WO2023005840A1 - 量子点材料及其制备方法、量子点显示器件、显示装置、量子点膜图案化的方法、量子点发光器件的制备方法 - Google Patents

量子点材料及其制备方法、量子点显示器件、显示装置、量子点膜图案化的方法、量子点发光器件的制备方法 Download PDF

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WO2023005840A1
WO2023005840A1 PCT/CN2022/107380 CN2022107380W WO2023005840A1 WO 2023005840 A1 WO2023005840 A1 WO 2023005840A1 CN 2022107380 W CN2022107380 W CN 2022107380W WO 2023005840 A1 WO2023005840 A1 WO 2023005840A1
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quantum dot
ligand
group
quantum
ligands
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French (fr)
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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 US18/265,687 priority Critical patent/US20240147838A1/en
Publication of WO2023005840A1 publication Critical patent/WO2023005840A1/zh

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    • C09K11/66—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing germanium, tin or lead
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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    • C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
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    • C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
    • C09K11/881—Chalcogenides
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
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    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots

Definitions

  • Embodiments of the present disclosure relate to but are not limited to the field of display technology, and in particular, relate to a quantum dot material and its preparation method, a quantum dot display device, a display device, a quantum dot film patterning method, and a quantum dot Preparation method of light-emitting device.
  • Quantum Dots Light Emitting Diode is a new type of display technology developed on the basis of organic light emitting displays.
  • the light-emitting layer in QLED is a quantum dot layer, and its principle is that electrons and holes are injected into the quantum dot layer and recombine and emit light in the quantum dot layer.
  • QLED is a potential next-generation self-luminous display technology. Compared with Organic Light Emitting Diode (OLED), QLED has outstanding advantages such as lower energy consumption, higher color purity, and wider color gamut.
  • the application goal of QLED technology is high-resolution dynamic full-color display.
  • the precise preparation of the QLED sub-pixel area is a prerequisite for realizing high-resolution dynamic full-color display, which requires precise patterning of the quantum dot light-emitting layer.
  • An embodiment of the present disclosure provides a quantum dot material, the quantum dot material includes: quantum dots and ligands modifying the quantum dots, the ligands coordinate with the quantum dots, and the ligands have photosensitive It is a derivative of azobenzene and contains ureido and pyrimidinone groups.
  • the ligand is configured to exhibit a cis structure after being irradiated with ultraviolet light, and a quadruple hydrogen bond is formed between molecules of the ligand; it can exhibit a trans structure after being irradiated with visible light, and Intramolecular hydrogen bonding of the ligands is formed.
  • the general structural formula of the ligand may be:
  • At least one of A, B, and C contains a coordination group capable of coordinating with the quantum dot.
  • A is (CH 2 ) x —Y, wherein, 0 ⁇ x ⁇ 12, Y is the coordination group;
  • C is hydrogen;
  • B can be selected from any one of the following groups:
  • R 0 is -CH 3 or phenyl
  • the thiophene- or polythiophene-containing group may include Wherein, R represents the connection end connected to the main body of the ligand, R is an alkyl group or an alkyl group connected to an amide bond or an amino group, R represents a free end, and R represents a methyl group, an ethyl group or a methoxy group , 1 ⁇ n ⁇ 10.
  • the thiophene- or polythiophene-containing group may include Wherein, R 1 represents a free terminal, R 1 is methyl, ethyl or methoxy, p ⁇ 3, 1 ⁇ n ⁇ 10.
  • the perfluoroalkyl group may include -(CF 2 )q-CF 3 , wherein q>5.
  • the group containing a carbon-carbon double bond or a segment may include Among them, R 2 , R 3 , and R 4 represent free ends, and R 2 , R 3 , and R 4 can each independently be hydrogen (H), fluorine (F), methyl (CH 3 ), ethyl (-CH 2 Any one of short-chain alkyl groups such as -CH 3 ), propyl, etc., R 5 represents the connection end connected to the main body of the ligand, R 5 can be an alkyl group or an alkyl group connected with an amide bond or an amino group R 5 represents a connection end connected to the main body of the ligand, and R 5 may be an alkyl group or an alkyl group connected with an amide bond or an amino group.
  • the group containing a carbon-carbon triple bond may include
  • R 6 represents the connection end connected to the main body of the ligand
  • R 6 can be an alkyl group or an alkyl group connected with an amide bond or an amino group
  • R 7 is a free end
  • R 7 can be hydrogen (H)
  • Any of short-chain alkyl groups such as methyl (CH 3 ), ethyl (-CH 2 -CH 3 ), propyl (-CH 2 -CH 2 -CH 3 ), etc.
  • positions 1 to 8 in the general structural formula of the ligand may each independently be hydrogen or fluorine.
  • positions 1 to 8 in the general structural formula of the ligand may all be fluorine.
  • the quantum dots may be selected from CdS, CdSe, ZnSe, InP, PbS, CsPbCl 3 , CsPbBr 3 , CsPhI 3 , CdS/ZnS, CdSe/ZnS, ZnSe, ZnTeSe, ZnSe/ZnS, ZnTeSe /ZnS, InP/ZnS, PbS/ZnS, CsPbCl 3 /ZnS, CsPbBr 3 /ZnS and CsPhI 3 /ZnS any one or more.
  • Embodiments of the present disclosure also provide a preparation method of the quantum dot material as described above, the preparation method comprising:
  • the ligand is used to exchange the oil-soluble ligand on the surface of the initial quantum dot to obtain the quantum dot material.
  • the use of ligands to perform ligand exchange on the oil-soluble ligands on the surface of the initial quantum dots to obtain the quantum dot materials may include:
  • the solution after the ligand exchange is added to the poor solvent of the ligand, so that the quantum dot containing the ligand is precipitated and separated from the solution to obtain the quantum dot material.
  • the concentration of the ligand in the ligand solution containing the initial quantum dots, may be 3 times to 100 times the mass concentration of the initial quantum dots.
  • the mass concentration of the ligand may be 100 mg/mL to 800 mg/mL, and the concentration of the initial quantum dots may be 10 mg/mL to 30 mg/mL. mL.
  • the time for the ligand exchange may be more than 4 hours.
  • the organic solvent may be selected from any one or more of toluene, xylene and chloroform.
  • the poor solvent may be selected from any one or more of acetone, ethyl acetate and methanol.
  • An embodiment of the present disclosure also provides a quantum dot display device.
  • the quantum dot display device can be at least one of a quantum dot light emitting device, a quantum dot-organic light emitting diode, a quantum dot-liquid crystal display device or a quantum dot-micro light emitting diode.
  • the quantum dot display device includes the quantum dot material as described above.
  • the quantum dot display device is a quantum dot light-emitting device
  • the quantum dot light-emitting device includes an anode, a cathode, and a quantum dot light-emitting layer interposed between the anode and the cathode, the The material of the quantum dot light-emitting layer is the quantum dot material mentioned above.
  • the quantum dot display device is at least one of a quantum dot-organic light emitting diode, a quantum dot-liquid crystal display device or a quantum dot-micro light emitting diode, and the quantum dot display device includes a color conversion layer , the material of the color conversion layer is the quantum dot material as mentioned above.
  • An embodiment of the present disclosure also provides a display device, which includes a plurality of quantum dot light emitting devices as described above.
  • An embodiment of the present disclosure also provides a method for patterning a quantum dot film, including:
  • the material of the quantum dot film is the quantum dot material as described above;
  • the quantum dot film in the non-retained area is removed to obtain a patterned quantum dot film.
  • An embodiment of the present disclosure also provides a method for preparing a quantum dot light-emitting device, including:
  • Fig. 1 is the conversion diagram of the cis/trans conformational change of the ligand molecule with the general structural formula (I) under ultraviolet/visible light in an exemplary embodiment of the present disclosure
  • Fig. 2 is a schematic diagram of quadruple hydrogen bonds formed between molecules of ligands with the general structural formula (I) in an exemplary embodiment of the present disclosure
  • Fig. 3 is a schematic diagram of the hydrogen bond formed in the molecule by the ligand molecule having the general structural formula (I) in an exemplary embodiment of the present disclosure
  • FIG. 4 is a schematic structural diagram of a QLED device with an upright structure according to an exemplary embodiment of the present disclosure
  • FIG. 5 is a schematic structural diagram of an inverted QLED device according to an exemplary embodiment of the present disclosure.
  • Fig. 6 is a conversion diagram of the cis/trans conformational change of the quantum dot material in an exemplary embodiment of the present disclosure under ultraviolet/visible light.
  • 100-anode 200-hole injection layer; 300-hole transport layer; 400-quantum dot light-emitting layer; 500-electron transport layer; 600-cathode.
  • film and “layer” are interchangeable.
  • quantum dot film can sometimes be replaced by “quantum dot layer”.
  • An embodiment of the present disclosure provides a quantum dot material, the quantum dot material includes: quantum dots and ligands modifying the quantum dots, the ligands coordinate with the quantum dots, and the ligands have photosensitive It is a derivative of azobenzene and contains ureido and pyrimidinone groups.
  • the quantum dot material in the embodiment of the present disclosure uses a compound with photosensitive isomerization properties as a ligand to modify the quantum dot.
  • the ligand can not only passivate the defect sites and dangling bonds on the surface of the quantum dot, but also make the quantum dot Dot materials have reversible photosensitive cross-linking properties.
  • the ligand is configured to exhibit a cis structure after being irradiated with ultraviolet light, and a quadruple hydrogen bond is formed between molecules of the ligand; it can exhibit a trans structure after being irradiated with visible light, and Intramolecular hydrogen bonding of the ligands is formed.
  • the ligand molecules of the quantum dot material in the exemplary embodiment of the present disclosure form a quadruple hydrogen bond, and the quantum dot material forms a cross-linked structure under the action of the quadruple hydrogen bond between the ligand molecules, which can improve the The stability of the dot material, when the quantum dot material is used to prepare the quantum dot film, a quantum dot film with good stability and not easy to dissolve can be obtained; under the irradiation of visible light, a hydrogen bond is formed in the ligand molecule, and the four molecules between the ligand molecule The heavy hydrogen bond is released, so that the intermolecular cross-linking of the quantum dot material is decomposed, and then the quantum dot material can be dissolved in the solvent.
  • the quantum dot light-emitting layer is prepared by using the quantum dot material of the exemplary embodiment of the present disclosure, and the quantum dot light-emitting device is prepared by using the quantum dot light-emitting layer, the following beneficial technical effects can be obtained:
  • the quantum dot material in the exemplary embodiment of the present disclosure can be cross-linked under ultraviolet light, the quantum dot material in the exemplary embodiment of the present disclosure can be used to prepare a patterned quantum dot light-emitting layer using photolithography technology;
  • the ligands of the quantum dot materials in the exemplary embodiments of the present disclosure are in the cis structure, and the ligand molecules are easy to combine with some common front film layers (that is, in the process of forming quantum dot light-emitting devices) Film layers formed before the light-emitting layer, such as electron transport layers (ETL) such as ZnO, ZnMgO, and ZnAlO, and hole transport layers (Hole Transport Layers) such as MoO 3 , nickel oxide NiO, and vanadium oxide V 2 O 5 .
  • ETL electron transport layers
  • Hole Transport Layers hole transport layers
  • HTL Hydrophilic Layer
  • other film layers rich in hydroxyl groups on the surface form hydrogen bonds, so that the quantum dot light-emitting layer in the area irradiated by ultraviolet light can be more tightly combined with the substrate, improving the stability of the quantum dot light-emitting layer;
  • the cross-linking between the molecules of the quantum dot material in the exemplary embodiment of the present disclosure is based on the reversible cross-linking of the molecular conformation change, it is possible to rework the quantum dot light-emitting layer during the mass production process in the production line.
  • a feasible way is provided.
  • the quantum dot luminescent layer can be irradiated with visible light to decompose the crosslinking of the quantum dot material, so that the quantum dot luminescent layer can be easily removed from the substrate (such as redissolving, etc.), and then reworked.
  • the preparation of related technological processes is conducive to cost saving in the mass production process.
  • the general structural formula of the ligand may be:
  • A, B, and C represent any chemical atom, chemical group or molecular fragment (including a single chemical group, and complex chemical molecular fragments composed of multiple groups or atoms) that can be at the site, but A At least one of , B, and C contains a coordinating group capable of coordinating with the quantum dot.
  • Fig. 1 is a transformation diagram of cis/trans conformational changes of a ligand molecule having the general structural formula (I) in an exemplary embodiment of the present disclosure under ultraviolet/visible light.
  • the ligand molecule after being irradiated by ultraviolet light, the ligand molecule presents a cis structure as shown in formula (I); after being irradiated by visible light, the ligand molecule presents a trans structure as shown in formula (I'). structure.
  • Fig. 2 is a schematic diagram of the quadruple hydrogen bond formed between molecules of the ligand with the general structural formula (I) in an exemplary embodiment of the present disclosure, and the dotted line indicates the site where the intermolecular hydrogen bond is formed.
  • a quadruple hydrogen bond can be formed between the two ligand molecules.
  • Fig. 3 is a schematic diagram of the hydrogen bond formed in the molecule by the ligand molecule with the general structural formula (I) in the exemplary embodiment of the present disclosure, and the dotted line indicates the site where the intermolecular hydrogen bond is formed.
  • Fig. 3 when the ligand molecule of the general formula (I) is in the trans structure, hydrogen bonds are formed in the molecule, and the quadruple hydrogen bonds between the ligand molecules are released.
  • the ligand shown is coordinated with the quantum dot through the coordination group, and plays the role of passivating defect sites and dangling bonds on the surface of the quantum dot.
  • the length of the ligand can be adjusted and designed according to the different requirements of the quantum dot on the length of the ligand molecule.
  • A is (CH 2 ) x —Y, wherein, 0 ⁇ x ⁇ 12, Y is the coordination group;
  • C is hydrogen;
  • B can be selected from any one of the following groups:
  • R 0 is -CH 3 or phenyl
  • B is (m ⁇ 10, R 0 is -CH 3 or phenyl)
  • B is a long-chain hydrocarbon, which can make the quantum dot material of the embodiment of the present disclosure play the role of blocking electrons, thereby reducing the injection of electrons and adjusting the current carrying capacity. Sub injection balance.
  • the thiophene- or polythiophene-containing group may include Wherein, R represents the connection end connected to the main body of the ligand, R is an alkyl group or an alkyl group connected to an amide bond or an amino group, R represents a free end, and R represents a methyl group, an ethyl group or a methoxy group , 1 ⁇ n ⁇ 10.
  • the thiophene- or polythiophene-containing group may include Wherein, R 1 represents a free terminal, R 1 is methyl, ethyl or methoxy, p ⁇ 3, 1 ⁇ n ⁇ 10.
  • the hole transport ability of the quantum dot material of the embodiment of the present disclosure can be improved, thereby improving the injection of holes, so that the quantum dot material of the embodiment of the present disclosure is used to prepare In QLED devices, it is beneficial to the balance of carrier injection.
  • the perfluoroalkyl group may include -(CF 2 )q-CF 3 , wherein q>5.
  • the group or segment containing a carbon-carbon double bond may include Among them, R 2 , R 3 , and R 4 represent free ends, and R 2 , R 3 , and R 4 can each independently be hydrogen (H), fluorine (F), methyl (CH 3 ), ethyl (-CH 2 Any one of short-chain alkyl groups such as -CH 3 ), propyl, etc., R 5 represents the connection end connected to the main body of the ligand, R 5 can be an alkyl group or an alkyl group connected with an amide bond or an amino group .
  • the group containing a carbon-carbon triple bond may include
  • R 6 represents the connection end connected to the main body of the ligand
  • R 6 can be an alkyl group or an alkyl group connected with an amide bond or an amino group
  • R 7 is a free end
  • R 7 can be hydrogen (H)
  • Any of short-chain alkyl groups such as methyl (CH 3 ), ethyl (-CH 2 -CH 3 ), propyl (-CH 2 -CH 2 -CH 3 ), etc.
  • B is a fluoroalkyl group or a perfluoroalkyl group, or a group or segment containing a carbon-carbon double bond
  • the repulsion of the quantum dot material in the embodiment of the present disclosure to moisture can be improved, and the quantum dot material to moisture can be reduced. Absorption, thereby reducing the adverse effects of moisture on quantum dot materials.
  • the embodiments of the present disclosure can consume a part of oxygen in the QLED device, and the group or chain segment containing carbon-carbon double bond or carbon-carbon triple bond itself is at the end of the ligand molecule of the quantum dot material in the embodiment of the present disclosure.
  • the quantum dot material itself has no influence, but it can reduce the sensitivity of the quantum dot material to oxygen and other oxides in the environment, and can improve the tolerance of the quantum dot material in the embodiment of the present disclosure to oxygen to a certain extent.
  • positions 1 to 8 in the general structural formula of the ligand may each independently be hydrogen or fluorine.
  • the No. 1 to No. 8 sites contain fluorine, the repulsion of the quantum dot material to water can be improved, and the performance of the quantum dot material is less affected by water.
  • positions 1 to 8 in the general structural formula of the ligand may all be fluorine.
  • the quantum dots may be selected from CdS, CdSe, ZnSe, InP, PbS, CsPbCl 3 , CsPbBr 3 , CsPhI 3 , CdS/ZnS, CdSe/ZnS, ZnSe, ZnTeSe, ZnSe/ZnS, ZnTeSe /ZnS, InP/ZnS, PbS/ZnS, CsPbCl 3 /ZnS, CsPbBr 3 /ZnS and CsPhI 3 /ZnS any one or more.
  • Embodiments of the present disclosure also provide a preparation method of the quantum dot material as described above, the preparation method comprising:
  • the ligand is used to exchange the oil-soluble ligand on the surface of the initial quantum dot to obtain the quantum dot material.
  • the use of ligands to perform ligand exchange on the oil-soluble ligands on the surface of the initial quantum dots to obtain the quantum dot materials may include:
  • the solution after the ligand exchange is added to the poor solvent of the ligand, so that the quantum dots containing the ligand are precipitated and separated from the solution to obtain the quantum dot material.
  • the mass concentration of the ligand may be 3 times to 100 times that of the initial quantum dots.
  • the ligand in the ligand solution containing the initial quantum dots, may have a mass concentration of 100 mg/mL to 800 mg/mL.
  • the mass concentration of the initial quantum dots may be 10 mg/mL to 30 mg/mL.
  • the ligand exchange time may be more than 4 hours, for example, 4 hours, 5 hours, 6 hours, 7 hours, etc.
  • the organic solvent may be selected from any one or more of toluene, xylene and chloroform.
  • the poor solvent may be selected from any one or more of acetone, ethyl acetate and methanol.
  • the quantum dots containing the ligand after the quantum dots containing the ligand are precipitated, they can be separated from the solution by centrifugation. Centrifuge until the supernatant solution is clear, and remove the supernatant to obtain the quantum dot material.
  • An embodiment of the present disclosure also provides a quantum dot display device, which can be a quantum dot light emitting device (QLED), a quantum dot-organic light emitting diode (Quantum Dots-Organic Light Emitting Diode, QD-OLED), a quantum dot display device At least one of a point-liquid crystal display device (Quantum Dots-Liquid Crystal Display, QD-LCD) or a quantum dot-micro light-emitting diode (Quantum Dots-Micro Light-Emitting Diode, QD-MicroLED), the quantum dot display device Including quantum dot materials as described above.
  • QLED quantum dot light emitting device
  • QD-OLED Quantum Dot-Organic Light Emitting Diode
  • QD-OLED Quantum Dot display device At least one of a point-liquid crystal display device (Quantum Dots-Liquid Crystal Display, QD-LCD) or a quantum
  • the quantum dot display device is a QLED
  • the QLED includes an anode, a cathode, and a quantum dot light-emitting layer sandwiched between the anode and the cathode, and the material of the quantum dot light-emitting layer is For the above-mentioned quantum dot material.
  • the quantum dot display device is at least one of QD-OLED, QD-LCD or QD-MicroLED, and the quantum dot display device includes a color conversion layer (or called a color filter), so The material of the color conversion layer is the quantum dot material as mentioned above.
  • An embodiment of the present disclosure also provides a display device, which includes a plurality of quantum dot display devices as described above.
  • the display device can be any product or component with a display function such as a mobile phone, a tablet computer, a television, a monitor, a notebook computer, a digital photo frame, a navigator, a vehicle display, a smart watch, and a smart bracelet.
  • a display function such as a mobile phone, a tablet computer, a television, a monitor, a notebook computer, a digital photo frame, a navigator, a vehicle display, a smart watch, and a smart bracelet.
  • An embodiment of the present disclosure also provides a method for patterning a quantum dot film, and the method for patterning a quantum dot film includes:
  • the material of the quantum dot film is the quantum dot material as described above;
  • the quantum dot film in the non-retained area is removed to obtain a patterned quantum dot film.
  • quadruple hydrogen bonds can be formed between the ligand molecules of the quantum dot materials in the embodiments of the present disclosure, which improves the stability of the quantum dot film and makes the quantum dot film in the reserved area not easy to be removed, and does not retain
  • the quantum dot film in the region has not been irradiated by ultraviolet light, hydrogen bonds are formed in the molecules, but quadruple hydrogen bonds are not formed between the molecules, so it is easy to be removed.
  • a mask plate when irradiating the quantum dot film in the reserved region with ultraviolet light, a mask plate may be used to block the quantum dot film in the non-retained region.
  • a good solvent for quantum dots may be used to wash off the quantum dot film in the non-retained area, and the good solvent for quantum dots may be selected from any one or more of toluene and chloroform.
  • the quantum dot light-emitting device may have an upright structure, at this time, the first electrode is an anode, and the second electrode is a cathode, and the preparation method may include:
  • the second electrode is formed on the electron transport layer.
  • FIG. 4 is a schematic structural diagram of a QLED device with an upright structure according to an exemplary embodiment of the present disclosure.
  • the QLED device with an upright structure may include: an anode 100, a hole injection layer 200 arranged on the anode 100, a hole transport layer 300 arranged on the side of the hole injection layer 200 away from the anode 100, a set The quantum dot light-emitting layer 400 on the side of the hole transport layer 300 away from the anode 100, the electron transport layer 500 disposed on the side of the quantum dot light-emitting layer 400 away from the anode 100, and the cathode disposed on the side of the electron transport layer 500 away from the anode 100 600.
  • the anode 100 can be a bottom emission substrate conductive glass or a common glass substrate deposited with a conductive layer.
  • the conductive layer can be made of indium tin oxide (Indium Tin Oxide, ITO), indium zinc oxide (Indium Zinc Oxide, IZO), fluorine-doped Formed from conductive transparent materials such as F-doped Tin Oxide (FTO);
  • the hole injection layer 200 can be prepared by spin coating, evaporation or inkjet printing; wherein, the organic hole injection layer can be selected from PEDOT:PSS 4083 (poly(3,4-ethylenedioxythiophene)/polyphenylene Ethylene sulfonate) or other compounds suitable for forming the hole injection layer; it can also be inorganic metal oxides such as NiO, MoO 3 , WoO 3 , V 2 O 5 , CuO, CuS, CuSCN, Cu:NiO, or Sulfide material; the film forming temperature of PEDOT can be 130°C to 150°C, and the speed of the homogenizer can be set at 500rpm to 2500rpm during film formation to adjust the thickness of the film layer;
  • PEDOT:PSS 4083 poly(3,4-ethylenedioxythiophene)/polyphenylene Ethylene sulfonate
  • other compounds suitable for forming the hole injection layer it can also be inorganic metal oxides such as Ni
  • the hole transport layer 300 can be prepared by spin coating, evaporation or inkjet printing, etc., and the material of the hole transport layer can be selected from, for example, poly(9,9-dioctylfluorene-CO-N -(4-butylphenyl)diphenylamine) (TFB), polyvinylcarbazole (PVK), N,N'-bis(3-methylphenyl)-N,N'-diphenyl-1 , 1'-biphenyl-4,4'-diamine (TPD), 4,4'-bis(9-carbazole)biphenyl (CBP) and other materials suitable for forming the hole transport layer;
  • the quantum dot luminescent layer 400 can be prepared by spin coating, evaporation or inkjet printing, electrojet printing, etc., and the quantum dots for preparing the quantum dot luminescent layer can be selected from CdS, CdSe, ZnSe, InP, PbS, CsPbCl 3 , CsPbBr 3 , CsPhI 3 , CdS/ZnS, CdSe/ZnS, ZnSe, ZnTeSe, ZnSe/ZnS, ZnTeSe/ZnS, InP/ZnS, PbS/ZnS, CsPbCl 3 /ZnS, CsPbBr 3 /ZnS and CsPhI 3 /ZnS any one or more;
  • the specific synthesis method is: under the condition of inert gas and about 100 ° C, dissolving selenium powder in octadecene to obtain a selenium solution; adding CdO and oleic acid to ten Octene and heated to about 280°C to obtain a cadmium precursor solution; add the selenium solution to the cadmium precursor solution, cool down to about 250°C for reaction, cool to room temperature after the reaction, and use methanol-hexane Extraction to remove unreacted precursors, precipitation with ethanol, and dissolution in octane to obtain a solution of CdSe initial quantum dots containing oil-soluble ligand oleic acid, and then through the preparation of quantum dot materials in the embodiments of the present disclosure
  • Methods Using the ligands of the embodiments of the present disclosure to carry out ligand exchange on the oil-soluble ligand
  • Dot film also can be formed by printing, printing, electrospray printing, etc., then irradiate the quantum dot film in the reserved area with ultraviolet light and wash off the quantum dot film in the non-retained area with a good solvent of quantum dots to obtain a pattern Quantum dot film, that is, the quantum dot light-emitting layer;
  • the material of the electron transport layer 500 can be selected from any one or more of aluminum oxide, barium fluoride, titanium dioxide, zinc sulfide, zirconium oxide, zinc selenide, magnesium oxide, zinc oxide, yttrium oxide and aluminum fluoride ;
  • the electron transport layer 500 can choose zinc oxide nanoparticle film or zinc oxide sol-gel film, etc.;
  • (a) Preparation of zinc oxide nanoparticle film for example, dissolving 90 ⁇ L to 120 ⁇ L of zinc oxide nanoparticles with a concentration of 10 mg/mL to 30 mg/mL in an alcoholic solvent (for example, methanol, ethanol, isopropanol, etc.) to obtain Add the solution dropwise to the quantum dot luminescent layer, set the speed of the homogenizer at 500rpm to 2500rpm and spin-coat to form a film, and form a film at room temperature or heating (the temperature can be 25°C to 120°C) to adjust the zinc oxide nanoparticles the thickness of the film;
  • an alcoholic solvent for example, methanol, ethanol, isopropanol, etc.
  • the material of the electron transport layer 500 can also be ion-doped zinc oxide nanoparticles, for example, Mg, In, Al or Ga-doped zinc oxide nanoparticles, etc.;
  • the cathode 600 can be prepared by evaporation or sputtering, and can be a metal film (such as an Al film) or an IZO film.
  • the quantum dot light-emitting device may have an inverted structure, at this time, the first electrode is a cathode, and the second electrode is an anode, and the preparation method may include:
  • the second electrode is formed on the hole injection layer.
  • FIG. 5 is a schematic structural diagram of an inverted QLED device according to an exemplary embodiment of the present disclosure.
  • the QLED device with an inverted structure may include: a cathode 600, an electron transport layer 500 disposed on the cathode 600, a quantum dot light-emitting layer 400 disposed on the side of the electron transport layer 500 away from the cathode 600, a quantum dot light-emitting layer 400 disposed on the quantum dot
  • the cathode 600 can be a bottom emission substrate conductive glass or an ordinary glass substrate deposited with a conductive layer.
  • the conductive layer can be made of conductive transparent materials such as ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), FTO (F-doped Tin Oxide), etc. form;
  • the anode 100 can be prepared by evaporation or sputtering, and can be a metal film (such as an Al film) or an IZO film;
  • the hole injection layer 200, the hole transport layer 300, the quantum dot light-emitting layer 400, and the electron transport layer 500 can be prepared by selecting the same materials and methods as the QLED device with the upright structure.
  • Exemplary embodiments of the present disclosure provide a quantum dot material, the quantum dot material includes quantum dots and ligands modifying the quantum dots, the ligands coordinate with the quantum dots, and the ligands
  • the general structural formula is:
  • positions 1 to 8 are all hydrogen;
  • A is (CH 2 ) x -Y, where, 0 ⁇ x ⁇ 12, Y is mercapto, hydroxyl, amine, amino, carboxyl, ester, phosphine or phosphine Oxygen (or called phosphine oxide);
  • B is -O-CH 3 ;
  • C is hydrogen.
  • A may be -(CH 2 ) 5 -SH, in which case the ligand is a compound represented by formula (II).
  • Fig. 6 is a conversion diagram of the cis/trans conformational change of the quantum dot material whose ligand is a compound represented by formula (II) according to an exemplary embodiment of the present disclosure under ultraviolet/visible light.
  • the preparation method of the quantum dot material comprises:
  • the concentration of the ligand can be 100 mg/ mL to 800mg/mL, the concentration of the initial quantum dots can be 10mg/mL to 30mg/mL; the ligand solution containing the initial quantum dots is fully stirred for more than 4 hours (for example, 4 hours, 5 hours, 6 hours , 7 hours), making the ligand shown in formula (II) carry out ligand exchange to the oil-soluble ligand on the surface of the initial quantum dot;
  • step (3) Add the solution after the ligand exchange in step (3) dropwise to the poor solvent of the ligand shown in formula (II) (for example, acetone, ethyl acetate, methanol and mixed solvents thereof), so that the ligand containing Precipitate the quantum dots of the body, separate the precipitate from the upper solution by centrifugation, remove the upper solution and then add a poor solvent to centrifuge until the upper solution is clear, and remove the supernatant to obtain the quantum dot material.
  • the poor solvent of the ligand shown in formula (II) for example, acetone, ethyl acetate, methanol and mixed solvents thereof
  • Exemplary embodiments of the present disclosure provide a quantum dot material, the quantum dot material includes quantum dots and ligands modifying the quantum dots, the ligands coordinate with the quantum dots, and the ligands
  • the general structural formula is:
  • positions 1 to 8 are all hydrogen;
  • A is (CH 2 ) x -Y, where, 0 ⁇ x ⁇ 12, Y is mercapto, hydroxyl, amine, amino, carboxyl, ester, phosphine or phosphine Oxygen (or called phosphine oxide);
  • C is hydrogen;
  • B can be a long chain alkane, such as Wherein, m ⁇ 10, R 0 is -CH 3 or phenyl;
  • B is a group containing thiophene or polythiophene, for example, B is Wherein, R represents the connection end connected to the main body of the ligand, R is an alkyl group or an alkyl group connected to an amide bond or an amino group, R represents a free end, and R represents a methyl group, an ethyl group or a methoxy group , 1 ⁇ n ⁇ 10.
  • R 1 represents a free terminal
  • R 1 is methyl, ethyl or methoxy, p ⁇ 3, 1 ⁇ n ⁇ 10.
  • the preparation method of the quantum dot material comprises:
  • the concentration of the ligand can be 100 mg/ mL to 800mg/mL, the concentration of the initial quantum dots can be 10mg/mL to 30mg/mL; the ligand solution containing the initial quantum dots is fully stirred for more than 4 hours (for example, 4 hours, 5 hours, 6 hours , 7 hours), making the ligand exchange ligands for the oil-soluble ligands on the surface of the initial quantum dots;
  • step (3) Add the solution after the ligand exchange in step (3) dropwise to a poor solvent for the ligand (for example, acetone, ethyl acetate, methanol and mixed solvents thereof), so that the quantum dots containing the ligand are precipitated,
  • a poor solvent for the ligand for example, acetone, ethyl acetate, methanol and mixed solvents thereof.
  • Exemplary embodiments of the present disclosure provide a quantum dot material, the quantum dot material includes quantum dots and ligands modifying the quantum dots, the ligands coordinate with the quantum dots, and the ligands
  • the general structural formula is:
  • positions 1 to 8 are all hydrogen;
  • A is (CH 2 ) x -Y, where, 0 ⁇ x ⁇ 12, Y is mercapto, hydroxyl, amine, amino, carboxyl, ester, phosphine or phosphine Oxygen (or called phosphine oxide);
  • C is hydrogen;
  • B can be a fluoroalkyl group or a perfluoroalkyl group, for example, B is -(CF 2 )q-CF 3 , where q>5;
  • B may be a group or segment containing a carbon-carbon double bond, and the group or segment containing a carbon-carbon double bond may include
  • R 2 , R 3 , and R 4 represent free ends, and R 2 , R 3 , and R 4 can each independently be any of short-chain alkyl groups such as hydrogen, fluorine, methyl, ethyl, and propyl
  • R 5 represents the connection end connected to the main body of the ligand
  • B may be a group or segment containing a carbon-carbon triple bond
  • the group containing a carbon-carbon triple bond may include
  • R 6 represents the connection end connected to the main body of the ligand
  • R 6 can be an alkyl group or an alkyl group connected with an amide bond or an amino group
  • R 7 is a free end
  • R 7 can be hydrogen, methyl, Any of short-chain alkyl groups such as ethyl and propyl.
  • the preparation method of the quantum dot material comprises:
  • the concentration of the ligand can be 100 mg/ mL to 800mg/mL, the concentration of the initial quantum dots can be 10mg/mL to 30mg/mL; the ligand solution containing the initial quantum dots is fully stirred for more than 4 hours (for example, 4 hours, 5 hours, 6 hours , 7 hours), making the ligand exchange ligands for the oil-soluble ligands on the surface of the initial quantum dots;
  • step (3) Add the solution after the ligand exchange in step (3) dropwise to a poor solvent for the ligand (for example, acetone, ethyl acetate, methanol and mixed solvents thereof), so that the quantum dots containing the ligand are precipitated,
  • a poor solvent for the ligand for example, acetone, ethyl acetate, methanol and mixed solvents thereof.

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Abstract

一种量子点材料及其制备方法、量子点显示器件、显示装置、量子点膜图案化的方法、量子点发光器件的制备方法，所述量子点材料包括：量子点和修饰所述量子点的配体，所述配体与所述量子点配位结合，所述配体具有光敏异构化性质，为偶氮苯的衍生物并且含有脲基和嘧啶酮基。

Description

量子点材料及其制备方法、量子点显示器件、显示装置、量子点膜图案化的方法、量子点发光器件的制备方法
本公开要求于2021年7月30日提交中国专利局、申请号为202110874634.X、发明名称为“量子点材料及其制备方法和应用、量子点膜图案化的方法、量子点发光器件的制备方法”的中国专利申请的优先权，其内容应理解为通过引用的方式并入本公开中。
技术领域
本公开实施例涉及但不限于显示技术领域，尤其涉及一种量子点材料及其制备方法、一种量子点显示器件、一种显示装置、一种量子点膜图案化的方法以及一种量子点发光器件的制备方法。
背景技术
量子点发光二极管(Quantum Dots Light Emitting Diode,QLED)是基于有机发光显示器的基础上发展起来的一种新型显示技术。QLED中的发光层为量子点层，它的原理是电子和空穴注入到量子点层后在量子点层中复合发光。QLED作为具有潜力的下一代自发光显示技术，与有机发光二极管(Organic Light Emitting Diode,OLED)相比，QLED具有能耗更低、色纯度更高、色域更广等突出优势。QLED技术的应用目标为高分辨率动态全彩显示。而QLED亚像素区域的精确制备是实现高分辨率动态全彩显示的前提，这就要求对量子点发光层进行精确的图案化。
发明概述
以下是对本文详细描述的主题的概述。本概述并非是为了限制本公开的保护范围。
本公开实施例提供一种量子点材料，所述量子点材料包括：量子点和修饰所述量子点的配体，所述配体与所述量子点配位结合，所述配体具有光敏异构化性质，为偶氮苯的衍生物并且含有脲基和嘧啶酮基。
在示例性实施例中，所述配体被配置为经紫外光照射后可以呈现顺式结构，并且所述配体的分子间形成四重氢键；经可见光照射后可以呈现反式结构，并且所述配体的分子内形成氢键。
在示例性实施例中，所述配体的结构通式可以为：
Figure PCTCN2022107380-appb-000001
其中，A、B、C中至少有一个含有能够与所述量子点进行配位结合的配位基团。
在示例性实施例中，所述配位基团可以选自巯基(-SH)、羟基(-OH)、胺基(-N-或-NH)、氨基(NH 2)、羧基(-COOH)、酯基(-COO-)、膦基(-P)和膦氧基(或称为氧化膦，O＝P)中的任意一种或多种。
在示例性实施例中，A为(CH 2) x—Y，其中，0≤x≤12，Y为所述配位基团；C为氢；
或者，A为氢；C为(CH 2) x—Y，其中，0≤x≤12，Y为所述配位基团。
在示例性实施例中，B可以选自下述基团中的任意一种：
(1)-O-CH 3；或者
(2)
Figure PCTCN2022107380-appb-000002
其中，m≥10，R 0为-CH 3或苯基；
(3)含有噻吩或聚噻吩的基团；
(4)氟代烷基或全氟代烷基；
(5)含有碳碳双键的基团或链段；
(6)含有碳碳三键的基团或链段。
在示例性实施例中，所述含有噻吩或聚噻吩的基团可以包括
Figure PCTCN2022107380-appb-000003
其中，R表示与所述配体的主体相连接的连接端，R为烷基或连接有酰胺键或氨基的烷基，R 1表示自由端，R 1为甲基、乙基或甲氧基，1≤n≤10。
在示例性实施例中，所述含有噻吩或聚噻吩的基团可以包括
Figure PCTCN2022107380-appb-000004
Figure PCTCN2022107380-appb-000005
其中，R 1表示自由端，R 1为甲基、乙基或甲氧基，p≤3，1≤n≤10。
在示例性实施例中，所述全氟代烷基可以包括-(CF 2)q-CF 3，其中，q＞5。
在示例性实施例中，所述含有碳碳双键或链段的基团可以包括
Figure PCTCN2022107380-appb-000006
其中，R 2、R 3、R 4表示自由端，R 2、R 3、R 4可以各自独立地为氢(H)、氟(F)、甲基(CH 3)、乙基(-CH 2-CH 3)、丙基等短链烷基中的任意一种，R 5表示与所述配体的主体相连接的连接端，R 5可以为烷基或连接有酰胺键或氨基的烷基R 5表示与所述配体的主体相连接的连接端，R 5可以为烷基或连接有酰胺键或氨基的烷基。
在示例性实施例中，所述含有碳碳三键的基团可以包括
Figure PCTCN2022107380-appb-000007
其中，R 6表示与所述配体的主体相连接的连接端，R 6可以为烷基或连接有酰胺键或氨基的烷基，R 7为自由端，R 7可以为氢(H)、甲基(CH 3)、乙基(-CH 2-CH 3)、丙基(-CH 2-CH 2-CH 3)等短链烷基中的任意一种。
在示例性实施例中，所述配体的结构通式中1至8号位点可以各自独立地为氢、氟。
在示例性实施例中，所述配体的结构通式中1至8号位点可以均为氟。
在示例性实施例中，所述量子点可以选自CdS、CdSe、ZnSe、InP、PbS、CsPbCl 3、CsPbBr 3、CsPhI 3、CdS/ZnS、CdSe/ZnS、ZnSe、ZnTeSe、ZnSe/ZnS、ZnTeSe/ZnS、InP/ZnS、PbS/ZnS、CsPbCl 3/ZnS、CsPbBr 3/ZnS和CsPhI 3/ZnS中的任意一种或多种。
本公开实施例还提供如上所述的量子点材料的制备方法，所述制备方法包括：
提供含有油溶性配体的初始量子点；
采用配体对所述初始量子点表面的油溶性配体进行配体交换，得到所述量子点材料。
在示例性实施例中，所述采用配体对所述初始量子点表面的油溶性配体进行配体交换，得到所述量子点材料可以包括：
将所述配体溶于有机溶剂中，得到配体溶液；
将所述初始量子点加入所述配体溶液中，得到含有初始量子点的配体溶液，搅拌，使所述配体对所述初始量子点表面的油溶性配体进行配体交换；
将配体交换之后的溶液加入所述配体的不良溶剂中，使含有配体的量子点进行沉淀，并从溶液中分离出来，得到所述量子点材料。
在示例性实施例中，在含有初始量子点的配体溶液中，所述配体的浓度可以为所述初始量子点的质量浓度的3倍至100倍。
在示例性实施例中，在含有初始量子点的配体溶液中，所述配体的质量浓度可以为100mg/mL至800mg/mL，所述初始量子点的浓度可以为10mg/mL至30mg/mL。
在示例性实施例中，所述配体交换的时间可以为4小时以上。
在示例性实施例中，所述有机溶剂可以选自甲苯、二甲苯和氯仿中的任意一种或多种。
在示例性实施例中，所述不良溶剂可以选自丙酮、乙酸乙酯和甲醇中的任意一种或多种。
本公开实施例还提供一种量子点显示器件，所述量子点显示器件可以为量子点发光器件、量子点-有机发光二极管、量子点-液晶显示器件或量子点-微型发光二极管中的至少一种，所述量子点显示器件包括如上所述的量子点材料。
在示例性实施例中，所述量子点显示器件为量子点发光器件，所述量子点发光器件包括阳极、阴极、夹设在所述阳极和所述阴极之间的量子点发光层，所述量子点发光层的材料为如上所述的量子点材料。
在示例性实施例中，所述量子点显示器件为量子点-有机发光二极管、量子点-液晶显示器件或量子点-微型发光二极管中的至少一种，所述量子点显示器件包括色转换层，所述色转换层的材料为如上所述的量子点材料。
本公开实施例还提供一种显示装置，所述显示装置包括多个如上所述的量子点发光器件。
本公开实施例还提供一种量子点膜图案化的方法，包括：
形成量子点膜，所述量子点膜的材料为如上所述的量子点材料；
对保留区域的量子点膜进行紫外光照射，使所述保留区域内的量子点材料的配体呈现顺式结构并且配体的分子间形成四重氢键；
除去不保留区域的量子点膜，得到图案化的量子点膜。
本公开实施例还提供一种量子点发光器件的制备方法，包括：
形成第一电极；
采用如上所述的量子点膜图案化的方法形成图案化的量子点膜，作为量子点发光层；
形成第二电极。
在阅读并理解了附图和详细描述后，可以明白其他方面。
附图概述
附图用来提供对本公开技术方案的理解，并且构成说明书的一部分，与本公开的实施例一起用于解释本公开的技术方案，并不构成对本公开技术方案的限制。
图1为本公开示例性实施例中结构通式为式(I)的配体分子在紫外/可见光下发生顺/反构象变化的转化图；
图2为本公开示例性实施例中结构通式为式(I)的配体在分子间形成的四重氢键的示意图；
图3为本公开示例性实施例中结构通式为式(I)的配体分子在分子内形成的氢键的示意图；
图4为本公开示例性实施例的正置结构的QLED器件的结构示意图；
图5为本公开示例性实施例的倒置结构的QLED器件的结构示意图；
图6为本公开示例性实施例的量子点材料在紫外/可见光下发生顺/反构象变化的转化图。
附图中的标记符号的含义为：
100-阳极；200-空穴注入层；300-空穴传输层；400-量子点发光层；500-电子传输层；600-阴极。
详述
本文中的实施方式可以以多个不同形式来实施。所属技术领域的普通技术人员可以很容易地理解一个事实，就是实现方式和内容可以在不脱离本公开的宗旨及其范围的条件下被变换为各种各样的形式。因此，本公开不应该被解释为仅限定在下面的实施方式所记载的内容中。在不冲突的情况下，本公开中的实施例及实施例中的特征可以相互任意组合。
在附图中，有时为了明确起见，可能夸大表示了构成要素的大小、层的厚度或区域。因此，本公开的任意一个实现方式并不一定限定于图中所示尺寸，附图中部件的形状和大小不反映真实比例。此外，附图示意性地示出了理想的例子，本公开的任意一个实现方式不局限于附图所示的形状或数值等。
在本说明书中，“膜”和“层”可以相互调换。例如，有时可以将“量子点膜” 换成为“量子点层”。
本公开实施例提供一种量子点材料，所述量子点材料包括：量子点和修饰所述量子点的配体，所述配体与所述量子点配位结合，所述配体具有光敏异构化性质，为偶氮苯的衍生物并且含有脲基和嘧啶酮基。
本公开实施例的量子点材料采用具有光敏异构化特性的化合物作为修饰所述量子点的配体，该配体不但可以对量子点表面的缺陷位点和悬挂键进行钝化，还使量子点材料具有可逆的光敏交联特性。
在示例性实施例中，所述配体被配置为经紫外光照射后可以呈现顺式结构，并且所述配体的分子间形成四重氢键；经可见光照射后可以呈现反式结构，并且所述配体的分子内形成氢键。
在紫外光照射下，本公开示例性实施例的量子点材料的配体分子间形成四重氢键，量子点材料在配体分子间四重氢键的作用下形成交联结构，可以提高量子点材料的稳定性，当采用该量子点材料制备量子点膜时，可以获得稳定性好、不易溶解的量子点膜；在可见光照射下，配体分子内形成氢键，配体分子间的四重氢键解除，使得量子点材料分子间解交联，进而使量子点材料能够溶解在溶剂中。
因此，当采用本公开示例性实施例的量子点材料制备量子点发光层，并采用该量子点发光层制备量子点发光器件时，可以获得下述有益技术效果：
1、由于本公开示例性实施例的量子点材料能够在紫外光下交联，使得采用本公开示例性实施例的量子点材料能够利用光刻技术进行图案化的量子点发光层的制备；
2、在紫外光照射下，本公开示例性实施例的量子点材料的配体为顺式结构，配体分子易于与一些常见的前膜层(即制备量子点发光器件过程中在形成量子点发光层之前就形成的膜层，例如，ZnO、ZnMgO、ZnAlO等电子传输层(Electron Transport Layer，简称ETL)以及MoO 3、氧化镍NiO、氧化钒V 2O 5等空穴传输层(Hole Transport Layer，简称HTL)等表面富含羟基的膜层)形成氢键，使得受到紫外光照射的区域的量子点发光层能够与基底结合得更加紧密，提高量子点发光层的稳定性；
3、由于本公开示例性实施例的量子点材料分子之间的交联是基于分子构象变化的可逆交联，这为产线中批量生产过程中可能针对量子点发光层的重新作业(rework)提供了可行途径，在需要重新作业(rework)时，可用可见光照照射量子点发光层使得量子点材料解交联，使量子点发光层易于从基板上除去(如再溶解等)，进而重新进行相关工艺流程的制备，有利于量产过程中成本的节约。
在示例性实施例中，所述配体的结构通式可以为：
Figure PCTCN2022107380-appb-000008
其中，A、B、C表示任意可在该位点的化学原子、化学基团或分子片段(包含单一的化学基团，以及多种基团或原子构成的复杂的化学分子片段)，但A、B、C中至少有一个含有能够与所述量子点进行配位结合的配位基团。
图1为本公开示例性实施例中结构通式为式(I)的配体分子在紫外/可见光下发生顺/反构象变化的转化图。如图1所示，经紫外光照射后，该配体分子呈现如式(I)所示的顺式结构；经可见光照射后，该配体分子呈现如式(I’)所示的反式结构。
图2为本公开示例性实施例中结构通式为式(I)的配体在分子间形成的四重氢键的示意图，虚线表示形成分子间氢键的位点。如图2所示，当通式为式(I)的配体分子为顺式结构时，两个配体分子之间可以形成4重氢键。
图3为本公开示例性实施例中结构通式为式(I)的配体分子在分子内形 成的氢键的示意图，虚线表示形成分子间氢键的位点。如图3所示，当通式为式(I)的配体分子为反式结构时，分子内形成氢键，而配体分子间的四重氢键解除。
在示例性实施例中，所述配位基团可以选自巯基(-SH)、羟基(-OH)、胺基(-N-或-NH)、氨基(NH 2)、羧基(-COOH)、酯基(-COO-)、膦基(-P)和膦氧基(或称为氧化膦，O＝P)中的任意一种或多种。所示配体通过该配位基团与所示量子点配位结合，起到钝化量子点表面的缺陷位点和悬挂键的作用。
在示例性实施例中，可以根据量子点对配体分子长度的不同需求，调节和设计配体的长度。
在示例性实施例中，A为(CH 2) x—Y，其中，0≤x≤12，Y为所述配位基团；C为氢；
或者，A为氢；C为(CH 2) x—Y，其中，0≤x≤12，Y为所述配位基团。
在示例性实施例中，B可以选自下述基团中的任意一种：
(1)-O-CH 3；或者
(2)
Figure PCTCN2022107380-appb-000009
其中，m≥10，R 0为-CH 3或苯基；
(3)含有噻吩或聚噻吩的基团；
(4)氟代烷基或全氟代烷基；
(5)含有碳碳双键的基团或链段；
(6)含有碳碳三键的基团或链段。
当B为
Figure PCTCN2022107380-appb-000010
(m≥10，R 0为-CH 3或苯基)时，B为长链烃，可以使本公开实施例的量子点材料起到挡电子的作用，从而使得电子的注入减少，调节载流子的注入平衡。
在示例性实施例中，所述含有噻吩或聚噻吩的基团可以包括
Figure PCTCN2022107380-appb-000011
其中，R表示与所述配体的主体相连接的连接端，R为烷基或连接有酰胺键或氨基的烷基，R 1表示自由端，R 1为甲基、乙基或甲氧基，1≤n≤10。
在示例性实施例中，所述含有噻吩或聚噻吩的基团可以包括
Figure PCTCN2022107380-appb-000012
Figure PCTCN2022107380-appb-000013
其中，R 1表示自由端，R 1为甲基、乙基或甲氧基，p≤3，1≤n≤10。
当B为含有噻吩或聚噻吩的基团时，可以使本公开实施例的量子点材料的空穴传输能力提高，从而提高空穴的注入，使得在采用本公开实施例的量子点材料制得的QLED器件中，有利于载流子注入的平衡。
在示例性实施例中，所述全氟代烷基可以包括-(CF 2)q-CF 3，其中，q＞5。
在示例性实施例中，所述含有碳碳双键的基团或链段可以包括
Figure PCTCN2022107380-appb-000014
其中，R 2、R 3、R 4表示自由端，R 2、R 3、R 4可以各自独立地为氢(H)、氟(F)、甲基(CH 3)、乙基(-CH 2-CH 3)、丙基等短链烷基中的任意一种，R 5表示与所述配体的主体相连接的连接端，R 5可以为烷基或连接有酰胺键或氨基的烷基。
在示例性实施例中，所述含有碳碳双键或链段的基团可以为-CF＝CF 2。
在示例性实施例中，所述含有碳碳三键的基团可以包括
Figure PCTCN2022107380-appb-000015
其中，R 6表示与所述配体的主体相连接的连接端，R 6可以为烷基或连接有酰胺键或氨基的烷基，R 7为自由端，R 7可以为氢(H)、甲基(CH 3)、乙基(-CH 2-CH 3)、丙基(-CH 2-CH 2-CH 3)等短链烷基中的任意一种。
当B为氟代烷基或全氟代烷基、或为含有碳碳双键的基团或链段时，可以提高本公开实施例的量子点材料对水分的斥力，减少量子点材料对水分的吸收，从而减少水分对量子点材料的不利影响。
当B为含有碳碳双键或碳碳三键的基团或链段时，由于含有碳碳双键或碳碳三键的基团或链段更容易被氧气等氧化，使得本公开实施例的量子点材料在QLED器件中能够消耗一部分氧气，而含有碳碳双键或碳碳三键的基团或链段本身处于本公开实施例的量子点材料的配体分子末端，被氧化后对量子点材料本身没有影响，但能够减少量子点材料对环境中氧气等氧化物的敏感性，能够在一定程度上提高本公开实施例的量子点材料对氧气的耐受度。
在示例性实施例中，所述配体的结构通式中1至8号位点可以各自独立地为氢、氟。当1至8号位点中含氟时，可以提高量子点材料对水分的斥力，量子点材料的性能受水分的影响较小。
在示例性实施例中，所述配体的结构通式中1至8号位点可以均为氟。
在示例性实施例中，所述量子点可以选自CdS、CdSe、ZnSe、InP、PbS、CsPbCl 3、CsPbBr 3、CsPhI 3、CdS/ZnS、CdSe/ZnS、ZnSe、ZnTeSe、ZnSe/ZnS、ZnTeSe/ZnS、InP/ZnS、PbS/ZnS、CsPbCl 3/ZnS、CsPbBr 3/ZnS和CsPhI 3/ZnS中的任意一种或多种。
本公开实施例还提供如上所述的量子点材料的制备方法，所述制备方法包括：
提供含有油溶性配体的初始量子点；
采用配体对所述初始量子点表面的油溶性配体进行配体交换，得到所述量子点材料。
在示例性实施例中，所述采用配体对所述初始量子点表面的油溶性配体进行配体交换，得到所述量子点材料可以包括：
将所述配体溶于有机溶剂中，得到配体溶液；
将所述初始量子点加入所述配体溶液中，得到含有初始量子点的配体溶液，搅拌，使所述配体对所述初始量子点表面的油溶性配体进行配体交换；
将配体交换之后的溶液加入所述配体的不良溶剂中，使含有配体的量子 点进行沉淀，并从溶液中分离出来，得到所述量子点材料。
在示例性实施例中，在含有初始量子点的配体溶液中，所述配体的质量浓度可以为所述初始量子点的质量浓度的3倍至100倍。
在示例性实施例中，在含有初始量子点的配体溶液中，所述配体的质量浓度可以为100mg/mL至800mg/mL。
在示例性实施例中，在含有初始量子点的配体溶液中，所述初始量子点的质量浓度可以为10mg/mL至30mg/mL。
在示例性实施例中，所述配体交换的时间可以为4小时以上，例如，4小时、5小时、6小时、7小时等。
在示例性实施例中，所述有机溶剂可以选自甲苯、二甲苯和氯仿中的任意一种或多种。
在示例性实施例中，所述不良溶剂可以选自丙酮、乙酸乙酯和甲醇中的任意一种或多种。
在示例性实施例中，在含有配体的量子点沉淀之后，可以通过离心的方法将其从溶液中分离出来，例如，通过离心使沉淀与上层溶液分离，去掉上层溶液后再次加入不良溶剂进行离心，直至上层溶液清澈，去掉上层清液后即可得到所述量子点材料。
本公开实施例还提供一种量子点显示器件，所述量子点显示器件可以为量子点发光器件(QLED)、量子点-有机发光二极管(Quantum Dots-Organic Light Emitting Diode,QD-OLED)、量子点-液晶显示器件(Quantum Dots-Liquid Crystal Display,QD-LCD)或量子点-微型发光二极管(Quantum Dots–Micro Light-Emitting Diode,QD-MicroLED)中的至少一种，所述量子点显示器件包括如上所述的量子点材料。
在示例性实施例中，所述量子点显示器件为QLED，所述QLED包括阳极、阴极、夹设在所述阳极和所述阴极之间的量子点发光层，所述量子点发光层的材料为如上所述的量子点材料。
在示例性实施例中，所述量子点显示器件为QD-OLED、QD-LCD或QD-MicroLED中的至少一种，所述量子点显示器件包括色转换层(或称为彩膜)， 所述色转换层的材料为如上所述的量子点材料。
本公开实施例还提供一种显示装置，所述显示装置包括多个如上所述的量子点显示器件。
所述显示装置可以为手机、平板电脑、电视机、显示器、笔记本电脑、数码相框、导航仪、车载显示器、智能手表、智能手环等任何具有显示功能的产品或部件。
本公开实施例还提供一种量子点膜图案化的方法，所述量子点膜图案化的方法包括：
形成量子点膜，所述量子点膜的材料为如上所述的量子点材料；
对保留区域的量子点膜进行紫外光照射，使所述保留区域内的量子点材料的配体呈现顺式结构并且配体的分子间形成四重氢键；
除去不保留区域的量子点膜，得到图案化的量子点膜。
由于在紫外光照射下，本公开实施例的量子点材料的配体分子间可以形成四重氢键，提高量子点膜的稳定性，使保留区域的量子点膜不容易被除去，而不保留区域的量子点膜未经过紫外光照射，分子内形成氢键，但分子间不会形成四重氢键，因此容易被除去。
在示例性实施例中，在对保留区域的量子点膜进行紫外光照射时，可以采用掩膜板遮挡不保留区域的量子点膜。
在示例性实施例中，可以采用量子点的良溶剂洗去不保留区域的量子点膜，所述量子点的良溶剂可以选自甲苯和氯仿中的任意一种或多种。
在示例性实施例中，所述量子点发光器件可以为正置结构，此时所述第一电极为阳极，所述第二电极为阴极，所述制备方法可以包括：
形成第一电极；
在所述第一电极上形成空穴注入层；
在所述空穴注入层上形成空穴传输层；
在所述空穴传输层上形成所述量子点发光层；
在所述量子点发光层上形成电子传输层；
在所述电子传输层上形成所述第二电极。
图4为本公开示例性实施例的正置结构的QLED器件的结构示意图。如图4所示，正置结构的QLED器件可以包括：阳极100、设置在阳极100上的空穴注入层200、设置在空穴注入层200远离阳极100一侧的空穴传输层300、设置在空穴传输层300远离阳极100一侧的量子点发光层400、设置在量子点发光层400远离阳极100一侧的电子传输层500、以及设置在电子传输层500远离阳极100一侧的阴极600。
在示例性实施例中，在正置结构的QLED器件中，
所述阳极100可以采用底发射基板导电玻璃或者采用沉积有导电层的普通玻璃基板，导电层可以由氧化铟锡(Indium Tin Oxide,ITO)、氧化铟锌(Indium Zinc Oxide,IZO)、氟掺杂氧化锡(F-doped Tin Oxide,FTO)等导电透明材料形成；
所述空穴注入层200可以通过旋涂、蒸镀或喷墨打印等方式制备；其中，有机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)或者其它适用于形成空穴注入层的化合物等；也能够是诸如NiO、MoO 3、WoO 3、V 2O 5、CuO、CuS、CuSCN、Cu:NiO等无机金属氧化物或硫化物材料；PEDOT的成膜温度可以为130℃至150℃，成膜时匀胶机转速可以设置为500rpm至2500rpm，以调整膜层的厚度；
所述空穴传输层300可以通过旋涂、蒸镀或喷墨打印等方式制备空穴传输层，空穴传输层的材料可以选自例如聚(9,9-二辛基芴-CO-N-(4-丁基苯基)二苯胺)(TFB)、聚乙烯基咔唑(PVK)、N,N′-双(3-甲基苯基)-N,N′-二苯基-1,1′-联苯-4,4′-二胺(TPD)、4,4'-二(9-咔唑)联苯(CBP)等适用于形成空穴传输层的材料；
所述量子点发光层400可以通过旋涂、蒸镀或喷墨打印、电喷印等方式制备，制备量子点发光层的量子点可以选自CdS、CdSe、ZnSe、InP、PbS、CsPbCl 3、CsPbBr 3、CsPhI 3、CdS/ZnS、CdSe/ZnS、ZnSe、ZnTeSe、ZnSe/ZnS、ZnTeSe/ZnS、InP/ZnS、PbS/ZnS、CsPbCl 3/ZnS、CsPbBr 3/ZnS和CsPhI 3/ZnS中的任意一种或多种；
以CdSe量子点合成量子点发光层为例，具体的合成方法是：在惰性气 体以及约100℃条件下，将硒粉溶解在十八烯中，得到硒溶液；将CdO和油酸加入到十八烯中并加热到280℃左右，得到镉的前驱体溶液；将硒溶液加入到镉的前驱体溶液中，降温到250℃左右进行反应，反应结束后冷却到室温，用甲醇-己烷进行萃取以除掉未反应的前驱体，用乙醇进行沉淀，并溶解于辛烷中，得到含有油溶性配体油酸的CdSe初始量子点的溶液，再通过本公开实施例的量子点材料的制备方法采用本公开实施例的配体对初始量子点表面的油溶性配体进行配体交，得到含有本公开实施例的配体的量子点材料，将量子点材料溶解后，并旋涂成量子点膜(也可以通过打印、印刷、电喷印等方式成膜)，再对保留区域的量子点膜进行紫外光照射以及用量子点的良溶剂洗去不保留区域的量子点膜，得到图案化的量子点膜，即量子点发光层；
所述电子传输层500的材料可以选自氧化铝、氟化钡、二氧化钛、硫化锌、氧化锆、硒化锌、氧化镁、氧化锌、氧化钇和氟化铝中的任意一种或多种；例如，所述电子传输层500可以选择氧化锌纳米粒子薄膜或氧化锌溶胶凝胶薄膜等；
(a)氧化锌纳米粒子薄膜的制备：例如，将90μL至120μL浓度为10mg/mL至30mg/mL的氧化锌纳米粒子溶解在醇类溶剂(例如，甲醇、乙醇、异丙醇等)中得到的溶液滴加至量子点发光层上，设置匀胶机转速为500rpm至2500rpm并旋涂成膜，在室温或加热(温度可以为25℃至120℃)下成膜，以调整氧化锌纳米粒子薄膜的厚度；
(b)氧化锌溶胶凝胶薄膜的制备：将2g醋酸锌加入至10mL乙醇胺和正丁醇的混合溶剂中，旋涂成膜，设置匀胶机转速为1000rpm至4000rpm，并于180℃至250℃的热台上加热成膜；
电子传输层500的材料还可以选择离子掺杂型氧化锌纳米粒子，例如，Mg、In、Al或Ga掺杂的氧化锌纳米粒子等；
阴极600可以通过蒸镀或溅射的方法制备，可以为金属膜(例如Al膜)或IZO膜。
在示例性实施例中，所述量子点发光器件可以为倒置结构，此时所述第一电极为阴极，所述第二电极为阳极，所述制备方法可以包括：
形成第一电极；
在所述第一电极上形成电子传输层；
在所述电子传输层上形成所述量子点发光层；
在所述量子点发光层上形成空穴传输层；
在所述空穴传输层上形成空穴注入层；
在所述空穴注入层上形成所述第二电极。
图5为本公开示例性实施例的倒置QLED器件的结构示意图。如图5所示，倒置结构的QLED器件可以包括：阴极600、设置在阴极600上的电子传输层500、设置在电子传输层500远离阴极600一侧的量子点发光层400、设置在量子点发光层400远离阴极600一侧的空穴传输层300、设置在空穴传输层300远离阴极600一侧的空穴注入层200、以及设置在空穴注入层200远离阴极600一侧的阳极100。
在示例性实施例中，在倒置结构的QLED器件中，
阴极600可以采用底发射基板导电玻璃或者采用沉积有导电层的普通玻璃基板，导电层可以由ITO(Indium Tin Oxide)、IZO(Indium Zinc Oxide)、FTO(F-doped Tin Oxide)等导电透明材料形成；
阳极100可以通过蒸镀或溅射的方法制备，可以为金属膜(例如Al膜)或IZO膜；
空穴注入层200、空穴传输层300、量子点发光层400、电子传输层500可以选择与正置结构的QLED器件相同的材料和方法制备得到。
本公开的示例性实施例提供一种量子点材料，所述量子点材料包括量子点和修饰所述量子点的配体，所述配体与所述量子点配位结合，所述配体的结构通式为：
Figure PCTCN2022107380-appb-000016
其中，1至8号位点均为氢；A为(CH 2) x-Y，其中，0≤x≤12，Y为巯基、羟基、胺基、氨基、羧基、酯基、膦基或膦氧基(或称为氧化膦)；B为-O-CH 3；C为氢。
例如，A可以为-(CH 2) 5-SH，此时所述配体为式(II)所示的化合物。
Figure PCTCN2022107380-appb-000017
图6为本公开示例性实施例的配体为式(II)所示的化合物的量子点材料在紫外/可见光下发生顺/反构象变化的转化图。
该量子点材料的制备方法包括：
(1)提供含有油胺、油酸等油溶性配体的初始量子点；
(2)将式(II)所示的配体加入有机溶剂(例如，甲苯、二甲苯、氯仿及其混合溶剂)中，得到配体溶液；
(3)将所述初始量子点加入所述配体溶液中，得到含有初始量子点的配体溶液，其中，在含有初始量子点的配体溶液中，所述配体的浓度可以为 100mg/mL至800mg/mL，所述初始量子点的浓度可以为10mg/mL至30mg/mL；将所述含有初始量子点的配体溶液充分搅拌4小时以上(例如，4小时、5小时、6小时、7小时)，使式(II)所示的配体对所述初始量子点表面的油溶性配体进行配体交换；
(4)将步骤(3)完成配体交换之后的溶液滴加到式(II)所示的配体的不良溶剂(例如，丙酮、乙酸乙酯、甲醇及其混合溶剂)中，使含有配体的量子点进行沉淀，通过离心使沉淀与上层溶液分离，去掉上层溶液后再次加入不良溶剂进行离心，直至上层溶液清澈，去掉上层清液后得到所述量子点材料。
本公开的示例性实施例提供一种量子点材料，所述量子点材料包括量子点和修饰所述量子点的配体，所述配体与所述量子点配位结合，所述配体的结构通式为：
Figure PCTCN2022107380-appb-000018
其中，1至8号位点均为氢；A为(CH 2) x-Y，其中，0≤x≤12，Y为巯基、羟基、胺基、氨基、羧基、酯基、膦基或膦氧基(或称为氧化膦)；C为氢；
B可以为长链烷烃，例如为
Figure PCTCN2022107380-appb-000019
其中，m≥10，R 0为-CH 3或苯基；
或者，B为含有噻吩或聚噻吩的基团，例如，B为
Figure PCTCN2022107380-appb-000020
其中，R表示与所述配体的主体相连接的连接端，R为烷基或连接有酰胺键或氨基的烷基，R 1表示自由端，R 1为甲基、乙基或甲氧基，1≤n≤10。
具体地，B可以为
Figure PCTCN2022107380-appb-000021
Figure PCTCN2022107380-appb-000022
其中，R 1表示自由端，R 1为甲基、乙基或甲氧基，p≤3，1≤n≤10。
该量子点材料的制备方法包括：
(1)提供含有油胺、油酸等油溶性配体的初始量子点；
(2)将配体加入有机溶剂(例如，甲苯、二甲苯、氯仿及其混合溶剂)中，得到配体溶液；
(3)将所述初始量子点加入所述配体溶液中，得到含有初始量子点的配体溶液，其中，在含有初始量子点的配体溶液中，所述配体的浓度可以为100mg/mL至800mg/mL，所述初始量子点的浓度可以为10mg/mL至30mg/mL；将所述含有初始量子点的配体溶液充分搅拌4小时以上(例如，4小时、5小时、6小时、7小时)，使配体对所述初始量子点表面的油溶性配体进行配体交换；
(4)将步骤(3)完成配体交换之后的溶液滴加到配体的不良溶剂(例如，丙酮、乙酸乙酯、甲醇及其混合溶剂)中，使含有配体的量子点进行沉淀，通过离心使沉淀与上层溶液分离，去掉上层溶液后再次加入不良溶剂进行离心，直至上层溶液清澈，去掉上层清液后得到所述量子点材料。
本公开的示例性实施例提供一种量子点材料，所述量子点材料包括量子点和修饰所述量子点的配体，所述配体与所述量子点配位结合，所述配体的结构通式为：
Figure PCTCN2022107380-appb-000023
其中，1至8号位点均为氢；A为(CH 2) x-Y，其中，0≤x≤12，Y为巯基、羟基、胺基、氨基、羧基、酯基、膦基或膦氧基(或称为氧化膦)；C为氢；
B可以为氟代烷基或全氟代烷基，例如，B为-(CF 2)q-CF 3，其中，q＞5；
或者，B可以为含有碳碳双键的基团或链段，所述含有碳碳双键的基团或链段可以包括
Figure PCTCN2022107380-appb-000024
其中，R 2、R 3、R 4表示自由端，R 2、R 3、R 4可以各自独立地为氢、氟、甲基、乙基、丙基等短链烷基中的任意一种，R 5表示与所述配体的主体相连接的连接端，R 5可以为烷基或连接有酰胺键或氨基的烷基，例如，B可以为全氟代氟烯基-CF＝CF 2；
或者，B可以为含有碳碳三键的基团或链段，所述含有碳碳三键的基团可以包括
Figure PCTCN2022107380-appb-000025
其中，R 6表示与所述配体的主体相连接的连接端，R 6可以为烷基或连接有酰胺键或氨基的烷基，R 7为自由端，R 7可以为氢、甲基、乙基、丙基等短链烷基中的任意一种。
该量子点材料的制备方法包括：
(1)提供含有油胺、油酸等油溶性配体的初始量子点；
(2)将配体加入有机溶剂(例如，甲苯、二甲苯、氯仿及其混合溶剂) 中，得到配体溶液；
(3)将所述初始量子点加入所述配体溶液中，得到含有初始量子点的配体溶液，其中，在含有初始量子点的配体溶液中，所述配体的浓度可以为100mg/mL至800mg/mL，所述初始量子点的浓度可以为10mg/mL至30mg/mL；将所述含有初始量子点的配体溶液充分搅拌4小时以上(例如，4小时、5小时、6小时、7小时)，使配体对所述初始量子点表面的油溶性配体进行配体交换；
(4)将步骤(3)完成配体交换之后的溶液滴加到配体的不良溶剂(例如，丙酮、乙酸乙酯、甲醇及其混合溶剂)中，使含有配体的量子点进行沉淀，通过离心使沉淀与上层溶液分离，去掉上层溶液后再次加入不良溶剂进行离心，直至上层溶液清澈，去掉上层清液后得到所述量子点材料。

Claims (25)

  1. 一种量子点材料，包括：量子点和修饰所述量子点的配体，所述配体与所述量子点配位结合，所述配体具有光敏异构化性质，为偶氮苯的衍生物并且含有脲基和嘧啶酮基。
  2. 根据权利要求1所述的量子点材料，其中，所述配体被配置为经紫外光照射后呈现顺式结构，并且所述配体的分子间形成四重氢键；经可见光照射后呈现反式结构，并且所述配体的分子内形成氢键。
  3. 根据权利要求2所述的量子点材料，其中，所述配体的结构通式为：
    Figure PCTCN2022107380-appb-100001
    其中，A、B、C中至少有一个含有能够与所述量子点进行配位结合的配位基团。
  4. 根据权利要求3所述的量子点材料，其中，所述配位基团选自巯基、羟基、胺基、氨基、羧基、酯基、膦基和膦氧基中的任意一种或多种。
  5. 根据权利要求4所述的量子点材料，其中，A为(CH 2) x—Y，其中，0≤x≤12，Y为所述配位基团；C为氢；
    或者，A为氢；C为(CH 2) x—Y，其中，0≤x≤12，Y为所述配位基团。
  6. 根据权利要求5所述的量子点材料，其中，B选自下述基团中的任意一种：
    (1)-O-CH 3；或者
    (2)
    Figure PCTCN2022107380-appb-100002
    其中，m≥10，R 0为-CH 3或苯基；
    (3)含有噻吩或聚噻吩的基团；
    (4)氟代烷基或全氟代烷基；
    (5)含有碳碳双键的基团或链段；
    (6)含有碳碳三键的基团或链段。
  7. 根据权利要求6所述的量子点材料，其中，所述含有噻吩或聚噻吩的基团包括
    Figure PCTCN2022107380-appb-100003
    其中，R表示与所述配体的主体相连接的连接端，R为烷基或连接有酰胺键或氨基的烷基，R 1表示自由端，R 1为甲基、乙基或甲氧基，1≤n≤10。
  8. 根据权利要求7所述的量子点材料，其中，所述含有噻吩或聚噻吩的基团包括
    Figure PCTCN2022107380-appb-100004
    Figure PCTCN2022107380-appb-100005
    其中，R 1表示自由端，R 1为甲基、乙基或甲氧基，p≤3，1≤n≤10。
  9. 根据权利要求6所述的量子点材料，其中，所述全氟代烷基包括-(CF 2)q-CF 3，其中，q＞5。
  10. 根据权利要求6所述的量子点材料，其中，所述含有碳碳双键的基团或链段包括
    Figure PCTCN2022107380-appb-100006
    其中，R 2、R 3、R 4表示自由端，R 2、R 3、R 4各自独立地为氢、氟、甲基、乙基和丙基中的任意一种，R 5表示与所述配体的主体相连接的连接端，R 5为烷基或连接有酰胺键或氨基的烷基。
  11. 根据权利要求6所述的量子点材料，其中，所述含有碳碳三键的基团包括
    Figure PCTCN2022107380-appb-100007
    其中，R 6表示与所述配体的主体相连接的连接端，R 6为烷基或连接有酰胺键或氨基的烷基，R 7为自由端，R 7为氢、甲基、乙基、和丙基中的任意一种。
  12. 根据权利要求3至11中任一项所述的量子点材料，其中，所述配体的结构通式中1至8号位点各自独立地为氢、氟。
  13. 根据权利要求12所述的量子点材料，其中，所述配体的结构通式中1至8号位点均为氟。
  14. 根据权利要求3至11中任一项所述的量子点材料，其中，所述量子点选自CdS、CdSe、ZnSe、InP、PbS、CsPbCl 3、CsPbBr 3、CsPhI 3、CdS/ZnS、CdSe/ZnS、ZnSe、ZnTeSe、ZnSe/ZnS、ZnTeSe/ZnS、InP/ZnS、PbS/ZnS、CsPbCl 3/ZnS、CsPbBr 3/ZnS和CsPhI 3/ZnS中的任意一种或多种。
  15. 一种根据权利要求1至14中任一项所述的量子点材料的制备方法，包括：
    提供含有油溶性配体的初始量子点；
    采用配体对所述初始量子点表面的油溶性配体进行配体交换，得到所述量子点材料。
  16. 根据权利要求15所述的制备方法，其中，所述采用配体对所述初始量子点表面的油溶性配体进行配体交换，得到所述量子点材料包括：
    将所述配体溶于有机溶剂中，得到配体溶液；
    将所述初始量子点加入所述配体溶液中，得到含有初始量子点的配体溶液，搅拌，使所述配体对所述初始量子点表面的油溶性配体进行配体交换；
    将配体交换之后的溶液加入所述配体的不良溶剂中，使含有配体的量子点进行沉淀，并从溶液中分离出来，得到所述量子点材料。
  17. 根据权利要求16所述的制备方法，其中，在含有初始量子点的配体溶液中，所述配体的质量浓度为所述初始量子点的质量浓度的3倍至100倍。
  18. 根据权利要求16所述的制备方法，其中，在含有初始量子点的配体溶液中，所述配体的质量浓度为100mg/mL至800mg/mL，所述初始量子点 的质量浓度为10mg/mL至30mg/mL。
  19. 根据权利要求16所述的制备方法，其中，所述配体交换的时间为4小时以上；
    所述有机溶剂选自甲苯、二甲苯和氯仿中的任意一种或多种；
    所述不良溶剂选自丙酮、乙酸乙酯和甲醇中的任意一种或多种。
  20. 一种量子点显示器件，所述量子点显示器件为量子点发光器件、量子点-有机发光二极管、量子点-液晶显示器件或量子点-微型发光二极管中的至少一种，所述量子点显示器件包括根据权利要求1至14中任一项所述的量子点材料。
  21. 根据权利要求20所述的量子点显示器件，其中，所述量子点显示器件为量子点发光器件，所述量子点发光器件包括阳极、阴极、夹设在所述阳极和所述阴极之间的量子点发光层，所述量子点发光层的材料为所述量子点材料。
  22. 根据权利要求20所述的量子点显示器件，其中，所述量子点显示器件为量子点-有机发光二极管、量子点-液晶显示器件或量子点-微型发光二极管中的至少一种，所述量子点显示器件包括色转换层，所述色转换层的材料为所述量子点材料。
  23. 一种显示装置，包括多个根据权利要求20至22中任一项所述的量子点显示器件。
  24. 一种量子点膜图案化的方法，包括：
    形成量子点膜，所述量子点膜的材料为根据权利要求1至14中任一项所述的量子点材料；
    对保留区域的量子点膜进行紫外光照射，使所述保留区域内的量子点材料的配体呈现顺式结构并且配体的分子间形成四重氢键；
    除去不保留区域的量子点膜，得到图案化的量子点膜。
  25. 一种量子点发光器件的制备方法，包括：
    形成第一电极；
    采用根据权利要求24所述的量子点膜图案化的方法形成图案化的量子点膜，作为量子点发光层；
    形成第二电极。
PCT/CN2022/107380 2021-07-30 2022-07-22 量子点材料及其制备方法、量子点显示器件、显示装置、量子点膜图案化的方法、量子点发光器件的制备方法 WO2023005840A1 (zh)

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