Figure PCTCN2021121925-appb-000013
其中，R选自
Figure PCTCN2021121925-appb-000014
n1、n2、n3各自独立地选自2-8的任意整数。
本公开中，环氧基团在PGMEA(丙二醇甲醚醋酸酯)等中极性到高极性溶剂里，有足够的溶解性，因此，本公开环氧基团除可作为光敏基团外，也可作为溶解基团，其与包含
Figure PCTCN2021121925-appb-000015
的结构连接，在保证本公开量子点配体具有光敏特性的同时，可共同增强量子点配体的溶解性。
本公开还提供一种量子点-配体体系，包括量子点、光致生酸剂和上述的量子点配体。
本公开中的量子点无机部分包括但不限于，CdS、CdSe、ZnSe、InP、PbS、CsPbCl 3、CsPbBr 3、CsPhI 3、CdS/ZnS、CdSe/ZnS、ZnSe、InP/ZnS、PbS/ZnS、CsPbCl 3/ZnS、CsPbBr 3/ZnS、CsPhI 3/ZnS，ZnSe，ZnTeSe/ZnSe等量子点；还包括ZnO，ZnMgO，ZnAlO，ZnLiO等纳米粒子材料。
光致生酸剂是一种光敏感的化合物，在光照下分解产生酸(H +)。光致生酸剂选自硫鎓盐类、三嗪类，磺酸酯类或重氮盐类。具体地，光致生酸剂选自六氟锑酸三苯基硫鎓盐、(4，6)-二(三氯甲基)-1,3,5三嗪衍生物，N-对甲苯磺酰氧邻苯二甲酰亚胺、重氮氟硼酸盐。
在该量子点-配体体系中，量子点和量子点配体可通过配位键连接形成量子点-配体单元，光致生酸剂可在光照下分解产生酸(H +)，促使量子点-配体单元中的含O或S的饱和杂环基团开环，量子点-配体单元之间交联。
本公开还提供一种量子点-配体材料，包括至少两个量子点-配体单元，量子点-配体单元包括量子点和上述的量子点配体，量子点-配体单元之间通过Z基团开环相互键合交联形成网状结构。
本公开还提供一种量子点膜层的制备方法，包括：
提供量子点-配体溶液，量子点-配体溶液为包括量子点、光致生酸剂和上述的量子点配体的混合溶液；
于基底上涂布量子点-配体溶液，进行曝光处理，使得光致生酸剂产生氢离子，并催化Z基团开环发生交联反应；
进行显影处理，形成量子点膜层。
本公开还提供一种量子点发光器件，包括阳极、阴极和设置于阳极和阴极之间的功能层，功能层包括量子点发光层，量子点发光层包括上述的量子点-配体材料。
功能层还包括空穴注入层、空穴传输层、电子传输层和电子注入层。
在本公开的一种具体实施方式中，量子点发光器件可以包括依次层叠设置的阳极、空穴传输层、量子点发光层、电子传输层和阴极。
可选地，阳极包括以下阳极材料，其优选地是有助于空穴注入至功能层中的具有大逸出功(功函数，work function)材料。阳极材料具体实例包括：金属如镍、铂、钒、铬、铜、锌和金或它们的合金；金属氧化物如氧化锌、氧化铟、氧化铟锡(ITO)和氧化铟锌(IZO)。优选包括包含氧化铟锡(铟锡氧化物，indium tin oxide)(ITO)作为阳极的透明电极。
可选地，空穴传输层可以包括一种或者多种空穴传输材料，空穴传输材料可以选自咔唑多聚体、咔唑连接三芳胺类化合物或者其他类型的化合物，本公开对此不做特殊的限定。
电子传输层可以为单层结构，也可以为多层结构，其可以包括一种或者多种电子传输材料，电子传输材料可以选自苯并咪唑衍生物、噁二唑衍生物、喹喔啉衍生物或者其他电子传输材料，本公开对此不做特殊的限定。
可选地，阴极包括以下阴极材料，其是有助于电子注入至功能层中的具有小逸出功的材料。阴极材料的具体实例包括：金属如镁、钙、钠、钾、钛、铟、钇、锂、钆、铝、银、锡和铅或它们的合金；或多层材料如LiF/Al、Liq/Al、LiO 2/Al、LiF/Ca、LiF/Al和BaF 2/Ca，但不限于此。
可选地，在阳极和空穴传输层之间还可以设置有空穴注入层，以增强向空穴传输层注入空穴的能力。在阴极和电子传输层之间还可以设置有电子注入层，以增强向电子传输层注入电子的能力。
本公开还提供一种量子点发光器件的制备方法，包括以下步骤：
提供绿色量子点-配体溶液，绿色量子点-配体溶液为包括绿色量子点、光致生酸剂和上述的量子点配体的混合溶液；
提供蓝色量子点-配体溶液，蓝色量子点-配体溶液为包括蓝色量子点、光致生酸剂和上述的量子点配体的混合溶液；
提供红色量子点-配体溶液，红色量子点-配体溶液为包括红色量子点、光致生酸剂和上述的量子点配体的混合溶液；
于基底上涂布绿色量子点-配体溶液，进行曝光显影，形成绿色子像素；
于基底上涂布蓝色量子点-配体溶液，进行曝光显影，形成蓝色子像素；
于基底上涂布红色量子点-配体溶液，进行曝光显影，形成红色子像素。
本公开还提供一种显示装置，包括上述量子点发光器件。本公开的显示装置可以是手机、平板电脑、电视等电子设备，在此不再一一列举。
量子点配体合成例：
(1)量子点配体
Figure PCTCN2021121925-appb-000016
以n1＝3为例
Figure PCTCN2021121925-appb-000017
硫辛酸(thioctic acid，CAS 62-46-4；20.6g，100mmol)与烯丙醇(prop-2-en-1-ol，CAS 107-18-6；5.81g，100mmol)、4-二甲氨基吡啶(4-dimethylaminopyridine，DMAP，CAS 1122-58-3；1.22g，10mmol)溶于100mL无水乙醚中，并将体系降至0℃。将二环己基碳二亚胺(1,3-dicyclohexylcarbodiimide，DCC,CAS 538-75-0；22.7g,110mmol)溶于50mL无水乙醚中，并在0℃下缓慢加入前者。在室温下搅拌过夜后，过滤除去沉淀；滤液低压浓缩后使用硅胶柱提纯，得到产物1(22.1g，90％产率)。 1H NMR(400MHz,CDCl3):δ＝1.25(2H)，1.51(2H)，1.66-1.96(4H)，2.32-2.34(3H),4.69(1H),5.31-5.32(2H),6.05(1H)
将产物1(12.3g，50mmol)，3-氯过氧苯甲酸(3-Chloroperoxybenzoic  acid，mCPBA，CAS 937-14-4；9.49g，55mmol)溶于200mL二氯甲烷中，于0℃搅拌2小时，然后加入1M氢氧化钠终止反应，加入食盐水萃取；将有机相收集，使用无水硫酸钠干燥后，浓缩后使用色谱柱分离得到产物2(11.1g，85％产率). 1H NMR(400MHz,CDCl3):δ＝1.25(2H)，1.51(2H)，1.66-1.96(4H)，2.32-2.34(3H),3.13(1H),4.07(1H),4.32(1H)(2)量子点配体
Figure PCTCN2021121925-appb-000018
通过以下合成式合成：
Figure PCTCN2021121925-appb-000019
(3)量子点配体
Figure PCTCN2021121925-appb-000020
通过以下合成式合成：
Figure PCTCN2021121925-appb-000021
(4)量子点配体
Figure PCTCN2021121925-appb-000022
通过以下合成式合成：
Figure PCTCN2021121925-appb-000023
(5)量子点配体
Figure PCTCN2021121925-appb-000024
通过以下合成式合成：
Figure PCTCN2021121925-appb-000025
上述量子点配体合成式及合成方法仅示例性说明本公开量子点配合的合成方法，本领域技术人员可参照上述方法合成本公开所保护的其他量子点配体。
光刻工艺形成量子点膜层
(1)提供量子点-配体溶液，量子点-配体溶液为包括量子点、光致生酸剂和量子点配体的混合溶液，具体步骤如下：
将油酸配体的量子点CdSe/ZnSe溶在甲苯溶液中，加入本公开提供的量子点配体，如表1所示配体，搅拌4-12小时后，使用乙酸乙酯/甲苯沉淀/溶解3次后，使用乙酸乙酯沉淀，烘干，并溶于甲苯中，获得带有本公开中量子点配体的量子点，如表2所示。
随后往该溶液中加入光致生酸剂，含量为1％-5％质量分数。在该步骤中，可通过控制量子点的尺寸分别制备绿色量子点-配体溶液、蓝色量子点-配体溶液、红色量子点-配体溶液。
表1
Figure PCTCN2021121925-appb-000026
带有本公开中量子点配体的量子点如下：
表2
Figure PCTCN2021121925-appb-000027
Figure PCTCN2021121925-appb-000028
2)于基底上涂布量子点-配体溶液，进行曝光处理，使得光致生酸剂产生氢离子，并催化Z开环发生交联反应；进行显影处理，形成量子点膜层，具体包括如下步骤：
如图1至图2所示，在基底1上涂布绿色量子点-配体溶液，形成绿色量子点膜层21，加第一道图形化(Photo Mask)工艺，采用紫外光对整体曝光，曝光后，将基板至于90℃环境中加热120s(促进Boc脱保护反应进行完全)；之后使用氯仿、甲苯、氯苯、四氢呋喃、正己烷、正庚烷、正辛烷的一种或多种混合溶剂作为显影剂进行冲洗、显影；显影后，再次将基板至于90℃环境中加热120s除去显影剂，形成绿光亚像素211。
如图3至图4所示，涂布蓝色量子点-配体溶液，形成蓝色量子点膜层22，加第二道Photo Mask，采用紫外光对整体曝光，而后显影、定影形成蓝光亚像素221；
如图5至图6所示，最后涂布红色量子点-配体溶液，形成红色量子点膜层23，加第三道Photo Mask，采用紫外光对整体曝光，而后显影、定影形成红光亚像素231。
以表1中的配体1为例，曝光后量子点的变化如下所示：
Figure PCTCN2021121925-appb-000029
其余配体曝光后量子点的变化可参照上述内容。
显示面板制备例
显示面板包括量子点发光器件，量子点发光器件包括依次层叠设置的阳极、空穴注入层、空穴传输层、量子点发光层、电子传输层、电子注入层和阴极。
显示面板制备方法具体包括以下步骤：
透明衬底采用标准方法清洗，之后依次沉积栅极金属Mo 200nm，并图形化；栅极介质SiO 2150nm；有源层IGZO 40nm，并图形化；源漏极金属Mo 200nm，并图形化；钝化层SiO 2 300nm，并图形化；像素电极ITO 40nm，并图形化；最后旋涂沉积亚克力系材料并光刻、固化出像素界定层，约1.5um，形成TFT背板；
制备量子点发光器件(QD-LED)前，采用等离子体处理TFT背板表面。
采用旋涂工艺制备空穴注入层和空穴传输层，如分别旋涂PEDOT(聚3,4-乙烯二氧噻吩)：PSS(聚苯乙烯磺酸)和TFB等；其整体厚度为50-100nm。
采用上述光刻工艺形成量子点膜层，具体包括，涂布绿色量子点-配 体溶液，加第一道Photo Mask，采用紫外光对整体曝光，而后显影、定影形成绿光亚像素；再涂布蓝色量子点-配体溶液，加第二道Photo Mask，采用紫外光对整体曝光，而后显影、定影形成蓝光亚像素；最后涂布红色量子点-配体溶液，加第三道Photo Mask，采用紫外光对整体曝光，而后显影、定影形成红光亚像素。
旋涂或蒸镀形成电子传输层和电子注入层，如ZnO纳米颗粒等。
蒸镀阴极金属薄层，阴极可采用Al层等，约为500-1000nm，蒸镀结束之后进行封装并切割，完成整个显示面板的制备。
该AMQLED器件的出光方式可以为底出光，可制备的亚像素最小面积在10-30微米，显示面板约300-800ppi。
需要说明的是，尽管在附图中以特定顺序描述了本公开中方法的各个步骤，但是，这并非要求或者暗示必须按照该特定顺序来执行这些步骤，或是必须执行全部所示的步骤才能实现期望的结果。附加的或备选的，可以省略某些步骤，将多个步骤合并为一个步骤执行，以及/或者将一个步骤分解为多个步骤执行等，均应视为本公开的一部分。
应可理解的是，本公开不将其应用限制到本说明书提出的部件的详细结构和布置方式。本公开能够具有其他实施方式，并且能够以多种方式实现并且执行。前述变形形式和修改形式落在本公开的范围内。应可理解的是，本说明书公开和限定的本公开延伸到文中和/或附图中提到或明显的两个或两个以上单独特征的所有可替代组合。所有这些不同的组合构成本公开的多个可替代方面。本说明书的实施方式说明了已知用于实现本公开的最佳方式，并且将使本领域技术人员能够利用本公开。

Claims (18)

  1. 一种量子点配体，包括X基团、Y基团和Z基团，
    其中，所述Y基团用于提供至少两个连接位点，其中至少一个连接位点用于与X连接，剩余连接位点用于与所述Z基团连接；
    所述X基团为配位基团，用于与量子点表面形成配位键；
    所述Z基团为含O或S的饱和3-5元杂环基团。
  2. 根据权利要求1所述的量子点配体，其中，所述量子点配体中的所述Z基团用于在外界作用下开环与相邻所述量子点配体发生交联反应。
  3. 根据权利要求1所述的量子点配体，其中，所述Y基团包括至少一个连接基团，所述连接基团提供至少两个连接位点，所述连接基团的连接位点中，其中一个连接位点用于与所述Z基团连接，所述连接基团选自碳原子数为2-12的亚烷基。
  4. 根据权利要求3所述的量子点配体，其中，所述Y基团还包括载流子传输调节基团，所述载流子传输调节基团连接于所述连接基团和所述Z基团之间。
  5. 根据权利要求4所述的量子点配体，其中，所述载流子传输调节基团选自苯胺结构、三苯胺类结构或咔唑类结构。
  6. 根据权利要求3所述的量子点配体，其中，所述Y基团还包括溶解基团，所述溶解基团连接于所述连接基团和所述Z基团之间，所述溶解基团选自包含
    Figure PCTCN2021121925-appb-100001
    的结构。
  7. 根据权利要求1所述的量子点配体，其中，所述配位基团选自氨基，羧酸基，巯基，膦基，膦氧基或含双硫键的饱和杂环基。
  8. 根据权利要求1所述的量子点配体，其中，所述Z基团选自环氧基。
  9. 根据权利要求1所述的量子点配体，其中，所述量子点配体选自如下结构所组成的组：
    Figure PCTCN2021121925-appb-100002
    Figure PCTCN2021121925-appb-100003
    其中，R 1、R 2、R 3和R 4各自独立地选自氨基，羧酸基，巯基，膦基，膦氧基或
    Figure PCTCN2021121925-appb-100004
    Ar 1选自含亚苯胺基、亚咔唑基或
    Figure PCTCN2021121925-appb-100005
    的结构，R 5选自
    Figure PCTCN2021121925-appb-100006
    n1、n2和n3各自独立地选自2-8的任意整数。
  10. 根据权利要求1所述的量子点配体，其中，所述量子点配体选自如下结构所组成的组：
    Figure PCTCN2021121925-appb-100007
    其中，R选自
    Figure PCTCN2021121925-appb-100008
    n1、n2、n3各自独立地选自2-8的任意整数。
  11. 一种量子点-配体体系，其中，包括量子点、光致生酸剂和如权利要求1-10任一项所述的量子点配体。
  12. 根据权利要求11所述的量子点-配体体系，其中，所述光致生酸剂选自硫鎓盐类、三嗪类，磺酸酯类或重氮盐类。
  13. 一种量子点-配体材料，其中，包括至少两个量子点-配体单元，所述量子点-配体单元包括量子点和如权利要求1-10任一项所述的量子点配体，所述量子点-配体单元之间通过所述Z基团开环相互键合交联形成网状结构。
  14. 一种量子点膜层的制备方法，其中，包括：
    提供量子点-配体溶液，所述量子点-配体溶液为包括量子点、光致生酸剂和如权利要求1-10任一项所述的量子点配体的混合溶液；
    于基底上涂布所述量子点-配体溶液，进行曝光处理，使得光致生酸剂产生氢离子，并催化所述Z基团开环发生交联反应；
    进行显影处理，形成所述量子点膜层。
  15. 一种量子点发光器件，其中，包括阳极、阴极和设置于所述阳极和所述阴极之间的功能层，所述功能层包括量子点发光层，所述量子点发光层包括如权利要求13所述的量子点-配体材料。
  16. 根据权利要求15所述的量子点发光器件，其中，所述功能层还包括空穴注入层、空穴传输层、电子传输层和电子注入层。
  17. 一种量子点发光器件的制备方法，其中，包括：
    提供绿色量子点-配体溶液，所述绿色量子点-配体溶液为包括绿色量子点、光致生酸剂和如权利要求1-10任一项所述的量子点配体的混合溶液；
    提供蓝色量子点-配体溶液，所述蓝色量子点-配体溶液为包括蓝色量子点、光致生酸剂和如权利要求1-10任一项所述的量子点配体的混合溶液；
    提供红色量子点-配体溶液，所述红色量子点-配体溶液为包括红色量子点、光致生酸剂和如权利要求1-10任一项所述的量子点配体的混合溶液；
    于基底上涂布所述绿色量子点-配体溶液，进行曝光显影，形成绿色子像素；
    于基底上涂布所述蓝色量子点-配体溶液，进行曝光显影，形成蓝色子像素；
    于基底上涂布所述红色量子点-配体溶液，进行曝光显影，形成红色子像素。
  18. 一种显示装置，其中，包括如权利要求15-16任一项所述的量子点发光器件。
PCT/CN2021/121925 2021-09-29 2021-09-29 量子点配体、量子点-配体体系及量子点材料 WO2023050214A1 (zh)

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