WO2023246369A1 - 量子点墨水、量子点层图案化方法和量子点光电器件 - Google Patents

量子点墨水、量子点层图案化方法和量子点光电器件 Download PDF

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WO2023246369A1
WO2023246369A1 PCT/CN2023/093982 CN2023093982W WO2023246369A1 WO 2023246369 A1 WO2023246369 A1 WO 2023246369A1 CN 2023093982 W CN2023093982 W CN 2023093982W WO 2023246369 A1 WO2023246369 A1 WO 2023246369A1
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quantum dot
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quantum
substituted
group
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卢少勇
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京东方科技集团股份有限公司
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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
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/50—Sympathetic, colour changing or similar inks
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/32—Liquid compositions therefor, e.g. developers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/381—Metal complexes comprising a group IIB metal element, e.g. comprising cadmium, mercury or zinc
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the embodiments of the present application relate to, but are not limited to, the technical field of quantum dot patterning, and specifically relate to a quantum dot ink, a quantum dot layer patterning method and a quantum dot optoelectronic device.
  • Colloidal nanocrystals are synthesized in solution from nanometer-sized inorganic nanoparticles whose surfaces are usually coated with ligands to provide colloidal stability to the nanocrystals.
  • the photoelectromagnetic and other physical and chemical properties of nanocrystals are determined by their inorganic core, and these properties are deeply affected by the composition, size and morphology of the inorganic core, while surface ligands give the nanocrystal solution processability and facilitate Build complex devices. These properties make colloidal nanocrystals important building blocks for the construction of advanced materials and devices. More refined control of the composition, size, morphology, crystal structure and surface properties of nanocrystals will also maximize the potential applications of nanomaterials.
  • quantum dots Semiconductor nanocrystals with a radius smaller than or close to the exciton Bohr radius are called quantum dots (usually 1-10 nm in size).
  • quantum dots Due to the quantum confinement effect, quantum dots have excellent luminescent properties such as broadband absorption, narrow-band emission, and continuously adjustable peak positions. As a new generation of luminescent and optoelectronic materials, quantum dots are expected to have a disruptive impact in many application fields such as displays and lighting, lasers, single photon sources, and biomedical imaging. Among them, quantum dots have emerged in the display field, and commercial quantum dot display products have been launched.
  • the performance of colloidal nanocrystals is mainly achieved through the integration of device units with multi-layer nanocrystal stack structures, and the construction of integrated devices usually requires patterning of device unit films or arrays, e.g. .
  • the construction of full-color quantum dot display devices relies on the precise patterning of red, green, and blue light-emitting device units. Therefore, the patterning research of colloidal nanocrystals is of great significance for the construction of low-cost, large-area, and efficient thin-film optoelectronic devices.
  • the inventor of the present disclosure has researched quantum dot patterning technology and found that the existing photolithography method uses a large amount of photoresist, and during the patterning process of the quantum dot layer, a large amount of organic solvent needs to be used to dissolve the photoresist for coating. cloth and development after exposure, increasing costs and causing environmental concerns. Therefore, there is a need to develop green and environmentally friendly quantum dot layer patterning methods.
  • an embodiment of the present disclosure provides a quantum dot ink, which includes:
  • Quantum dot material which includes quantum dots and organic ligands on the surface of the quantum dots.
  • the organic ligands contain: cross-linking units, and coordination functional groups coordinated with the quantum dots;
  • the cross-linking unit in the organic ligand can undergo a cross-linking reaction with the cross-linking agent under the catalysis of hydrogen ions generated by the photoacid generator under ultraviolet light.
  • the present disclosure also provides a method for patterning a quantum dot layer, the method including the following steps:
  • the present disclosure also provides a quantum dot layer, which includes a plurality of sub-pixels, the material of each sub-pixel includes a quantum dot material, and the surface of the quantum dot material is connected with an organic compound as described above.
  • a quantum dot layer which includes a plurality of sub-pixels, the material of each sub-pixel includes a quantum dot material, and the surface of the quantum dot material is connected with an organic compound as described above.
  • the present disclosure also provides a quantum dot optoelectronic device, which includes the quantum dot layer as described above.
  • the present disclosure also provides a method of manufacturing a quantum dot optoelectronic device, including the step of forming a quantum dot layer using the aforementioned quantum dot patterning method.
  • the present disclosure also provides a display device including a quantum dot light-emitting diode, and the quantum dot light-emitting diode includes the aforementioned quantum dot layer.
  • At least one of A, B and C has the same meaning as “at least one of A, B or C” and includes the following combinations of A, B and C: A only, B only, C only, A and B The combination of A and C, the combination of B and C, and the combination of A, B and C.
  • a and/or B includes the following three combinations: A only, B only, and the combination of A and B.
  • hydrocarbyl refers to a hydrocarbon group that does not contain heteroatoms in the main structure, such as alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl and combinations thereof.
  • the hydrocarbyl group may be substituted Substituted with a group, the substituent can be selected from halogen, carboxyl, sulfonic acid group, hydroxyl, mercapto, amino, nitro (-NO 2 ), cyano (-CN), alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, alkoxy, alkenyloxy, alkynyloxy, cycloalkoxy, cycloalkenyloxy, aryloxy, heteroaryl, heterocyclyl and combinations thereof, but not limited thereto.
  • the resulting group is replaced with a heteroatom group.
  • C1-C6 C2-C6
  • C3-C6 C6-C10
  • hetero means that a functional group includes at least 1 heteroatom selected from B, N, O, S, Se, Si, P, etc.
  • alkyl may include straight or branched chain alkyl groups. Unless otherwise limited, an alkyl group may have 1 to 10 carbon atoms, and in this disclosure, a numerical range such as “1 to 10" refers to each integer in the given range; for example, “1 to 10 carbon atoms” It means that it can contain 1 carbon atom, 2 carbon atoms, 3 carbon atoms, 4 carbon atoms, 5 carbon atoms, 6 carbon atoms, 7 carbon atoms, 8 carbon atoms, 9 carbon atoms or 10 Alkyl group of carbon atoms.
  • the alkyl group may also be lower alkyl having 1 to 6 carbon atoms.
  • alkyl groups may be substituted or unsubstituted.
  • Unsubstituted alkyl groups may be "saturated alkyl groups" without any double or triple bonds.
  • the alkyl group is selected from alkyl groups with 1 to 6 carbon atoms, including but not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl and hexyl.
  • alkenyl may include straight or branched alkenyl groups containing at least one carbon-carbon double bond. Unless otherwise limited, the alkenyl group may have 2 to 10 carbon atoms, and in this disclosure, a numerical range such as “2 to 10" refers to each integer in the given range; for example, “2 to 10 carbon atoms” Refers to an alkene that can contain 2 carbon atoms, 3 carbon atoms, 4 carbon atoms, 5 carbon atoms, 6 carbon atoms, 7 carbon atoms, 8 carbon atoms, 9 carbon atoms, or 10 carbon atoms. base.
  • the alkenyl group can also be a lower alkenyl group having 2 to 6 carbon atoms.
  • alkenyl groups may be substituted or unsubstituted.
  • the alkenyl group is selected from alkenyl groups with 2-6 carbon atoms, including but not limited to vinyl, propen-1-yl, propen-2-yl, butenyl, pentenyl, hexenyl wait.
  • alkynyl may include straight or branched chain alkynyl groups containing at least one carbon-carbon triple bond.
  • an alkynyl group may have 2 to 10 carbon atoms, and in this disclosure, a numerical range such as “2 to 10" refers to each integer within the given range; for example, "2 to 10 carbon atoms” Refers to an alkyne that can contain 2 carbon atoms, 3 carbon atoms, 4 carbon atoms, 5 carbon atoms, 6 carbon atoms, 7 carbon atoms, 8 carbon atoms, 9 carbon atoms, or 10 carbon atoms base.
  • the alkynyl group can also be a lower alkynyl group having 2 to 6 carbon atoms.
  • alkynyl groups may be substituted or unsubstituted.
  • the alkynyl group is selected from an alkynyl group with a carbon number of 2-6, including but not limited to, ethynyl, propynyl, butynyl, pentyne base, hexynyl, etc.
  • cycloalkyl refers to a group derived from a saturated cyclic carbon chain structure. Unless otherwise limited, a cycloalkyl group may have 3 to 10 carbon atoms, and in this disclosure, a numerical range such as "3 to 10" refers to each integer in the given range; for example, “3 to 10 carbon atoms” ” refers to a cycloalkyl group that can contain 3 carbon atoms, 4 carbon atoms, 5 carbon atoms, 6 carbon atoms, 7 carbon atoms, 8 carbon atoms, 9 carbon atoms, or 10 carbon atoms. Cycloalkyl groups may be substituted or unsubstituted. Alternatively, examples of cycloalkyl may include, but are not limited to, cyclopentyl, cyclohexyl, and the like.
  • aryl refers to an optional functional group or substituent derived from an aromatic carbocyclic ring.
  • the aryl group can be a single-ring aryl group (such as phenyl) or a polycyclic aryl group.
  • the aryl group can be a single-ring aryl group, a fused-ring aryl group, or two or more single-ring aryl groups conjugated through a carbon-carbon bond.
  • Ring aryl groups monocyclic aryl groups conjugated through carbon-carbon bonds and fused-ring aryl groups, two or more fused-ring aryl groups conjugated through carbon-carbon bonds.
  • two or more aromatic groups conjugated through carbon-carbon bonds can also be regarded as aryl groups in the present disclosure.
  • Aryl groups do not contain heteroatoms such as B, N, O, S, P, Se and Si.
  • Examples of aryl groups may include, but are not limited to, phenyl, naphthyl, and the like.
  • heteroaryl refers to a monovalent aromatic ring containing at least one, such as 1, 2, 3, 4 or 5 heteroatoms in the ring.
  • the heteroatoms can be selected from B, O, N, P, Si, Se and at least one of S.
  • the heteroaryl group can be a monocyclic heteroaryl group or a polycyclic heteroaryl group.
  • the heteroaryl group can be a single aromatic ring system or multiple aromatic ring systems connected by conjugation, and any aromatic ring system is An aromatic single ring or an aromatic fused ring.
  • heteroaryl groups may include thienyl, furyl, pyrrolyl, imidazolyl, thiazolyl, oxazolyl, oxadiazolyl, triazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, acridine Aldyl, pyridazinyl, pyrazinyl, quinolyl, etc., but are not limited thereto.
  • heterocyclyl is a monovalent non-aromatic ring containing at least one, such as 1, 2, 3, 4 or 5 heteroatoms in the ring.
  • the heteroatoms can be selected from B, O, N, P, Si At least one of , Se and S.
  • Heterocyclyl groups may be monocyclic or polycyclic.
  • the heterocyclyl group may include, but is not limited to, dihydropyridinyl, piperidinyl, tetrahydrothienyl, 4-piperidinonyl, pyrrolidinyl, 2-pyrrolidonyl, pyrrolinyl, tetrahydrofuranyl, tetrahydrofuranyl, Hydropyranyl, acridinyl, pyrimidinyl, imidazolidinyl, imidazolinyl, pyrazolidinyl, pyrazolinyl, piperazinyl, morpholinyl, oxazolidinyl, etc.
  • One embodiment of the present disclosure provides a quantum dot ink, which includes: (1) quantum dot material; (2) cross-linking agent; (3) photoacid generator.
  • the weight ratio of quantum dot material, cross-linking agent, and photoacid generator can be 100:(1-30):(0.1-10), optionally, 100:( 2-10): (1-10), for example, 100:5:1, 100:10:1, 100:20:1, 100:30:1, 100:5:2, 100:10:2, 100:20:2, 100:30: 2. 100:5:3, 100:10:3, 100:20:3, 100:30:3, 100:5:4, 100:10:4, 100:20:4, 100:30:4, 100:5:5, 100: 10:5,100:20:5 100:30:5.
  • the quantum dots can have colloidal stability, which facilitates subsequent solution processing into a uniform film, and can achieve better photolithography patterning effects.
  • the quantum dot material includes quantum dots and organic ligands on the surface of the quantum dots.
  • the organic ligands contain: cross-linking units and coordination functional groups coordinated with the quantum dots.
  • the organic ligand is soluble in water.
  • the cross-linking unit of the organic ligand has the structure shown in the following formula I:
  • R 3 is a leaving group, for example, it can be selected from substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C3-C6 cycloalkyl, etc., and the substituted substituent can be selected from halogen, C6 -C8 aryl group (such as phenyl, tolyl, xylyl, ethylphenyl, etc.), in particular, R 3 can be selected from C1-C4 alkyl, benzyl.
  • the coordination functional group included in the organic ligand can be selected from carboxyl (-COOH), sulfonic acid group (-SO 3 H), hydroxyl (-OH), thiol (-SH), amino (- NH 2 ), etc., but are not limited to these.
  • the organic ligand may include one or more, such as 1, 2, or 3 coordination functional groups, and each of the coordination functional groups is independently selected from the above groups.
  • the organic ligand has a structure represented by the following formula II:
  • R 1 and R 2 are each independently selected from linear, branched or cyclic saturated or unsaturated hydrocarbon groups and heterohydrocarbyl groups, and at least one of R 1 and R 2 contains one or more coordination functional groups;
  • R3 is defined as above.
  • R 1 and R 2 may each be independently selected from a linear or branched C1-C6 alkyl group substituted by one or more coordination functional groups, or one of R 1 and R 2 may be selected from one or more coordination functional groups.
  • R 1 and R 2 can each be independently selected from the group consisting of carboxyl (-COOH), sulfonate (-SO 3 H), hydroxyl (-OH), thiol (-SH), amino (-NH) 2 )
  • a linear or branched C1-C4 alkyl group substituted by a coordination functional group or one of R 1 and R 2 is selected from the group consisting of carboxyl (-COOH), sulfonic acid group (-SO 3 H), hydroxyl (- A linear or branched C1-C4 alkyl group substituted by a coordination functional group of OH), mercapto group (-SH), or amino group (-NH 2 ), and the other one is selected from a linear or branched chain C1-C4 alkyl group.
  • organic ligand represented by formula II may be selected from:
  • the organic ligand has a structure represented by the following formula III:
  • R 1 , R 2 and R 4 are each independently selected from linear, branched or cyclic saturated or unsaturated hydrocarbon groups and heterohydrocarbyl groups, and at least one of R 1 , R 2 and R 4 contains one or more Coordinating functional groups;
  • R3 is defined as above.
  • n represents the number of polymerized monomer units, that is, the degree of polymerization.
  • the resulting group is substituted with a group, or one of R 1 , R 2 and R 4 can each be independently selected from a linear, branched or cyclic C1-C6 alkyl group substituted by one or more coordinating functional groups , the other is selected from linear or branched C1-C6 alkyl
  • R 1 , R 2 and R 4 can each be independently selected from the group consisting of carboxyl (-COOH), sulfonate (-SO 3 H), hydroxyl (-OH), thiol (-SH), amino A linear or branched C1-C4 alkyl group substituted by the coordination functional group of (-NH 2 ), or two of R 1 , R 2 and R 4 can each be independently selected from the group consisting of carboxyl (-COOH), sulfonate A linear or branched C1-C4 alkyl group substituted by the coordination functional group of an acid group (-SO 3 H), a hydroxyl group (-OH), a mercapto group (-SH), or an amino group (-NH 2 ), and the other one is selected from a linear group Or branched C1-C4 alkyl, linear or branched C2-C4 alkenyl, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, C6-
  • the C1-C4 alkyl group can be, for example, carboxymethyl, carboxyethyl, carboxypropyl, carboxybutyl, sulfonatemethyl, sulfonateethyl, sulfonatepropyl, sulfonatebutyl, hydroxymethyl hydroxyethyl, hydroxypropyl, hydroxybutyl, mercaptomethyl, mercaptoethyl, mercaptopropyl, mercaptobutyl, aminomethyl, aminoethyl, aminopropyl, aminobutyl, etc., but not limited to this.
  • the organic ligand represented by Formula III can be selected from:
  • the quantum dots can be selected from: II-VI group quantum dots, such as CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgSe, HgTe, HgS, Hg x Cd 1-x Te, Hg x Cd 1-x S, Hg x Cd 1-x Se, Hg x Zn 1-x Te, Cd x Zn 1-x Se, or Cd x Zn 1-x S, where 0 ⁇ x ⁇ 1; or III-V quantum dots, such as InP , InAs, InSb, GaAs, GaP, GaN, GaSb, InN, InSb, AlP, AlN, AlAs; or VI-VI group quantum dots, such as PbS, PbSe, PbTe; or quantum dots with core-shell structure, including CdSe @ZnS, CdSe@CdS, InP@ZnS, CdTe@CdSe, CdSe@
  • the weight ratio of quantum dots and organic ligands can be 100: (1-30), for example, it can be 100:1, 100:2, 100:3, 100:4, 100:5, 100:6, 100:7, 100:8, 100:9, 100:10, 100:11, 100:12, 100:13, 100:14, 100:15, 100:16, 100:17, 100: 18, 100:19, 100:20, 100:21, 100:22, 100:23, 100:24, 100:25, 100:26, 100:27, 100:28, 100:29, 100:30,
  • it is 100: (2:10), such as 100:2, 100:3, 100:4, 100:5, 100:6, 100:7, 100:8, 100:9, 100:10 , but not limited to this.
  • the method of obtaining the quantum dot material of the present disclosure is not particularly limited, and it can be prepared according to any suitable method in the art.
  • quantum dot materials of the present disclosure can be prepared by a ligand exchange method, including:
  • a ligand exchange reaction occurs between the first quantum dot material and the second ligand to obtain a second quantum dot material.
  • the second quantum dot material includes a quantum dot and a second ligand on the surface of the quantum dot.
  • the second ligand is a ligand of the present disclosure as described above.
  • any of the above-mentioned quantum dots whose surface is coated with organic ligands can be applied.
  • the first organic ligand can be organic acids (such as oleic acid), organic amines (such as oleylamine), organic phosphorus (such as trioctylphosphine and trioctylphosphine oxide), thiols (such as isooctyl Thiols and mercaptopropionic acid), polymers (polyvinylpyrrolidone), etc.
  • organic acids such as oleic acid
  • organic amines such as oleylamine
  • organic phosphorus such as trioctylphosphine and trioctylphosphine oxide
  • thiols such as isooctyl Thiols and mercaptopropionic acid
  • polymers polyvinylpyrrolidone
  • the cross-linking agent in the quantum dot ink of the present disclosure is used to cause a cross-linking reaction with the organic ligands in the quantum dot material when the quantum dot layer is exposed to ultraviolet irradiation.
  • polyhydroxy compounds are used as cross-linking agents.
  • Polyols refer to compounds containing two or more hydroxyl groups in the molecule, which can also be called polyols.
  • the polyhydroxy compound is selected from compounds with the following general formula IV: R-(OH) m (IV)
  • R is an m-valent group, for example, it can be an m-valent substituted or unsubstituted C1-C6 alkyl group, a substituted or unsubstituted C1-C6 alkoxyalkyl group, a substituted or unsubstituted C1-C6 alkylthio group Alkyl, substituted or unsubstituted C3-C8 cycloalkyl, substituted or unsubstituted C3-C8 cycloalkenyl, substituted or unsubstituted C6-C10 aryl, substituted or unsubstituted 5-10 membered heteroaryl , substituted or unsubstituted 5-10 membered heterocyclic groups, polyethylene glycol chains, polypropylene glycol chains, etc.
  • the substituents may contain ester groups, ether groups, amide groups, carbonyl groups, etc., but are not limited to these,
  • n is an integer ⁇ 2, such as an integer from 2 to 4.
  • the polyhydroxy compound can be selected from C2-C8 diol, C3-C8 triol, C4-C8 tetraol, polyethylene glycol, polypropylene glycol, etc.
  • the polyhydroxy compound may be selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, pentanediol, hexylene glycol, glycerol, isopenterythritol, pentaerythritol, polyethylene glycol, polyethylene glycol, One or more types of propylene glycol.
  • the photoacid generator in the quantum dot ink of the present disclosure is used to release acidic protons when the quantum dot layer is exposed to ultraviolet irradiation to catalyze the cross-linking reaction between the cross-linking agent and the organic ligand.
  • a suitable photoacid generator as long as it can release acidic protons when the quantum dot layer is exposed to ultraviolet irradiation.
  • suitable photoacid generators can be selected from: diazo salts, including but not limited to diazo sulfate, diazo hydrochloride, diazo sulfonate, diazo hexafluoride Small molecule diazonium salts such as phosphates, diazohexafluoroantimonates, diazoperchlorates, and polymer diazonium salts such as diphenylamine formaldehyde resin; organic polyhalides, including but not limited to trichlorobenzene Ethyl ketone, tribromomethylphenyl sulfone, etc., 4-phenoxydichloroethyl ketone, triazine derivatives (such as 4,6-bis(trichloromethyl)-1,3,5 triazine derivatives) ; Onium salts, including but not limited to phosphonium salts, arsenium salts, selenium salts, sulfonium salts (such
  • the quantum dot ink of the embodiments of the present disclosure may also contain a solvent.
  • the solvent can be selected from water or an organic solvent that is miscible with water, including but not limited to lower alcohols (i.e., C1-C6 alkanols, including but not limited to methanol, ethanol, n-propanol, isopropanol), ethers ( Tetrahydrofuran), acetone, etc., optionally, it is water, methanol, ethanol, tetrahydrofuran, acetone.
  • the solvent can be water or a mixture of water and the above-mentioned organic solvent. In the mixture of water and organic solvent, the volume content of water may be more than 1% and less than 100%, optionally, 50-100%. Within this dosage range, it can be stably dispersed into a colloidal solution state in the mixed solvent.
  • the solvent in the quantum dot ink of the embodiment of the present disclosure is water.
  • the quantum dot ink of the embodiments of the present disclosure may also include additives such as thickeners, but is not limited thereto.
  • the thickener content can be adjusted as needed.
  • the thickener may be selected from methylvinyl MQ silicone, polymethacrylate, polycyanoacrylate.
  • methylvinyl MQ silicone resin is a long-chain spherical molecular structure with a three-dimensional (nonlinear) structure with Si-O bonds as the skeleton. It has high light transmittance and good film-forming properties.
  • the quantum dot layer has good mechanical properties and excellent properties such as high and low temperature resistance, electrical insulation, moisture resistance, and waterproofing.
  • Another embodiment of the present disclosure relates to a method for patterning a quantum dot layer, the method including the following steps:
  • the above steps a-c can be repeated multiple times as needed. In some embodiments, by repeating the above steps a-c, full-color patterning of the red, green, and blue quantum dot film layers can be achieved.
  • step a a film is formed using quantum dot ink according to the present disclosure.
  • any suitable film forming method can be used, such as spin coating, screen printing, blade coating, drop coating, dip coating, Langmuir–Blodgett deposition film forming method, etc.
  • the light intensity of ultraviolet light irradiation can be determined as needed, for example, it can be 1-10000mJ/cm 2 , optionally, the range is 10-1000mJ/cm 2 , but is not limited thereto.
  • the photoacid generator During the exposure process, under the excitation of ultraviolet light, the photoacid generator generates hydrogen ions, activates the functional groups of the organic ligand cross-linking unit, and then undergoes a cross-linking reaction with the functional groups in the cross-linking agent, and finally forms a network with the target molecule. thereby changing the solubility of the target molecule.
  • photoacid generator generates hydrogen ions under light
  • cross-linking reaction occurs between the polyhydroxy compound R-(OH) m and the cross-linking unit of the organic ligand shown in Formula I.
  • the cross-linking reaction is as shown in the following formula, but is not limited to this:
  • polyhydroxy compound R-(OH) m may also have some hydroxyl groups that do not participate in the cross-linking reaction.
  • the partial cross-linking reaction product may be as follows: Those skilled in the art can envision other cross-linking reaction products.
  • carboxylic acid-terminated polymethyl 2-acrylamido-2-methoxyacetate is used as the quantum dot ligand
  • 1,4-butanediol is used as the cross-linking agent
  • 2,4-di When hydroxyphenyldimethylsulfonium trifluoromethanesulfonate is used as a photoacid generator, the following reaction will occur:
  • the generated trifluorosulfonic acid group ionizes to produce hydrogen ions H + :
  • the generated H + causes the surface ligand of quantum dots, polymethyl 2-acrylamido-2-methoxyacetate, to undergo a cross-linking reaction with 1,4-butanediol.
  • Cross-linking reactions can occur between cross-linking units on different molecular chains or between cross-linking units on the same molecular chain.
  • the cross-linking reaction is as shown in the following formula, but is not limited to this:
  • the cross-linking reaction can be as shown in the following formula, but is not limited to this:
  • step c the quantum dot layer exposed in step b is developed with a developer to elute and remove the quantum dots in the unexposed areas to obtain a patterned quantum dot layer.
  • the developer used can be selected according to the structure of the organic ligand used and the structure of the cross-linked product.
  • the developer can be selected from water or water-miscible solvents, including but not limited to lower alcohols (i.e., C1-C6 alkanols, including but not limited to methanol, ethanol, n-propanol, isopropanol , propylene alcohol), polyols (ethylene glycol, glycol oil), lower aldehydes (formaldehyde, acetaldehyde, propionaldehyde), lower carboxylic acids (formic acid, acetic acid, propionic acid, n-butyric acid, n-valeric acid), ethers (tetrahydrofuran, diglyme and 1,4 -Epoxide), acetone, NN dimethylformamide, dimethyl sulfoxide, lower amines (ethylamine and ethylenediamine), pyridine, etc., optionally selected from water, methanol, ethanol, tetrahydrofuran, pyridine , acetone
  • the developer is water.
  • the method for patterning the quantum dot layer according to the embodiment of the present disclosure may also include steps such as baking and vacuum drying as needed, but is not limited thereto.
  • the disclosed quantum dot layer patterning method takes advantage of the processability of quantum dot solutions, introduces polyhydroxy compounds as photo-crosslinking agent molecules, and formulates them together with photoacid generators and quantum dot materials with specific structural unit ligands.
  • the new quantum dot ink forms a quantum dot layer through film-forming methods such as spin coating, and then is exposed and developed to directly pattern the quantum dots. Since the photo-crosslinking molecules directly participate in the patterning of the quantum dot layer, compared with existing photoresist patterning methods, there is no need to wash off the photoresist sacrificial layer, thus greatly simplifying the process flow.
  • the existing indirect photoresist method requires 7 steps, but the method of the present disclosure only requires 4 steps.
  • the ink system can be water-soluble, but is insoluble in water after light cross-linking, water can be used as a developer, which is a green and environmentally friendly direct photolithography patterning method.
  • Another embodiment of the present disclosure relates to a quantum dot layer, which includes a plurality of sub-pixels.
  • the material of each sub-pixel includes a quantum dot material, and the surface of the quantum dot material is connected with a cross-linked structure represented by the following formula V:
  • R and m are the same as in the general formula IV.
  • cross-linked structure of the surface connection of the quantum dot material is shown in Formula V-1:
  • R is the same as that in general formula IV.
  • the quantum dot layer of the present disclosure is prepared using the quantum dot layer patterning method of the present disclosure.
  • Embodiments of the present disclosure also relate to a quantum dot optoelectronic device, which includes the quantum dot layer described in the above technical solution.
  • the quantum dot optoelectronic device may be a quantum dot light emitting diode, a photodetector, a photovoltaic solar cell, etc., but Not limited to this.
  • the quantum dot optoelectronic device may have the structure of a conventional optoelectronic device without particular limitation.
  • the quantum dot optoelectronic device may be a quantum dot light emitting diode.
  • the quantum dot light-emitting diode may also include a cathode, an anode, an electron injection layer, an electron transport layer, a hole transport layer, a hole injection layer, an ultraviolet light isolation layer, a pixel definition layer, Passivation layer, encapsulation layer, etc., but not limited to these.
  • the cathode, anode, electron injection layer, electron transport layer, hole transport layer, hole injection layer, ultraviolet light isolation layer, pixel definition layer, passivation layer, packaging layer, etc. of the quantum dot light-emitting diode according to the embodiment of the present disclosure The structure, material composition and preparation method may adopt any suitable structure, material composition and preparation method without particular limitation. The present disclosure does not involve improvements to these components, so these components are not described in detail to avoid obscuring the main technical ideas of the present disclosure.
  • the quantum dot light-emitting diode according to the embodiment of the present disclosure can be configured as a single-side light-emitting quantum dot device and a double-side light-emitting type quantum dot device, or as a top-emitting light type, a bottom-emitting type, or a double-side light-emitting type.
  • Embodiments of the present disclosure also relate to a method of manufacturing a quantum dot light-emitting device, which method includes the step of forming a quantum dot layer using the above-mentioned quantum dot patterning method.
  • the manufacturing method of the quantum dot optoelectronic device can adopt a conventional optoelectronic device manufacturing process without special limitations.
  • the present disclosure does not involve improvements to processes other than the method of patterning the quantum dot layer, and therefore these processes are not described in detail to avoid obscuring the main technical idea of the present disclosure.
  • An embodiment of the present disclosure also relates to a display device, including the above-mentioned quantum dot light-emitting diode according to the present disclosure.
  • the display device may include a plurality of quantum dot light emitting diodes, at least one of which is a quantum dot light emitting diode according to the present disclosure.
  • the quantum dot light-emitting diode in the display device may be a blue, green or red organic electroluminescent device, but is not limited thereto.
  • the display device can be, for example, a mobile phone, a tablet computer, a television, a monitor, a notebook computer, a digital photo frame, a navigator, a car display, a smart watch, a smart bracelet, or any other product or component with a display function.
  • Other essential components of the display device can be understood by those of ordinary skill in the art, and will not be described in detail here, nor should they be used to limit the present invention.
  • quantum dot ink quantum dot layer patterning method, and quantum dot light emitting diode (QLED) of the present disclosure will be described in detail below with reference to the examples.
  • QLED quantum dot light emitting diode
  • This disclosure proposes a green and environmentally friendly quantum dot patterning method.
  • the main principle is that a photoacid generator generates hydrogen ions by illuminating light, and the functional groups on the catalytic cross-linking agent (such as hydroxyl groups on polyhydroxy compounds) are combined with the quantum dot surface.
  • the functional groups on the body undergo a cross-linking reaction (such as a condensation reaction) to achieve the purpose of cross-linking the quantum dots.
  • the uncross-linked quantum dots are removed through an appropriate developer elution treatment, and finally a patterned quantum dot layer is obtained.
  • the inventor developed a quantum dot ink suitable for this method, and used this method to prepare a quantum dot layer and a quantum dot optoelectronic device containing the quantum dot layer.
  • the quantum dot layer patterning method is a photoresist-less photopatterning method, which can avoid problems such as complex processes, increased costs, and poor solvent compatibility caused by traditional photoresist methods.
  • the construction of multi-layer patterned quantum dot layers only requires repeated spin coating, exposure and development steps, making it easy to construct multi-quantum dot layers with full colors of red, green and blue. Patterned devices.
  • polyhydroxy compounds are used as cross-linking agents to form network molecules in the form of covalent bonds forming carbon-oxygen single bonds.
  • the covalent bonding effect is strong and the cross-linked network structure is stable; and
  • the hydroxyl compound is compatible with the photoacid generator and the solvent of the quantum dot material, and can be directly spin-coated, exposed and developed, avoiding the glue removal step in the traditional photolithography method, and the method is simple and reliable.
  • water can be used as the developer, the processing technology is green and environmentally friendly, and there is a low-cost advantage in mass production.
  • CdSe/ZnS red quantum dots with original ligands of octanethiol were selected and mixed with the above-synthesized poly(2-acrylamido-2-methoxymethyl acetate) (PMAGME-COOH) whose end group was carboxyl group in water. body exchange.
  • the operation is as follows: use 100 mg of quantum dot powder, add it to 2 mL of aqueous solution in which 0.1 g of PMAGME-COOH is dissolved, stir at room temperature for 8 hours, the quantum dots gradually disperse in the aqueous solution, and filter the resulting solution with a polyvinylidene fluoride membrane (PVDF). , the filtrate is the quantum dots whose solvent is water and whose surface ligand is PMAGME-COOH.
  • PVDF polyvinylidene fluoride membrane
  • the water-soluble quantum dots in Example 2 are mixed with the cross-linking agent 1,4-butanediol and the photoacid generator 2,4-dihydroxyphenyldimethylsulfonium trifluoromethanesulfonate.
  • the quantum dots are mixed at a weight ratio of 100:10:1, and the quantum dots, cross-linking agent, and photoacid generator concentrations in the ink are 20 mg/mL, 2 mg/mL, and 0.4 mg respectively. /mL of quantum dot ink.
  • Example 4 Inverted bottom emission patterned QLED device preparation:
  • ITO indium tin oxide
  • zinc oxide nanoparticles 2000 rpm, 30 s, 75 mg/mL
  • the quantum dot ink of Example 3 was then spin-coated (2000 rpm, 30 s).
  • the hole transport layer N,N'-bis(1-naphthyl)-N,N'-diphenyl-1,1'-diphenyl-4,4'-diamine ( NPB)
  • NPB hole transport layer
  • MoO 3 hole injection layer

Abstract

本申请涉及一种量子点墨水、量子点层图案化方法和量子点光电器件。上述量子点墨水包含：量子点材料；交联剂和光致产酸剂，量子点材料包括量子点和在量子点表面的有机配体，有机配体含有交联单元和与量子点配位的配位官能团，其中有机配体中的交联单元可以在光致产酸剂在紫外光照下产生的氢离子催化下与多羟基化合物交联剂发生交联反应。上述量子点墨水由于光交联分子直接参与了量子点层的图案化，相比于已有光刻胶图案化方法无需洗掉光刻胶牺牲层，从而大大简化了工艺流程。

Description

量子点墨水、量子点层图案化方法和量子点光电器件
本申请要求于2022年6月21日提交中国专利局、申请号为202210706849.5、发明名称为“量子点墨水、量子点层图案化方法和量子点光电器件”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申请中。
技术领域
本申请实施例涉及但不限于涉及量子点图案化技术领域，具体涉及一种量子点墨水、量子点层图案化方法和量子点光电器件。
背景技术
胶体纳米晶体是在溶液合成的，具有纳米尺寸的无机纳米颗粒，其表面通常包覆有配体，从而为纳米晶体提供胶体稳定性。通常，纳米晶体的光电磁等物理化学性质由其无机内核决定，并且这些性质深受无机内核的组分，尺寸和形貌影响，而表面配体则赋予了纳米晶体溶液的可加工性，便于构筑复杂器件。这些性质使得胶体纳米晶体成为构建先进材料和器件的重要构筑基元。对纳米晶体的组分，尺寸，形貌，晶体结构和表面性质等方面更加精细地调控也会更大限度地发挥纳米材料的潜在应用。
根据经典的量子限域效应，当半导体纳米晶的几何半径小于其体相材料的激子波尔半径时，价带和导带的能级会呈现离散分布形式，此时纳米晶的性质变得与尺寸相关。半径尺寸小于或接近激子波尔半径的半导体纳米晶称之为量子点(通常尺寸为1-10nm)。
由于量子限域效应，量子点具有宽带吸收、窄带发射且峰位连续可调等优异的发光性质。量子点作为新一代发光和光电材料，有望在显示和照明、激光、单光子源、生物医学成像等众多应用领域产生颠覆性的影响。其中，量子点在显示领域已崭露头角，已有商业化的量子点显示产品问世。
在许多器件应用中，胶体纳米晶体性能的发挥主要是通过具有多层纳米晶堆叠结构的器件单元的集成而实现的，而集成化器件的构建通常需要对器件单元薄膜或阵列进行图案化，例如，全色量子点显示器件的构建依赖于对红绿蓝发光器件单元进行精确的图案化排布。因此，胶体纳米晶体的图案化研究对低成本、大面积、高效薄膜光电器件的构建具有重要意义。
目前，面对量子点的光电应用需求，人们开发出多种图案化方法，如喷墨打印法，转印法和光刻法等等，这些方法有着各自的优缺点。光刻法由于低成本，易于量产和图案分辨率高清等特点，有望成为极具前景的量子点图案化技术。
发明内容
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权利要求的保护范围。
本公开发明人对量子点图案化技术的研究发现：已有的光刻法使用大量的光刻胶，并且在量子点层的图案化过程中需要使用大量的有机溶剂以溶解光刻胶进行涂布以及在曝光后进行显影，从而增加了成本并导致环境问题。因此，需要开发绿色环保的量子点层图案化方法。
一方面，本公开一个实施例提供一种量子点墨水，其包含：
(1)量子点材料，其包括量子点和在量子点表面的有机配体，所述有机配体含有：交联单元，以及与量子点配位的配位官能团；
(2)交联剂；
(3)光致产酸剂，
其中，有机配体中的交联单元可以在光致产酸剂在紫外光照下产生的氢离子催化下与交联剂发生交联反应。
作为本公开实施例的第二方面，本公开还提供一种量子点层图案化的方法，所述方法包括如下步骤：
a.用根据本公开的量子点墨水形成量子点层；
b.在掩膜的遮挡下，将所述量子点层在紫外光照射下曝光，发生交联反应；
c.用显影液洗脱除去未曝光区域的所述量子点，得到图案化的所述量子点层。
作为本公开实施例的第三方面，本公开还提供一种量子点层，其包括多个子像素，每个子像素的材料包括量子点材料，所述量子点材料表面连接有如上所述的有机配体和交联剂的交联产物。
作为本公开实施例的第四方面，本公开还提供一种量子点光电器件，其包括如上所述的量子点层。
作为本公开实施例的第五方面，本公开还提供了一种制作量子点光电器件的方法，包括采用前述的量子点图案化方法形成量子点层的步骤。
作为本公开实施例的第六方面，本公开还提供了一种显示装置，包括量子点发光二极管，量子点发光二极管包括前述量子点层。
在阅读并理解了详细描述后，可以明白其他方面。
详述
以下，将通过实施例对本公开所提供的技术方案进行详细地示例性地描述。提供这些实施例使得本公开将更加全面和完整，并将示例性实施例的构思全面地传达给本领域的技术人员。这些示例性实施例所描述的特征、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，从而能够以多种形式实施，因此不应被理解为限于在此阐述的范例。显然，所描述的实施例仅仅是本公开一部分实施例，而不是全部的实施例。在不冲突的情况下，本公开的实施例及实施例中的特征可以相互组合以得到新的实施例。基于本公开所提供的实施例，本领域普通技术人员所获得的所有其他实施例，都属于本公开保护的范围。
除非另有定义，否则本文所使用的所有技术和科学术语具有与本发明所属领域的普通技术人员通常理解的相同含义。在有冲突的情况下，以本说明书(包括定义)为准。
本公开中使用的“第一”、“第二”以及类似的词语并不表示任何顺序、数量或者重要性，而只是用来区分不同的组成部分。“上”、“下”、“左”、“右”等仅用于表示相对位置关系， 当被描述对象的绝对位置改变后，则该相对位置关系也可能相应地改变。可以理解，当诸如层、膜、区域或基板之类的元件被称作位于另一元件“上”或“下”时，该元件可以“直接”位于另一元件“上”或“下”，或者可以存在中间元件。
本公开中，词语“包括”或其变化，如“包含”、“含有”、“具有”将会被理解为包括所陈述的元素、整数或步骤，或者元素、整数或步骤的组合，但并不排除添加其它的元素、整数或步骤，或者元素、整数或步骤的组合。
“A、B和C中的至少一个”与“A、B或C中的至少一个”具有相同含义，均包括以下A、B和C的组合：仅A，仅B，仅C，A和B的组合，A和C的组合，B和C的组合，及A、B和C的组合。“A和/或B”，包括以下三种组合：仅A，仅B，及A和B的组合。
本公开中，除非另有说明，“多个”的含义是两个或两个以上。
本公开中，烃基指的是主体结构中不包含杂原子的碳氢化合物基团，例如烷基、烯基、炔基、环烷基、环烯基、芳基及其组合，烃基可以被取代基取代，取代基可以选自卤素、羧基、磺酸基、羟基、巯基、氨基、硝基(-NO2)、氰基(-CN)、烷基、烯基、炔基、环烷基、环烯基、芳基、烷氧基、烯氧基、炔氧基、环烷氧基、环烯氧基、芳氧基、杂芳基、杂环基及其组合，但不限于此。
本公开中，杂烃基指的是如上所述的烃基的主体结构中的一个或多个碳被选自，例如但不限于，O、S、N、B、P、Si、Se、C＝O的杂原子基团替换所得的基团。
本公开中，基团前的“C1-C6”、“C2-C6”、“C3-C6”、“C6-C10”等指的是该基团包含的碳原子数。
本公开中，当没有另外提供具体的定义时，“杂”是指在一个官能团中包括至少1个选自B、N、O、S、Se、Si、P等的杂原子。
本公开中，“烷基”可以包括直链或支链烷基。除非另有限定，烷基可具有1至10个碳原子，在本公开中，诸如“1至10”的数值范围是指给定范围中的各个整数；例如，“1至10个碳原子”是指可包含1个碳原子、2个碳原子、3个碳原子、4个碳原子、5个碳原子、6个碳原子、7个碳原子、8个碳原子、9个碳原子或10个碳原子的烷基。烷基还可为具有1至6个碳原子的低级烷基。此外，烷基可为取代的或未取代的。未取代的烷基可以是没有任何双键或三键的“饱和烷基基团”。可选地，烷基选自碳原子数为1-6的烷基，包括但不限于，甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、戊基和己基。
本公开中，“烯基”可以包括含有至少一个碳-碳双键的直链或支链烯基。除非另有限定，烯基可具有2至10个碳原子，在本公开中，诸如“2至10”的数值范围是指给定范围中的各个整数；例如，“2至10个碳原子”是指可包含2个碳原子、3个碳原子、4个碳原子、5个碳原子、6个碳原子、7个碳原子、8个碳原子、9个碳原子或10个碳原子的烯基。烯基还可为具有2至6个碳原子的低级烯基。此外，烯基可为取代的或未取代的。可选地，烯基选自碳原子数为2-6的烯基，包括但不限于，乙烯基、丙烯-1-基、丙烯-2-基、丁烯基、戊烯基、己烯基等。
本公开中，“炔基”可以包括含有至少一个碳-碳三键的直链或支链炔基。除非另有限定，炔基可具有2至10个碳原子，在本公开中，诸如“2至10”的数值范围是指给定范围中的各个整数；例如，“2至10个碳原子”是指可包含2个碳原子、3个碳原子、4个碳原子、5个碳原子、6个碳原子、7个碳原子、8个碳原子、9个碳原子或10个碳原子的炔基。炔基还可为具有2至6个碳原子的低级炔基。此外，炔基可为取代的或未取代的。可选地，炔基选自碳原子数为2-6的炔基，包括但不限于，乙炔基、丙炔基、丁炔基、戊炔 基、己炔基等。
在本公开中，环烷基指的是衍生自饱和环状碳链结构的基团。除非另有限定，环烷基可具有3至10个碳原子，在本公开中，诸如“3至10”的数值范围是指给定范围中的各个整数；例如，“3至10个碳原子”是指可包含3个碳原子、4个碳原子、5个碳原子、6个碳原子、7个碳原子、8个碳原子、9个碳原子、10个碳原子的环烷基。环烷基可为取代的或未取代的。可选地，环烷基的实例可以包括但不限于环戊基、环己基等。
本公开中，芳基指的是衍生自芳香碳环的任选官能团或取代基。芳基可以是单环芳基(例如苯基)或多环芳基，换言之，芳基可以是单环芳基、稠环芳基、通过碳碳键共轭连接的两个或者更多个单环芳基、通过碳碳键共轭连接的单环芳基和稠环芳基、通过碳碳键共轭连接的两个或者更多个稠环芳基。即，除非另有说明，通过碳碳键共轭连接的两个或者更多个芳香基团也可以视为本公开的芳基。芳基中不含有B、N、O、S、P、Se和Si等杂原子。芳基的实例可以包括但不限于，苯基、萘基等。
本公开中，杂芳基是指环中包含至少一个，例如1、2、3、4或5个杂原子的一价芳香环，杂原子可以是选自B、O、N、P、Si、Se和S中的至少一种。杂芳基可以是单环杂芳基或多环杂芳基，换言之，杂芳基可以是单个芳香环体系，也可以是通过共轭连接的多个芳香环体系，且任一芳香环体系为一个芳香单环或者一个芳香稠环。例如，杂芳基可以包括噻吩基、呋喃基、吡咯基、咪唑基、噻唑基、噁唑基、噁二唑基、三唑基、吡啶基、联吡啶基、嘧啶基、三嗪基、吖啶基、哒嗪基、吡嗪基、喹啉基等，但不限于此。
本公开中，杂环基是环中包含至少一个，例如1、2、3、4或5个杂原子的一价非芳香性环，杂原子可以是选自B、O、N、P、Si、Se和S中的至少一种。杂环基可以是单环或多环。例如，杂环基可以包括，但不限于，二氢吡啶基、哌啶基、四氢噻吩基、4-哌啶酮基、吡咯烷基、2-吡咯烷酮基、吡咯啉基、四氢呋喃基、四氢吡喃基、吖啶基、嘧啶基、咪唑烷基、咪唑啉基、吡唑烷基、吡唑啉基、哌嗪基、吗啉基、噁唑烷基等。
为了保持本公开实施例的以下说明清楚且简明，本公开省略了已知功能和已知部件的详细说明。
1.量子点墨水
本公开一个实施例提供一种量子点墨水，其包含：(1)量子点材料；(2)交联剂；(3)光致产酸剂。
本公开实施例的量子点墨水中，量子点材料、交联剂、光致产酸剂的重量比可以为100:(1-30):(0.1-10)，可选地，为100:(2-10):(1-10)，例如100:5:1，100:10:1,100:20:1,100:30:1，100:5:2，100:10:2,100:20:2,100:30:2，100:5:3，100:10:3,100:20:3,100:30:3，100:5:4，100:10:4,100:20:4,100:30:4，100:5:5，100:10:5,100:20:5 100:30:5。在该范围内，可以实现量子点具有胶体稳定性，利于后续通过溶液加工成均匀薄膜的效果，并且可实现较好的光刻图案化的效果。
(1)量子点材料
所述量子点材料包括量子点和在量子点表面的有机配体，所述有机配体含有：交联单元和与量子点配位的配位官能团。
在实施例中，所述有机配体可溶于水。
在实施例中，所述有机配体的交联单元具有下式I所示的结构：
其中，R3为离去基团，例如可以选自取代或未取代的C1-C6烷基、取代或未取代的C3-C6环烷基等，所述取代的取代基可以选自卤素、C6-C8芳基(例如苯基、甲苯基、二甲苯基、乙苯基等)，特别地，R3可以选自C1-C4烷基、苄基。
在实施例中，所述有机配体中包含的配位官能团可以选自羧基(-COOH)、磺酸基(-SO3H)、羟基(-OH)、巯基(-SH)、氨基(-NH2)等，但不限于此。此外，所述有机配体可以包含一个或多个，例如1、2、3个配位官能团，所述配位官能团各自独立地选自上述基团。
在实施例中，所述有机配体具有下式II所示的结构：
其中，
R1和R2各自独立地选自直链、支链或环状的饱和或不饱和的烃基和杂烃基，且R1和R2中的至少一个包含一个或多个配位官能团；
R3定义如上所述。
在实施例中，R1和R2可以各自独立地选自由一个或多个配位官能团取代的直链或支链的C1-C6烷基，或者R1和R2之一为由一个或多个配位官能团取代的直链或支链的C1-C6烷基，另一个选自直链或支链的C1-C6烷基。
在实施例中，R1和R2可以各自独立地选自由选自羧基(-COOH)、磺酸基(-SO3H)、羟基(-OH)、巯基(-SH)、氨基(-NH2)的配位官能团取代的直链或支链C1-C4烷基，或者R1和R2之一为由选自羧基(-COOH)、磺酸基(-SO3H)、羟基(-OH)、巯基(-SH)、氨基(-NH2)的配位官能团取代的直链或支链的C1-C4烷基，另一个选自直链或支链的C1-C4烷基。
在实施例中，式II所示的有机配体例如可以选自：
在实施例中，所述有机配体具有下式III所示的结构：
其中，
R1、R2和R4各自独立地选自直链、支链或环状的饱和或不饱和的烃基和杂烃基，且R1、R2和R4中的至少一个包含一个或多个配位官能团；
R3定义如上所述。
在式III中，n表示聚合的单体单元数，即聚合度。
在实施例中，R1、R2和R4可以各自独立地选自由一个或多个配位官能团取代的直链或支链C1-C6烷基，或者R1、R2和R4中的两个可以各自独立地选自由一个或多个配位官能团取代的直链、支链或环状的C1-C6烷基，另一个选自直链或支链C1-C6烷基、直链或支链C2-C6烯基、C3-C6环烷基、C3-C6环烯基、C6-C10芳基或上述基团中的一个或多个碳被选自O、S、N、C＝O的基团取代所得的基团，或者R1、R2和R4中的一个可以各自独立地选自由一个或多个配位官能团取代的直链、支链或环状的C1-C6烷基，另一个选自直链或支链C1-C6烷基、直链或支链C2-C6烯基、C3-C6环烷基、C3-C6环烯基、C6-C10芳基或上述基团中的一个或多个碳被选自O、S、N、C＝O的基团取代所得的基团；
在实施例中，R1、R2和R4可以各自独立地选自由选自羧基(-COOH)、磺酸基(-SO3H)、羟基(-OH)、巯基(-SH)、氨基(-NH2)的配位官能团取代的直链或支链C1-C4烷基，或者R1、R2和R4中的两个可以各自独立地选自由选自羧基(-COOH)、磺酸基(-SO3H)、羟基(-OH)、巯基(-SH)、氨基(-NH2)的配位官能团取代的直链或支链C1-C4烷基，另一个选自直链或支链C1-C4烷基、直链或支链C2-C4烯基、C3-C6环烷基、C3-C6环烯基、C6-C10芳基或上述基团中的一个或多个碳被选自O、S、N、C＝O的基团替换所得的基团，或者R1、R2和R4之一为由选自羧基(-COOH)、磺酸基(-SO3H)、羟基(-OH)、巯基(-SH)、氨基(-NH2)的配位官能团取代的直链或支链的C1-C4烷基，另一个选自直链或支链C1-C4烷基、直链或支链C2-C4烯基、C3-C6环烷基、C3-C6环烯基、C6-C10芳基或上述基团中的一个或多个碳被选自O、S、N、C＝O的基团取代所得的基团。
所述由选自羧基(-COOH)、磺酸基(-SO3H)、羟基(-OH)、巯基(-SH)、氨基(-NH2)的配位官能团取代的直链或支链C1-C4烷基例如可以为羧甲基、羧乙基、羧丙基、羧丁基、磺酸基甲基、磺酸基乙基、磺酸基丙基、磺酸基丁基、羟甲基、羟乙基、羟丙基、羟丁基、巯基甲基、巯基乙基、巯基丙基、巯基丁基、氨基甲基、氨基乙基、氨基丙基、氨基丁基等，但不限于此。在实施例中，式III所示的有机配体例如可以选自：
所述量子点可以选自：II-VI族量子点，如CdS、CdSe、CdTe、ZnS、ZnSe、ZnTe、HgSe、HgTe、HgS、HgxCd1-xTe、HgxCd1-xS、HgxCd1-xSe、HgxZn1-xTe、CdxZn1-xSe、或CdxZn1-xS,其中0<x<1；或者III-V族量子点，如InP、InAs、InSb、GaAs、GaP、GaN、GaSb、InN、InSb、AlP、AlN、AlAs；或者Ⅵ-VI族量子点，如PbS、PbSe、PbTe；或者，具备核壳结构的量子点，包括CdSe@ZnS、CdSe@CdS、InP@ZnS、CdTe@CdSe、CdSe@ZnTe、ZnTe@CdSe、ZnSe@CdS或Cd1-xZnxS@ZnS；或者ABX3型钙钛矿量子点，A为CH3NH3 +(甲胺)、NH2CH＝NH2(甲脒)、Cs+中的一种或多种，B为Pb2+、Sn2+中的一种或两种，X为Cl-、Br-、I-中的一种或多种，包括CH3NH3PbBr3、CH3NH3PbCl3、CH3NH3PbI3、CsPbBr3、CsPbCl3、CsPbI3；或其他量子点，如CuInS2、CuInSe2、AgInS2等。
本公开的量子点材料中，量子点和有机配体的重量比可以为100：(1-30)，比如可以为100:1，100:2，100:3，100:4，100:5，100:6，100:7，100:8，100:9，100:10，100:11，100:12，100:13，100:14，100:15，100:16，100:17，100:18，100:19，100:20，100:21，100:22，100:23，100:24，100:25，100:26，100:27，100:28，100:29，100:30，可选地，为100：(2:10)，比如为100:2，100:3，100:4，100:5，100:6，100:7，100:8，100:9，100:10，但不限于此。
本公开的量子点材料的获取方式没有特别限制，其可以按照本领域中任何适合的方法制备。
在实施例中，例如，本公开的量子点材料可以通过配体交换法制备，包括：
(1)提供第一量子点材料，其包括量子点和在量子点表面的第一配体；
(2)使第一量子点材料与第二配体发生配体交换反应，得到第二量子点材料，所述第二量子点材料包括量子点和在量子点表面的第二配体，所述第二配体为如上所述的本公开的配体。
作为第一量子点材料，只要表面包覆有机配体的上述量子点均可以适用。
例如，第一有机配体可以为有机酸类(如油酸)，有机胺类(如油胺)，有机磷类(如三辛基膦和三辛基氧膦)，硫醇(如异辛硫醇和巯基丙酸)，聚合物类(聚乙烯吡咯烷酮)等。
(2)交联剂
本公开的量子点墨水中的交联剂用于在对量子点层进行紫外照射曝光时与量子点材料中的有机配体发生交联反应。
在实施例中，采用多羟基化合物作为交联剂。
多羟基化合物指的是分子中含有两个或更多个羟基的化合物，也可以称为多元醇。
本公开实施例中，所述多羟基化合物选自具有如下通式IV的化合物：
R-(OH)m   (IV)
其中，
R是一m价基团，例如可以是m价的取代或未取代的C1-C6烷基、取代或未取代的C1-C6烷氧基烷基、取代或未取代的C1-C6烷硫基烷基、取代或未取代的C3-C8环烷基、取代或未取代的C3-C8环烯基、取代或未取代的C6-C10芳基、取代或未取代的5-10元杂芳基、取代或未取代的5-10元杂环基、聚乙二醇链、聚丙二醇链等，取代基可以含有酯基，醚基，酰胺基，羰基等，但不限于此，
m为≥2的整数，例如2-4的整数。
例如m＝2时，分子可以为乙二醇，丙二醇、丁二醇(例如1,4-丁二醇)；m＝3时，分子可以为丙三醇；m＝4时，分子可以为异戊四醇。羟基数目越多，交联度越高。
本公开实施例中，所述多羟基化合物可以选自C2-C8二醇、C3-C8三醇、C4-C8四醇、聚乙二醇、聚丙二醇等。
本公开实施例中，所述多羟基化合物可以为选自乙二醇、丙二醇、丁二醇、戊二醇、己二醇、丙三醇、异戊四醇、季戊四醇、聚乙二醇、聚丙二醇中的一种或多种。
(3)光致产酸剂
本公开的量子点墨水中的光致产酸剂用于在对量子点层进行紫外照射曝光时，释放酸性质子，以催化交联剂与有机配体的交联反应。
本公开中，对于适合的光致产酸剂没有特别限制，只要其在对量子点层进行紫外照射曝光时能够释放酸性质子即可。
本公开实施例中，例如，适合的光致产酸剂可以选自：重氮盐类，包括但不限于重氮硫酸盐、重氮盐酸盐、重氮磺酸盐，重氮六氟合磷酸酸盐，重氮六氟合锑酸盐，重氮高氯酸盐等小分子重氮盐，以及二苯胺甲醛树脂等聚合物重氮盐；有机多卤化物，包括但不限于三氯苯乙酮、三溴甲基苯基砜等，4-苯氧基二氯乙酮，三嗪衍生物(如4,6-二(三氯甲基)-1,3,5三嗪衍生物)；鎓盐类，包括但不限于磷鎓盐，砷鎓盐，硒鎓盐，硫鎓盐(如2,4-二羟基苯基二甲基锍三氟甲烷磺酸盐)和碘鎓盐；磺酸酯类，包括但不限于N-对甲苯磺酰氧邻苯二甲酰亚胺，N-三氟甲烷磺酰氧琥珀酰亚胺，N-三氟甲烷磺酰氧萘二甲酰亚胺、二硝基苄基对甲苯磺酸酯，α-羟甲基安息香的对甲苯磺酸酯等；其他类，包括但不限于α,α-二(芳基磺酰)重氮甲烷和α-碳酰-α-磺酰重氮甲烷等。
此外，为了便于混合和涂布，本公开实施例的量子点墨水中还可以包含溶剂。所述溶剂可以选自水或能与水互溶的有机溶剂，包括但不限于低级醇(即C1-C6烷醇，包括但不限于甲醇、乙醇、正丙醇、异丙醇)，醚类(四氢呋喃)，丙酮等，可选地，为水，甲醇，乙醇，四氢呋喃，丙酮，特别地，溶剂可以为水或者水与上述有机溶剂的混合物。在水与有机溶剂的混合物中，水的体积含量可以为1％以上至小于100％，可选地，为50-100％。在该用量范围内，可以实现在混合溶剂中可以稳定分散呈胶体溶液状态。
在实施例中，本公开实施例的量子点墨水中的溶剂为水。
此外，本公开实施例的量子点墨水中还可以包括增稠剂等添加剂，但不限于此。增稠剂的含量可以根据需要进行调整。例如，增稠剂可以选自甲基乙烯基MQ硅树脂、聚甲基丙烯酸酯、聚氰基丙烯酸酯。例如，甲基乙烯基MQ硅树脂是以Si-O键为骨架而构成的立体(非线性)结构的长链球状分子结构，具有高透光性能、良好的成膜性能。作为增稠剂添加到量子点层中，使得量子点层具有良好的机械性能和耐高低温、电气绝缘、防潮、防水等优良性能。
2.量子点层图案化的方法
本公开另一实施例涉及一种量子点层图案化的方法，所述方法包括如下步骤：
a.用根据本公开的量子点墨水形成量子点层；
b.在掩膜的遮挡下，将量子点层在紫外光照射下曝光，发生交联反应；
c.用显影液洗脱除去未曝光区域的量子点，得到图案化的量子点层。
本公开实施例中，根据需要，上述步骤a-c可以重复多次。在一些实施例中，通过重复上述步骤a-c，可以实现红绿蓝量子点膜层全色图案化。
(a)形成量子点层
在步骤a中，用根据本公开的量子点墨水形成薄膜。
对于形成薄膜的方法没有特别限制，可以采用任何适合的成膜方式，例如旋涂法，丝网印刷法，刮涂法，滴涂法，浸涂法，Langmuir–Blodgett沉积成膜法等。
(b)曝光
在实施例中，紫外光照射的光强度可以根据需要而确定，例如可以为1-10000mJ/cm2，可选地，区间为10-1000mJ/cm2，但不限于此。
在曝光过程中，在紫外光激发下，光致产酸剂生成氢离子，活化有机配体交联单元的官能团，进而与交联剂中的官能团发生交联反应，最终与目标分子形成网络，从而改变目标分子的溶解度。
在实施例中，会发生如下反应：
首先，光致产酸剂(PAG)在光照下产生氢离子
然后，在H+作用下，多羟基化合物R-(OH)m与式I所示的所述有机配体的交联单元发生交联反应。例如，交联反应如下式所示，但不限于此：
此外，多羟基化合物R-(OH)m也可能有部分羟基未参与交联反应，例如部分交联反应产物可能如下式所示：本领域技术人员可以设想其他的交联反应产物。
在实施例中，使用羧酸封端的聚甲基2-丙烯酰胺基-2-甲氧基乙酸酯作为量子点配体，1,4-丁二醇作为交联剂，2,4-二羟基苯基二甲基锍三氟甲烷磺酸盐作为光致产酸剂的情况下，会发生如下反应：
首先，在光照下光致产酸剂2,4-二羟基苯基二甲基锍三氟甲烷磺酸盐会与含活泼氢的 1,2-丁二醇发生如下夺氢反应：
生成的三氟磺酸基电离出氢离子H+:
生成的H+使量子点的表面配体聚甲基2-丙烯酰胺基-2-甲氧基乙酸酯与1,4-丁二醇发生交联反应。交联反应可以发生在不同分子链上的交联单元之间，也可以发生在同一分子链上的交联单元之间。例如，交联反应如下式所示，但不限于此：
在实施例中，聚合度n为3的羧酸封端的聚甲基2-丙烯酰胺基-2-甲氧基乙酸酯作为量子点配体与1,4-丁二醇发生交联反应时，交联反应可以如下式所示，但不限于此：
(c)显影
在步骤c中，将经步骤b曝光后的量子点层用显影液显影，洗脱除去未曝光区域的量子点，得到图案化的量子点层。
所采用的显影液可以根据所采用的有机配体的结构以及交联产物的结构而选择。
在实施例中，所述显影液可以选自水或能与水互溶的溶剂，包括但不限于低级醇(即C1-C6烷醇，包括但不限于甲醇、乙醇、正丙醇、异丙醇、丙烯醇)，多元醇(乙二醇、甘 油)，低级醛(甲醛、乙醛、丙醛)，低级羧酸(甲酸、乙酸、丙酸、正丁酸、正戊酸)，醚类(四氢呋喃、二甘醇二甲醚和1,4-环氧六环)，丙酮，N-N二甲基甲酰胺，二甲亚砜，低级胺(乙胺和乙二胺)，吡啶等，可选地，选自水，甲醇，乙醇，四氢呋喃，吡啶，丙酮，N-N二甲基甲酰胺和二甲亚砜等。特别地，溶剂可以为水或者水与上述有机溶剂的混合物。在水与有机溶剂的混合物中，水的体积含量可以为1％以上至小于100％，可选地，为50-100％。
在实施例中，显影液为水。
根据本公开实施例的量子点层图案化的方法还可以根据需要包括烘烤、真空干燥等步骤，但不限于此。
本公开的量子点层图案化的方法利用量子点溶液可加工的特点，引入多羟基化合物作为光交联剂分子，与光致产酸剂和具有特定结构单元配体的量子点材料一起配制成新型量子点墨水，经过旋涂等成膜方式形成量子点层，然后曝光显影，从而直接实现量子点的图案化。由于光交联分子直接参与了量子点层的图案化，相比于已有光刻胶图案化方法无需洗掉光刻胶牺牲层，从而大大简化了工艺流程。比如为了构筑量子点层，已有间接光刻胶方法需要7步，而本公开的方法仅需4步即可。另外由于墨水体系可以是水溶性的，而光照交联后不溶于水，因此可以用水作为显影液，是一种绿色环保的直接光刻图案化方法。
3.量子点层
本公开另一实施例涉及一种量子点层，其包括多个子像素，每个子像素的材料包括量子点材料，所述量子点材料表面连接有下式V所示的交联结构：
其中，R和m的定义与通式IV中相同。
在实施例中，所述量子点材料表面连接的交联结构如式V-1所示：
其中，R的定义与通式IV中相同。
在实施例中，本公开的量子点层采用上述本公开的量子点层图案化的方法制备。
4.量子点光电器件
本公开实施例还涉及一种量子点光电器件，其包括上述技术方案所述的量子点层。
所述量子点光电器件可以是量子点发光二极管、光电探测器、光伏太阳能电池等，但 不限于此。
除了根据本公开的量子点层以外，所述量子点光电器件可以具有常规光电器件的结构而没有特别限制。
在实施例中，所述量子点光电器件可以为量子点发光二极管。除了根据本公开的量子点层以外，所述量子点发光二极管还可以包括阴极、阳极、电子注入层、电子传输层、空穴传输层、空穴注入层、紫外光隔绝层、像素界定层、钝化层、封装层等，但不限于此。
根据本公开实施例的量子点发光二极管的阴极、阳极、电子注入层、电子传输层、空穴传输层、空穴注入层、紫外光隔绝层、像素界定层、钝化层、封装层等的结构、材料组成和制备方法可以采用任何适合的结构、材料组成和制备方法而没有特别限制。本公开不涉及对这些组件的改进，因此对于这些组件不做详细描述，以避免模糊本公开的主要技术创意。
根据需要，根据本公开实施例的量子点发光二极管可以设置成单面出光型量子点器件和双面出光型量子点器件，或者设置成顶出光型、底出光型和双面出光型。
5.量子点光电器件的制作方法
本公开实施例还涉及一种制作量子点发光器件的方法，所述方法包括采用上述的量子点图案化的方法形成量子点层的步骤。
除了使用根据本公开的量子点图案化的方法形成量子点层以外，所述量子点光电器件的制作方法可以采用常规光电器件的制作工艺而没有特别限制。本公开不涉及对除了量子点层图案化的方法之外的工艺的改进，因此对于这些工艺不做详细描述，以避免模糊本公开的主要技术创意。
6.显示装置
本公开实施例还涉及一种显示装置，包括上述根据本公开的量子点发光二极管。
在实施例中，所述显示装置可以包括多个量子点发光二极管，其中至少一个为根据本公开的量子点发光二极管。例如，所述显示装置中的量子点发光二极管可以为蓝色、绿色或红色有机电致发光器件，但不限于此。
例如，该显示装置中的其他结构可参见常规设计。该显示装置例如可以为手机、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。对于该显示装置的其它必不可少的组成部分均为本领域的普通技术人员可以理解具有的，在此不做赘述，也不应作为对本发明的限制。
为了进一步理解本公开，下面结合实施例对本公开的量子点墨水、量子点层图案化方法、量子点发光二极管(QLED)进行详细说明，本公开的保护范围不受以下实施例的限制。
本公开提出了一种绿色环保的量子点图案化方法，主要原理是光致产酸剂光照产生氢离子，通过催化交联剂上的官能团(例如多羟基化合物上的羟基)与量子点表面配体上的官能团发生交联反应(例如缩合反应)，达到交联量子点的目的，再通过合适的显影液洗脱处理，除去未交联的量子点，最终得到图案化的量子点层。在此基础上，发明人开发了适用于该方法的量子点墨水，并使用该方法制备了量子点层以及包含所述量子点层的量子点光电器件。
根据本公开实施例的量子点层图案化的方法是一种无光刻胶光致图案化方法，可以避免传统光刻胶方法导致的工艺复杂、成本增加、溶剂兼容性差等问题。此外，多层图案化量子点层的构建仅需进行重复旋涂、曝光和显影步骤，易于构建红绿蓝全色的多量子点层 图案化器件。在根据本公开的一些实施例中，采用多羟基化合物作为交联剂，以形成碳氧单键的共价键形式形成网络分子，共价键合作用较强，交联网络结构稳定；并且多羟基化合物与光致产酸剂与量子点材料的溶剂兼容，可直接进行旋涂、曝光和显影，避免了传统光刻方法中的去胶步骤，方法简单可靠。在根据本公开的一些实施例中，可用水作为显影液，加工工艺绿色环保，且量产上有低成本优势。
实施例1：水溶性高分子聚甲基2-丙烯酰胺基-2-甲氧基乙酸酯(PMAGME-COOH)的合成
参照文献Chem.Mater.1997,9,1725中公开的方法，在40mL甲苯与30mL正丁醇的混合溶剂中，以7g2-丙烯酰胺基-2-甲氧基乙酸甲酯(MAGME)为单体，以0.03g偶氮二异丁腈(AIBN)为引发剂，用113mg 4-氰基-4-(硫代苯甲酰)戊酸代替四溴化碳作为链转移试剂，利用可逆加成断裂合成末端基为羧基的聚2-丙烯酰胺基-2-甲氧基乙酸甲酯(PMAGME-COOH)。
实施例2：配体交换得到水溶性量子点
选用原有配体为辛硫醇的CdSe/ZnS红色量子点，与上述合成的末端基为羧基的聚2-丙烯酰胺基-2-甲氧基乙酸甲酯(PMAGME-COOH)在水中进行配体交换。操作如下：用100mg量子点粉末，加入到溶解有0.1g的PMAGME-COOH的2mL水溶液中，常温搅拌8小时，量子点逐渐分散在水溶液中，用聚偏二氟乙烯膜(PVDF)过滤所得溶液，滤液即为溶剂为水，表面配体为PMAGME-COOH的量子点。
实施例3：量子点图案化
量子点墨水的制备
将实施例2中的水溶性量子点与交联剂1,4-丁二醇，光致产酸剂2,4-二羟基苯基二甲基锍三氟甲烷磺酸盐混合，按照量子点：交联剂：光致产酸剂为100:10:1的重量比混合，配制成墨水中量子点，交联剂，光致产酸剂浓度分别为20mg/mL、2mg/mL、0.4mg/mL的量子点墨水。
量子点层的图案化
用前面制备的量子点墨水在玻璃基底上旋涂成膜，在掩模版下紫外曝光，然后用水作为显影液洗去未交联的量子点，然后在100℃烘烤后得到图案化的量子点膜层。
实施例4：倒置底发射图案化QLED器件制备：
在氧化铟锡(ITO)基板上，在空气中，使用溶胶凝胶法旋涂旋涂氧化锌纳米粒子(2000rpm，30s，75mg/mL)，180℃退火1分钟。再旋涂实施例3的量子点墨水(2000rpm，30s)。之后置于光掩膜版下，用10mW/cm2的254nm低压汞灯进行曝光30s。然后浸泡于水中2分钟显影，100℃退火10分钟，得到图案化量子点膜层。
之后通过蒸镀设备制备空穴传输层(N,N’-双(1-萘基)-N,N’-二苯基-1,1’-二苯基-4,4’-二胺(NPB))和空穴注入层(MoO3)，蒸镀银电极120nm，封装后完成器件制备。
实施例5：正置底发射图案化QLED器件制备
分别用去离子水和异丙醇清洗ITO基板，之后在plasma清洗仪(紫外加臭氧)处理15分钟；空气中旋涂聚(3,4-乙烯二氧噻吩):聚苯乙烯磺酸盐(PEDOT:PSS)(2000rpm，30s)，120℃烘烤10分钟，除去水溶剂。然后在氮气氛围的手套箱中旋涂交联化的聚[(9,9-二辛基芴-2,7-二基)-共-(4,4′-(N-(4-仲丁基苯基)二苯胺)](TFB)氯苯溶液(8mg/mL，2000rpm，30s)，150℃下退火30分钟。再旋涂实施例3的量子点墨水(2000rpm，30s)。之后置于光掩膜版下，用10mW/cm2的254nm低压汞灯进行曝光30s，然后浸泡于水中2分钟显影，100℃退火10分钟，得到图案化量子点膜层。
然后在手套箱中旋涂氧化锌纳米粒子(30mg/mL，3000rpm，30s)，之后在120℃下烘烤10分钟，除去溶剂；蒸镀铝电极120nm，最后点胶封装完成器件制备。
虽然已经如上描述了本公开，但所述的内容仅为便于理解本公开而采用的实施方案，并非用以限定本公开。任何所属技术领域内的技术人员，在不脱离本公开所揭露的精神和范围的前提下，可以在实施的形式及细节上进行任何的修改与变化，但本申请的专利保护范围，仍须以所附的权利要求书所界定的范围为准。

Claims (20)

  1. 一种量子点墨水，包含：量子点材料，交联剂，光致产酸剂；
    其中，所述量子点材料包括量子点和在所述量子点表面的有机配体，所述有机配体含有：交联单元和与所述量子点配位的配位官能团；
    所述有机配体的交联单元具有下式I所示的结构：
    其中，R3为离去基团，
    所述交联剂为多羟基化合物，如下通式IV所示：
    R-(OH)m   (IV)
    其中，
    R是一m价基团，
    m为≥2的整数。
  2. 根据权利要求1所述的量子点墨水，其中，R3选自取代或未取代的C1-C6烷基、取代或未取代的C3-C6环烷基。
  3. 根据权利要求1所述的量子点墨水，其中，R3选自C1-C4烷基、苄基。
  4. 根据权利要求1-3任一项所述的量子点墨水，其中，所述有机配体具有下式II所示的结构：
    其中，
    R1和R2各自独立地选自直链、支链或环状的饱和或不饱和的烃基和杂烃基，且R1和R2中的至少一个包含一个或多个配位官能团；
    R3定义如式I。
  5. 根据权利要求1-3任一项所述的量子点墨水，其中，所述有机配体具有下式III所示的结构：
    其中，
    R1、R2和R4各自独立地选自直链、支链或环状的饱和或不饱和的烃基和杂烃基，且R1、R2和R4中的至少一个包含一个或多个配位官能团；
    R3定义如式I。
  6. 根据权利要求1所述的量子点墨水，其中，所述量子点材料中的所述量子点和所述有机配体的重量比为100：(1-30)。
  7. 根据权利要求1所述的量子点墨水，其中，R选自m价的取代或未取代的C1-C6烷基、取代或未取代的C1-C6烷氧基烷基、取代或未取代的C1-C6烷硫基烷基、取代或未取代的C3-C8环烷基、取代或未取代的C3-C8环烯基、取代或未取代的C6-C10芳基、取代或未取代的5-10元杂芳基、取代或未取代的5-10元杂环基、聚乙二醇链、聚丙二醇，
    m为2-4的整数。
  8. 根据权利要求1所述的量子点墨水，其中，所述多羟基化合物选自C2-C8二醇、C3-C8三醇、C4-C8四醇、聚乙二醇、聚丙二醇。
  9. 根据权利要求1所述的量子点墨水，其中，所述多羟基化合物选自乙二醇、丙二醇、丁二醇、戊二醇、己二醇、丙三醇、异戊四醇、季戊四醇、聚乙二醇、聚丙二醇。
  10. 根据权利要求1所述的量子点墨水，其中，所述量子点材料、所述交联剂、所述光致产酸剂的重量比为100:(1-30):(0.1-10)。
  11. 根据权利要求1所述的量子点墨水，其还包含溶剂。
  12. 根据权利要求11所述的量子点墨水，其中，所述溶剂为水。
  13. 一种量子点层图案化方法，其中，所述方法包括如下步骤：
    a.用权利要求1-12任一项所述的量子点墨水形成量子点层；
    b.在掩膜的遮挡下，将所述量子点层在紫外光照射下曝光，发生交联反应；
    c.用显影液洗脱除去未曝光区域的所述量子点，得到图案化的所述量子点层。
  14. 根据权利要求13所述的量子点层图案化方法，其中，所述显影液选自水或能与水互溶的溶剂。
  15. 根据权利要求13所述的量子点图案化方法，其中，所述显影液为水。
  16. 根据权利要求13所述的量子点图案化方法，其中，所述步骤a-c重复多次。
  17. 一种量子点层，包括多个子像素，每个子像素的材料包括量子点材料，所述量子点材料表面连接有下式V所示的交联结构：
    其中，R和m的定义与权利要求1和7-9任一项相同。
  18. 根据权利要求17所述的量子点层，其中，所述量子点材料表面连接的交联结构如式V-1所示：
  19. 一种量子点光电器件，包括权利要求17或18所述的量子点层。
  20. 一种显示装置，包括量子点发光二极管，所述量子点发光二极管包括权利要求17或18所述的量子点层。
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