WO2019119613A1 - 电致发光材料墨水及其电致发光器件 - Google Patents

电致发光材料墨水及其电致发光器件 Download PDF

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WO2019119613A1
WO2019119613A1 PCT/CN2018/074172 CN2018074172W WO2019119613A1 WO 2019119613 A1 WO2019119613 A1 WO 2019119613A1 CN 2018074172 W CN2018074172 W CN 2018074172W WO 2019119613 A1 WO2019119613 A1 WO 2019119613A1
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organic
tetrahydronaphthalene
electroluminescent
solvent
ink
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PCT/CN2018/074172
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English (en)
French (fr)
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李哲
谢相伟
宋晶尧
付东
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广东聚华印刷显示技术有限公司
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Priority to US16/768,243 priority Critical patent/US11637257B2/en
Publication of WO2019119613A1 publication Critical patent/WO2019119613A1/zh

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/56—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing sulfur
    • C09K11/562—Chalcogenides
    • C09K11/565—Chalcogenides with zinc cadmium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/02—Halogenated hydrocarbons
    • C08K5/03—Halogenated hydrocarbons aromatic, e.g. C6H5-CH2-Cl
    • 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
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • 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
    • C09D11/30—Inkjet printing inks
    • C09D11/36—Inkjet printing inks based on non-aqueous solvents
    • 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
    • C09D11/30—Inkjet printing inks
    • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
    • C09K11/881—Chalcogenides
    • C09K11/883—Chalcogenides with zinc or cadmium
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H10K71/13—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing
    • H10K71/135—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing using ink-jet printing
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H10K71/15—Deposition of organic active material using liquid deposition, e.g. spin coating characterised by the solvent used
    • 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
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
    • 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
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/10—Triplet emission
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/20—Delayed fluorescence emission
    • 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

Definitions

  • the present invention relates to the field of photovoltaic device technology, and in particular to an electroluminescent material ink and an electroluminescent device thereof.
  • Ink-jet printing technology has been widely studied and applied in optoelectronic device manufacturing in recent years, especially in flat panel display devices, such as OLED and QLED display manufacturing technologies, which are considered to solve high cost and realize large area.
  • An effective way to combine OLED-based functional materials with advanced inkjet printing equipment to create OLED or QLED displays that increase material utilization and productivity, reduce manufacturing costs, and increase productivity.
  • inkjet printing equipment requires higher inks, such as suitable boiling point, viscosity, surface tension, and uniform and stable dispersion of solutes, which poses great difficulties for ink formulation.
  • an electroluminescent material ink and an electroluminescent device thereof are provided.
  • An electroluminescent material ink comprising: a quantum dot material, an organic light emitting material, and an organic solvent, the organic solvent comprising a first solvent represented by the general formula (I):
  • R 0 is C m H 2m+1 ;
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently C n H 2n+1 ;
  • the electroluminescent material ink has suitable boiling point, viscosity, surface tension, and uniformly dispersed quantum dots and organic luminescent materials, which can better match the requirements of inkjet printing equipment and printing process conditions, and make inkjet printing film uniform.
  • the nozzle clogging is effectively prevented, and the ink solvent can be removed by vacuum evaporation or heating evaporation, etc., so that the solvent in the electroluminescent layer prepared by printing can be completely evaporated to maintain the performance of the formed luminescent layer film.
  • the alkyl-substituted tetralin has good compatibility with the quantum dot and the organic light-emitting material, and the quantum dot material and the organic light-emitting material have good solubility in the same solvent system at the same time, and the material can be prevented. Precipitation produces a precipitate that blocks the nozzle.
  • the alkyl substituent in the alkyl-substituted tetrahydronaphthalene molecule has good compatibility with quantum dot materials coated with long-chain alkanes, and the alkyl groups at positions 1, 2, 3, and 4 have Strong steric hindrance can effectively prevent the agglomeration of quantum dot materials and organic material molecules.
  • the alkyl-substituted tetrahydronaphthalene molecule also has good solubility for an organic material having a conjugated structure. Therefore, the alkyl-substituted tetralin is an ideal solvent for the light-emitting layer ink formed by blending a quantum dot material and an organic light-emitting material.
  • the main function of the quantum dot material is to emit light, so that the quantum dot material has the advantages of narrow emission spectrum and high color purity.
  • the main function of the organic luminescent material is to combine electrons and holes in whole or in part on the molecules of the organic luminescent material to generate exciton, and then transfer the exciton energy to the quantum dots.
  • quantum dot materials have a deeper highest occupied molecular orbital energy level (HOMO), and holes are injected from the hole transporting layer into the quantum dot emitting layer to have a larger barrier, while the HOMO level of the organic light emitting material is relatively Lighter, it is more advantageous for holes to be injected from the hole transport layer to the light-emitting layer. Therefore, the electroluminescent material ink can have higher luminescence performance and a longer service life, and the performance of the electroluminescent material ink is effectively ensured.
  • HOMO highest occupied molecular orbital energy level
  • the electroluminescent material ink has a viscosity of 2 cP to 15 cP and a surface tension of 25 mN/m to 40 mN/m.
  • the ink having the fluid property prevents the ink from forming an ink droplet, and directly forms a liquid column to flow out from the ink discharge port, and prevents the ink from clogging the nozzle.
  • the first solvent is selected from the group consisting of: 1-methyl-1,2,3,4-tetrahydronaphthalene, 2-methyl-1,2,3,4-tetrahydronaphthalene, 5 -Methyl-1,2,3,4-tetrahydronaphthalene, 6-methyl-1,2,3,4-tetrahydronaphthalene, 1,5-dimethyl-1,2,3,4-tetra Hydrogen naphthalene, 1,2,3,4-tetrahydro-6,7-dimethylnaphthalene, 1,2,3,4-tetrahydro-1,1-dimethylnaphthalene, 1,2,3,4 -tetrahydro-1,4-dimethylnaphthalene, 1,2,3,4-tetrahydro-1,8-dimethylnaphthalene, 1,2,3,4-tetrahydro-2,7-dimethyl Naphthyl, 5,8-dimethyl-1,2,3,4-tetrahydronaphthalene,
  • the organic solvent further includes a second solvent, and the second solvent is a halogenated aromatic hydrocarbon solvent.
  • the second solvent is mixed with the first solvent to form a mixed solvent, which can make the quantum dot material and the organic light-emitting material have better dispersing performance and better solubility in an organic solvent, and can further prevent nozzle clogging.
  • the quantum dot material comprises: a group II-IV compound semiconductor, a group III-V compound semiconductor, a group IV-VI compound semiconductor or a group I-III-VII semiconductor nanocrystal;
  • the organic luminescent material comprises: a phosphorescent material, a delayed fluorescent material, a rare earth complex material or an exciplex material.
  • the quantum dot material has an average size of 2 nm to 20 nm; the quantum dot material is a uniform hybrid type, a gradient hybrid type, a core-shell type, or a joint type.
  • the quantum dot material is encapsulated with a long chain ligand selected from the group consisting of: an organic carboxylic acid ligand, an organic thiol ligand, an organic amine ligand, and an organic (oxy)phosphine ligand.
  • a long chain ligand selected from the group consisting of: an organic carboxylic acid ligand, an organic thiol ligand, an organic amine ligand, and an organic (oxy)phosphine ligand.
  • a phospholipid a soft phospholipid, and a polyvinylpyridine.
  • the electroluminescent material ink has suitable boiling point, viscosity, surface tension, and uniformly dispersed quantum dots and organic luminescent materials, which can better match the requirements of inkjet printing equipment and printing process conditions, and make inkjet printing film uniform.
  • the nozzle clogging is effectively prevented, and the ink solvent can be removed by vacuum evaporation or heating evaporation, etc., so that the solvent in the electroluminescent layer prepared by printing can be completely evaporated to maintain the performance of the formed luminescent layer film, so the electrolysis Luminescent inks are suitable for use in display or illumination devices.
  • An electroluminescent device comprising a light-emitting layer prepared from the above-described electroluminescent material ink.
  • the electroluminescent device including the ink has More uniform luminescent properties and better service life.
  • a display or illumination device comprising the electroluminescent device described above.
  • the display or illumination device using the electroluminescent device has better display or illumination effect and has a better service life.
  • FIG. 1 is a schematic view of a spray printing apparatus according to an embodiment
  • FIG. 2 is a schematic view of an electroluminescent device according to an embodiment.
  • an electroluminescent material ink having good physical parameters, that is, to prevent the ink from forming an ink droplet, and directly forming a liquid column to flow out from the ink discharge port, and preventing the ink from clogging the nozzle. It comprises: a quantum dot material, an organic luminescent material, and an organic solvent, wherein the organic solvent comprises the first solvent represented by the general formula (I):
  • R 0 is C m H 2m+1 ;
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently C n H 2n+1 ;
  • m and n cannot be zero at the same time (ie, tetralin is not included), and the alkyl-substituted tetralin has a higher boiling point and a lower saturated vapor pressure than tetralin, and the quantum dots and organic
  • the material has better compatibility, thereby effectively preventing precipitation of the material to cause precipitation and clogging the nozzle.
  • the alkyl-substituted tetralin solvent (first solvent) has a saturated vapor pressure of less than 0.08 kPa at room temperature (25 ° C), and the alkyl-substituted tetralin solvent can be evaporated from the solvent system by vacuum drying or heat drying. Remove.
  • the first solvent comprises: 1,2,3,4-tetrahydronaphthalene, 1-methyl-1,2,3,4-tetrahydronaphthalene, 2-methyl-1,2,3 , 4-tetrahydronaphthalene, 5-methyl-1,2,3,4-tetrahydronaphthalene, 6-methyl-1,2,3,4-tetrahydronaphthalene, 1,5-dimethyl-1 , 2,3,4-tetrahydronaphthalene, 1,2,3,4-tetrahydro-6,7-dimethylnaphthalene, 1,2,3,4-tetrahydro-1,1-dimethylnaphthalene 1,2,3,4-tetrahydro-1,4-dimethylnaphthalene, 1,2,3,4-tetrahydro-1,8-dimethylnaphthalene, 1,2,3,4-tetra Hydrogen-2,7-dimethylnaphthalene, 5,8-dimethyl-1,2,3,4-tetrahydronaphthalene,
  • the organic solvent may further include a second solvent
  • the second solvent may be a halogenated aromatic hydrocarbon solvent
  • the halogenated aromatic hydrocarbon solvent may be: chlorobenzene, bromobenzene, iodobenzene. 1,2-dichlorobenzene, 1,3-trichlorobenzene, 1,2-dibromobenzene, 1,3-dibromobenzene, o-chlorotoluene, o-bromotoluene, p-bromotoluene.
  • the second solvent is chlorobenzene.
  • the electroluminescent material ink used needs to have a suitable viscosity and surface tension.
  • the ink has a viscosity of 2 cP to 15 cP and a surface tension of 25 mN/m to 40 mN/m.
  • quantum dots also known as nanocrystals
  • nanocrystals are quasi-zero-dimensional nanomaterials composed of a finite number of atoms. The three dimensions are all in the order of nanometers. They look like a tiny dot with internal electron motion in three dimensions. Both are limited, and the quantum confinement effect is particularly significant.
  • the quantum dots are combined to be excited by the excitation of the segmental wavelength or the electric field, and the quantum dots emit light with high purity of light color, high luminous efficiency, adjustable color and long service life.
  • quantum dot electroluminescence also known as "quantum dot light-emitting diode”
  • quantum dot light-emitting diode which is a quantum dot material as a light-emitting layer
  • the quantum dot material has good luminescence stability, and its essence is that the nanocrystalline semiconductor material is very stable to the energy of the (single-state) exciton. Therefore, electrons and holes are combined to form excitons on an energy illuminating material based on an organic luminescent material, and then the exciton energy of the organic energy is transferred to the quantum dots, and the quantum dots serve as energy receptors (energy). Acceptor), you can get efficient and stable QLED devices.
  • the quantum dot may be a group II-IV compound semiconductor, a group III-V compound semiconductor, a group IV-VI compound semiconductor or a group I-III-VII semiconductor nanocrystal.
  • the Group II-IV compound semiconductor may be: CdS or CdSe or CdS/ZnS or CdSe/ZnS or CdSe/CdS/ZnS.
  • the III-V or IV-VI compound semiconductor may be: GaAs or InP and PbS/ZnS or PbSe/ZnS.
  • the quantum dot material has an average size of 2-20 nm. Also, it may be a uniform mixture type, a gradient mixture type, a core-shell type, or a joint type.
  • the quantum dot material is an oil soluble quantum dot
  • the quantum dot material is selected from doped or undoped quantum dots.
  • the ligand of the quantum dot is one of an organic carboxylic acid ligand, an organic thiol ligand, an organic amine ligand, an organic phosphine ligand, an organophosphine ligand, a phospholipid, a soft phospholipid, a polyvinyl pyridine, or the like. Or a variety.
  • the organic acid ligand includes one or more of decalic acid, undecylenic acid, myristic acid, oleic acid, and stearic acid;
  • the organic thiol ligand includes one or more of octaalkyl thiol, dodecyl thiol, and octadecyl thiol;
  • the organic amine ligand includes one or more of oleylamine, octadecylamine and octaamine;
  • the organophosphine ligand includes trioctylphosphine
  • the organophosphine oxide ligand includes trioctylphosphine oxide.
  • organic materials suitable for energy donors interacting with quantum dots some basic conditions must be met: (1) the energy band gap of the organic material needs to be larger than the quantum dot, or the peak wavelength of the emission spectrum of the organic material. It is smaller than the peak wavelength of the emission spectrum of the quantum dot material; (2) The decay state of the excited state of the organic material measured under a nitrogen atmosphere at room temperature needs to be longer than the excited state decay lifetime of the quantum dot luminescent material. .
  • suitable energy donors can usually be found from the following types of organic materials: phosphorescent materials, delayed fluorescent materials, rare earth complex materials or exciplex materials.
  • the phosphorescent material comprises: a ruthenium complex, a platinum complex, a ruthenium complex or a gold complex;
  • the delayed fluorescent material comprises: a pure organic compound, copper having an electron-donating group and an electron-withdrawing group and having an excited state decay lifetime of greater than 500 nanoseconds measured in a room temperature nitrogen atmosphere in a molecular structure.
  • Complex or silver complex
  • the exciplex material is a mixture of two organic materials having an electron donating group and an electron withdrawing group, respectively.
  • suitable energy donor organic materials in the luminescent layer of the quantum dot electroluminescent device can utilize organic materials having a shallower highest occupied orbital energy level (HOMO).
  • HOMO shallower highest occupied orbital energy level
  • Both the quantum dot material and the organic material can be dissolved in an organic solvent and prepared into an electroluminescent device by solution processing.
  • Solution processing methods include spin coating, knife coating, slit coating, screen printing, letterpress or gravure printing, and inkjet printing.
  • the quantum dot material and the organic light-emitting material account for
  • the electroluminescent material ink has a weight percentage of 0.1%-20%; the organic solvent accounts for 80.0%-99.9% by weight of the electroluminescent material ink.
  • the present invention provides an apparatus for ink-jet printing the above-described electroluminescent material ink.
  • the inkjet printing apparatus 10 includes a stage 110, a hermetic container 120, a printing nozzle 130, an infusion tube 140, a print controller 200, a positive pressure generator 210, and a tube 220.
  • the ink jet printing of the ink jet printing apparatus basically operates on the principle that the ink is ejected from a minute nozzle under the control of the controller to land at a specified position on the substrate, and finally a pre-designed pattern is formed.
  • the stage 110 is used to mount the substrate 150 to be inkjet printed; the closed container 120 is used to carry the electroluminescent material ink 100; and the printing nozzle 130 is used to inkjet print the electroluminescent material ink 100 to the substrate 150.
  • the infusion tube 140 is connected to the closed container 120 and the printing nozzle 130 for conveying the electroluminescent material ink 100 from the sealed container 120 to the printing nozzle 130; the printing controller 200 is connected to the stage 110, and the printing controller 200 passes
  • the pipe 220 is in communication with the hermetic container 120 for controlling inkjet printing; the positive pressure generator 210 is in communication with the printing controller 200, and is controlled by the printing controller 200 to supply pressure to the hermetic container 120 to pass the electroluminescent material ink 100.
  • the infusion tube 140 is inkjet printed from the print nozzle 130 onto the substrate 150.
  • connection between the print controller 200 and the stage 110 may be an electrical connection or a magnetic connection.
  • the print controller 200 can control the movement of the stage 110, so that the ink can be controlled on the substrate.
  • the shape on the 150 It is also possible to control the movement of the printing nozzle 130 to control the shape of the ink on the substrate 150.
  • the printing controller 2000 can also control the pressure in the sealed container 120 by controlling the air flow of the positive pressure generator 210, thereby controlling the amount of ink ejected from the printing nozzle 130 to control the formation on the substrate 150. The thickness of the film.
  • the inkjet printing apparatus further includes a bracket 230 for securing the entire device.
  • the above electroluminescent material ink may be printed or applied to the substrate by other means, and is not limited to the above-described inkjet printing apparatus.
  • An electroluminescent device comprising a light-emitting layer prepared from the above-described electroluminescent material ink. It can be prepared by spin coating, knife coating, slit coating, screen printing, relief or gravure printing, and ink jet printing. In one embodiment, the luminescent layer is prepared using the printing inkjet apparatus shown in FIG.
  • the electroluminescent device 20 includes a substrate 200, a first electrode 210, a second electrode 220, and a functional layer 230.
  • the functional layer 230 is at the first electrode 210 and the second electrode 220.
  • the functional layer 230 includes a hole injection layer 2301, a hole transport layer 2302, a light-emitting layer 2303, and an electron transport layer 2304, wherein the light-emitting layer 2303 is Electroluminescent material inks are prepared by inkjet printing.
  • the above device structure is only an example, and other functional layers may be appropriately added or removed as needed.
  • an electron blocking layer, a hole blocking layer, a single sub-injection layer, an exciton blocking layer, or the like may be added.
  • the specific structure of the electroluminescent device does not limit the application of the luminescent layer ink of the present invention to the preparation of an electroluminescent device.
  • the invention also includes a display or illumination device comprising the electroluminescent device described above.
  • the present invention does not indicate a reagent or instrument of a specific source, and is a conventional reagent or instrument purchased from the market.
  • Example 1 - Example 5 Example 1 - Example 5, and Comparative Example 1 and Comparative Example 2 were prepared as follows.
  • the luminescent layer ink of this embodiment is composed of 6-methyltetralin, red CdSe/ZnS quantum dots (luminescence peak wavelength 625 nm), green phosphor material Ir(ppy) 3 , and 6-methyltetralin solvent 97% of the total weight of the ink, red CdSe/ZnS quantum dots accounted for 2% of the total weight of the ink, and green phosphor material Ir(ppy) 3 accounted for 1% of the total weight of the ink.
  • the luminescent layer ink of this embodiment is composed of 5-methyltetralin, red CdSe/ZnS quantum dots (luminescence peak wavelength 625 nm), green phosphorescent material Ir(ppy) 3 , and 5-methyltetralin solvent 97% of the total weight of the ink, red CdSe/ZnS quantum dots accounted for 2% of the total weight of the ink, and green phosphor material Ir(ppy) 3 accounted for 1% of the total weight of the ink.
  • Example 2 The following components were separately added to an approximately 500 mL single-necked flask in the order of: 2 wt% red CdSe/ZnS quantum dots, 1 wt% green phosphorescent material Ir(ppy) 3 , 97 wt% of 5-methyltetralin, The mixture was stirred for 60 minutes and filtered to obtain Ink Composition 2 (Example 2).
  • the luminescent layer ink of this embodiment is composed of 1,1,4,4-tetramethyl-1,2,3,4-tetrahydronaphthalene, red CdSe/ZnS quantum dots (luminescence peak wavelength 625 nm), blue retardation fluorescent material.
  • CZ-PS composition, 1,1,4,4-tetramethyl-1,2,3,4-tetrahydronaphthalene solvent accounts for 97% of the total weight of the ink
  • the red CdSe/ZnS quantum dots account for the total weight of the ink.
  • the 2% blue light retardation fluorescent material CZ-PS accounts for 1% of the total weight of the ink.
  • the luminescent layer ink of this embodiment is composed of 1,1,4,4,6-pentamethyl-1,2,3,4-tetrahydronaphthalene, red CdSe/ZnS quantum dots (luminescence peak wavelength 625 nm), blue light retardation Fluorescent material CZ-PS composition, 1,1,4,4,6-pentamethyl-1,2,3,4-tetrahydronaphthalene solvent accounted for 97% of the total weight of the ink, red CdSe / ZnS quantum dots accounted for 2% of the total weight of the ink, the blue retardation fluorescent material CZ-PS accounts for 1% of the total weight of the ink.
  • the luminescent layer ink of this embodiment comprises two solvents, namely chlorobenzene, 1,1,4,4,6-pentamethyl-1,2,3,4-tetrahydronaphthalene, red CdSe/ZnS quantum dots ( The luminescence peak wavelength is 625 nm), the blue retardation fluorescent material CZ-PS is composed, and the chlorobenzene solvent accounts for 20% of the total weight of the ink, 1,1,4,4,6-pentamethyl-1,2,3,4-tetra
  • the hydrogenated naphthalene solvent accounts for 77% of the total weight of the ink
  • the red CdSe/ZnS quantum dots account for 2% of the total weight of the ink
  • the blue retardation fluorescent material CZ-PS accounts for 1% of the total weight of the ink.
  • the luminescent layer ink of this embodiment is composed of tetralin, red CdSe/ZnS quantum dots (luminescence peak wavelength 625 nm), and green phosphorescent material Ir(ppy) 3 , and the tetralin solvent accounts for 97% of the total weight of the ink.
  • the red light CdSe/ZnS quantum dots account for 2% of the total weight of the ink, and the green phosphor material Ir(ppy) 3 accounts for 1% of the total weight of the ink.
  • the luminescent layer ink of this embodiment is composed of tetralin, chlorobenzene, red CdSe/ZnS quantum dots (luminescence peak wavelength 625 nm), and green phosphorescent material Ir(ppy) 3 , and the tetralin solvent accounts for the total weight of the ink. 97%, the red light CdSe/ZnS quantum dots accounted for 2% of the total weight of the ink, and the green phosphor material Ir(ppy) 3 accounted for 1% of the total weight of the ink.
  • Embodiment 2 Performance test
  • Example 1 - Example 5 and Comparative Example 1 and Comparative Example 2 were printed by means of spray printing to determine the number of clogging of the nozzles.
  • the total number of nozzles on the nozzle is 128, and the experimental results are shown in Table 1 below.

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Abstract

本发明涉及一种电致发光材料墨水，包括：量子点材料、有机发光材料以及有机溶剂，该有机溶剂包括通式(I)所示的第一溶剂： R 0为C mH 2m+1；R 1、R 2、R 3、R 4各自独立地为C nH 2n+1；其中，0≤m≤8且0＜n≤8，或者0＜m≤8且0≤n≤8；该电致发光材料墨水具有较好的物理参数，可以有效地防止喷嘴堵塞。

Description

电致发光材料墨水及其电致发光器件 技术领域
本发明涉及光电器件技术领域，特别涉及电致发光材料墨水及其电致发光器件。
背景技术
喷墨打印(Ink-jet printing)技术近年来在光电子器件制造得到广泛的研究和应用，特别是用作平板显示器件、例如OLED和QLED显示制造技术中被认为是解决高成本和实现大面积的有效途径，这种技术可结合基于溶液的功能性材料和先进的喷墨打印设备来制作OLED或QLED显示屏，可提高材料的利用率和生产效率，降低制造成本，提高产能。但喷墨打印设备对墨水要求较高，例如合适的沸点、粘度、表面张力、以及分散均匀稳定的溶质，给墨水配制带来较大的困难。
传统地，为了调控墨水的物理参数，防止墨水堵塞打印设备的喷嘴，向墨水中加入一些诸如醇类聚合物的添加剂，但该具有绝缘性质的聚合物添加剂不易除去，且引入这类聚合物往往会降低薄膜的电荷传输能力，对器件的光电性能具有负面影响，限制了其光电器件的应用。因此，需要对墨水进行改进，在不添加添加剂的情况下，使该墨水具有良好的物理参数，从而即可以防止该墨水不能形成墨滴，而直接形成液柱从喷墨口流出，又可以防止墨水堵塞喷嘴。
发明内容
基于此，为了解决喷嘴堵塞的问题，提供一种电致发光材料墨水及其电致发光器件。
一种电致发光材料墨水，包括：量子点材料、有机发光材料以及有机溶剂，所述有机溶剂包括通式(I)所示的第一溶剂：
Figure PCTCN2018074172-appb-000001
R 0为C mH 2m+1；
R 1、R 2、R 3、R 4、R 5、R 6各自独立地为C nH 2n+1；
其中，0≤m≤8且0＜n≤8，或者0＜m≤8且0≤n≤8。
该电致发光材料墨水具有合适的沸点、粘度、表面张力、以及分散均匀稳定的量子点和有机发光材料，可以较好匹配喷墨打印设备和打印工艺条件要求，使喷墨打印成膜均匀的同时，有效地防止喷嘴堵塞，且墨水溶剂可以通过真空蒸发或加热蒸发等方法去除，可以使得打印制备的电致发光层中溶剂挥发完全，以维持形成的发光层薄膜的性能。
具体地，该烷基取代四氢化萘对于量子点与有机发光材料都具有良好的相容性，可以使量子点材料与有机发光材料同时在相同的溶剂体系中具有良好的溶解性，能够防止材料析出产生沉淀而堵塞喷头。一方面，该烷基取代四氢化萘分子中的烷基取代基对于外部包裹长链烷烃的量子点材料具有很好的相容性，且1、2、3、4号位置的烷基具有较强的空间位阻，能有效防止量子点材料和有机材料分子的团聚。另一方面，烷基取代四氢化萘分子中的苯环结构单元对于具有共轭结构的有机材料也具有良好的溶解性。因此，对于量子点材料与有机发光材料共混形成的发光层墨水，该烷基取代四氢化萘是一种理想的溶剂。
另外，在量子点与有机材料的混合墨水中，量子点材料的主要作用是发光，这样可以充分发挥量子点材料发射光谱窄、色纯度高的优势。
有机发光材料的主要作用是让电子与空穴全部或部分地在有机发光材料分子上复合产生激子(exciton)，然后再将激子能量转移给量子点。一般来说，量子点材料具有较深的最高占有分子轨道能级(HOMO)，空穴从空穴传输层注入到量子点发光层具有较大的势垒，而有机发光材料的HOMO能级相对较浅，更加有利于空穴从空穴传输层注入到发光层。因此可以使该电致发光材料墨水具有较高的发光性能和较长的使用寿命，有效地保证了该电致发光材料墨水的性能。
在其中一实施例中，通式(I)中0≤m≤4且0＜n≤4，或者0＜m≤4且0≤n≤4。
在其中一实施例中，所述电致发光材料墨水的粘度为2cP-15cP，表面张力为25mN/m-40mN/m。
具有该流体特性的墨水，即可以防止该墨水不能形成墨滴，而直接形成液柱从喷墨口流出，又可以防止墨水堵塞喷嘴。
在其中一实施例中，所述第一溶剂选自：1-甲基-1，2，3，4-四氢化萘、2-甲基-1，2，3，4-四氢化萘、5-甲基-1，2，3，4-四氢化萘、6-甲基-1，2，3，4-四氢化萘、1，5-二甲基-1，2，3，4-四氢萘、1，2，3，4-四氢-6，7-二甲基萘、1，2，3，4-四氢-1，1-二甲基萘、1，2，3，4-四氢-1，4-二甲基萘、1，2，3，4-四氢-1，8-二甲基萘、1，2，3，4-四氢-2，7-二甲基萘、5，8-二甲基-1，2，3，4-四氢萘、1，1，4，4-四甲基-1，2，3，4-四氢萘、6-乙基-1，2，3，4-四氢-1，1，4，4-四甲基萘、1，2，3，4-四氢-1-丙基萘、5-乙基-1，2，3，4-四氢萘、1，1，4，4，6-五甲基-1，2，3，4-四氢化萘中的一种或多种。
在其中一实施例中，所述有机溶剂还包括第二溶剂，所述第二溶剂为卤代芳烃溶剂。
第二溶剂与第一溶剂混合形成混合溶剂，可以使量子点材料和有机发光材料在有机溶剂中具有更好的分散性能、更好溶解性，可以进一步防止喷嘴堵塞。
在其中一实施例中，所述量子点材料包括：II-IV族化合物半导体、III-V族化合物半导体、IV-VI族化合物半导体或I-III-VII族半导体纳米晶；
所述的有机发光材料包括：磷光材料、延迟荧光材料、稀土配合物材料或激基复合物材料。
在其中一实施例中，所述量子点材料的平均尺寸为2nm-20nm；所述量子点材料为均一混合类型、梯度混合类型、核-壳类型或联合类型。
在其中一实施例中，所述量子点材料包裹有长链配体，所述配体选自：有机羧酸配体、有机硫醇配体、有机胺配体、有机(氧)膦配体、磷脂、软磷脂、聚乙烯基吡啶中的一种或多种。上述的电致发光材料墨水在显示或照明装置中的应用。
该电致发光材料墨水具有合适的沸点、粘度、表面张力、以及分散均匀稳定 的量子点和有机发光材料，可以较好匹配喷墨打印设备和打印工艺条件要求，使喷墨打印成膜均匀的同时，有效地防止喷嘴堵塞，且墨水溶剂可以通过真空蒸发或加热蒸发等方法去除，可以使得打印制备的电致发光层中溶剂挥发完全，以维持形成的发光层薄膜的性能，因此该电致发光材料墨水适宜用于显示或照明装置中。
一种电致发光器件，其特征在于，包括由上述的电致发光材料墨水制备而成发光层。
由于上述电致发光材料墨水具有较好的分散性，且该墨水中的溶剂在电致发光层的制备中可以挥发完全，具有形成发光层薄膜的性能，因此包含该墨水的电致发光器具有更均匀的发光特性、以及较好的使用寿命。
一种显示或照明装置，包括上述的电致发光器件。
由于上述电致发光器具有更均匀的发光特性、以及较好的使用寿命，故使用该电致发光器件的显示或照明装置具有更好的显示或照明效果，以及具有较好的使用寿命。
附图说明
图1为一实施例涉及的喷涂打印设备的示意图；
图2为一实施例涉及的电致发光器件的示意图。
具体实施方式
为了获得具有良好物理参数的电致发光材料墨水，即防止该墨水不能形成墨滴，而直接形成液柱从喷墨口流出，又可以防止墨水堵塞喷嘴，提供了一种电致发光材料墨水，其包括：量子点材料、有机发光材料以及有机溶剂，其中，该有机溶剂包括通式(I)所示的第一溶剂：
Figure PCTCN2018074172-appb-000002
R 0为C mH 2m+1；
R 1、R 2、R 3、R 4、R 5以及R 6各自独立地为C nH 2n+1；
其中，0≤m≤8且0＜n≤8，或者0＜m≤8且0≤n≤8；
即，m、n不能同时为零(即不包括四氢化萘)，相比于四氢化萘，烷基取代四氢化萘具有更高的沸点和较低的饱和蒸气压，且对量子点与有机材料具有更好的相容性，从而有效地防止材料析出产生沉淀而堵塞喷嘴。
该烷基取代四氢化萘溶剂(第一溶剂)室温条件下(25℃)的饱和蒸汽压低于0.08kPa，该烷基取代四氢化萘溶剂可以用真空干燥或加热干燥等方法从溶剂体系中蒸发去除。
在一实施例中，第一溶剂包括：1，2，3，4-四氢化萘、1-甲基-1，2，3，4-四氢化萘、2-甲基-1，2，3，4-四氢化萘、5-甲基-1，2，3，4-四氢化萘、6-甲基-1，2，3，4-四氢化萘、1，5-二甲基-1，2，3，4-四氢萘、1，2，3，4-四氢-6，7-二甲基萘、1，2，3，4-四氢-1，1-二甲基萘、1，2，3，4-四氢-1，4-二甲基萘、1，2，3，4-四氢-1，8-二甲基萘、1，2，3，4-四氢-2，7-二甲基萘、5，8-二甲基-1，2，3，4-四氢萘、1，1，4，4-四甲基-1，2，3，4-四氢萘、6-乙基-1，2，3，4-四氢-1，1，4，4-四甲基萘、1，2，3，4-四氢-1-丙基萘、5-乙基-1，2，3，4-四氢萘、1，1，4，4，6-五甲基-1，2，3，4-四氢化萘中的一种或多种。
另外，为了更进一步提高该墨水的物理性能参数，上述有机溶剂还可以包括第二溶剂，该第二溶剂可以为卤代芳烃溶剂，该卤代芳烃溶剂可以为：氯苯、溴苯、碘苯、1，2-二氯苯、1，3-三氯苯、1，2-二溴苯、1，3-二溴苯、邻氯甲苯、邻溴甲苯、对溴甲苯。在一实施例中，第二溶剂为氯苯。
为了防止堵塞喷涂，所使用的电致发光材料墨水需要具有合适的粘度和表面张力。在一实施例中，该墨水的粘度为2cP-15cP，表面张力为25mN/m-40mN/m。
另外，量子点又称纳米晶，是准零维的纳米材料，由有限数目的原子组成，三个维度尺寸均在纳米数量级，外观似一极小的点状物，其内部电子运动在三维空间都受到了限制，量子限域效应特别显著。量子点受到段波长光激发或电场激发会复合发光，量子点发光具有光色纯度高、发光量子效率高、发光颜色可调、使用寿命长等优良特性。这些特点使得以量子点材料可作为发光层的量 子点电致发光(也称作“量子点发光二极管”，QLED)在固态照明、平板显示等领域具有广泛的应用前景，受到了学术界以及产业界的广泛关注。量子点材料发光稳定性很好，其本质是纳米晶体半导体材料对于(单线态)激子的能量十分稳定。因此，电子与空穴在基于有机发光材料能量给体(energy donnor)材料上复合形成激子，再将有机能量给体材料上的激子能量传递给量子点，量子点作为能量受体(energy acceptor)，可以获得高效稳定的QLED器件。
另外，该量子点可以是II-IV族化合物半导体、III-V族化合物半导体、IV-VI族化合物半导体或I-III-VII族半导体纳米晶。
其中，II-IV族化合物半导体可以为：CdS或CdSe或CdS/ZnS或CdSe/ZnS或CdSe/CdS/ZnS。III-V或IV-VI族化合物半导体可以为：GaAs或InP和PbS/ZnS或PbSe/ZnS。
在一实施例中，该量子点材料的平均尺寸为2-20nm。并且，其可以是均一混合类型、梯度混合类型、核-壳类型或联合类型。
在一实施例中，该量子点材料为油溶性量子点；
在一实施例中，该量子点材料选自掺杂或非掺杂的量子点。
其中，量子点的配体为有机羧酸配体、有机硫醇配体、有机胺配体、有机膦配体、有机氧膦配体、磷脂、软磷脂、聚乙烯基吡啶等中的一种或多种。
有机酸配体包括：十酸、十一烯酸、十四酸、油酸和硬脂酸中的一种或多种；
有机硫醇配体包括：八烷基硫醇、十二烷基硫醇和十八烷基硫醇中的一种或多种；
有机胺配体包括：油胺、十八胺和八胺中的一种或多种；
有机膦配体包括三辛基膦；
有机氧膦配体包括三辛基氧膦。
另外，对于适合与量子点共同作用的能量给体的有机材料，需要满足一些基本条件：(1)有机材料的能量带隙(band gap)需要大于量子点，或者有机材料的发射谱的峰值波长要小于量子点材料的发射谱的峰值波长；(2)在室温氮 气环境下所测量出的有机材料的激发态(excited state)衰减寿命(decay lifetime)须要长于量子点发光材料的激发态衰减寿命。能够满足以上条件的有机材料，通常可以从以下类型的有机材料中找到合适的能量给体：磷光材料、延迟荧光材料、稀土配合物材料或激基复合物材料等。
在一实施例中，磷光材料包括：铱配合物、铂配合物、钌配合物或金配合物；
在一实施例中，延迟荧光材料包括：在一种分子结构中同时含有供电子基团与吸电子基团且室温氮气环境下所测量的激发态衰减寿命大于500纳秒的纯有机化合物、铜配合物或银配合物；
在一实施例中，激基复合物材料为分别具有供电子基团和吸电子基团的两种有机材料的混合物。
在量子点电致发光器件的发光层中引入合适的能量给体有机材料，例如将量子点与能量给体有机材料共混，可以利用有机材料具有较浅的最高占有轨道能级(HOMO)而缩小空穴从空穴传输材料注入量子点发光层的势垒，以有效降低器件的驱动电压和提高器件的工作稳定性。
量子点材料和有机材料均可以溶于有机溶剂中，使用溶液加工法制备成电致发光器件。溶液加工法包括：旋涂、刮涂、狭缝涂布、丝网印刷、凸版或凹版印刷，以及喷墨打印等方法。
为了保证量子点材料和有机发光材料在有机溶剂中具有较好的溶解度，又需要防止其析出而产生沉淀堵塞喷嘴，需要选择合适的浓度，在本实施例中，量子点材料和有机发光材料占电致发光材料墨水的重量百分含量为0.1％-20％；有机溶剂占电致发光材料墨水的重量百分含量为80.0％-99.9％。
另外，本发明还提供了一种喷墨打印上述的电致发光材料墨水的设备。如图1所示，该喷墨打印设备10包括：载物台110、密闭容器120、打印喷嘴130、输液管140、打印控制器200、正压发生器210以及管道220。该喷墨打印设备的喷墨打印基本工作原理是：在控制器的控制下将墨水从微小的喷嘴喷射出而在承印物上的指定位置着落，最后形成预先设计好的图案。
具体地，载物台110用于载置待喷墨打印的基板150；密闭容器120用于承载电致发光材料墨水100；打印喷嘴130用于将电致发光材料墨水100喷墨打印至基板150上；输液管140连通密闭容器120和打印喷嘴130，用于将电致发光材料墨水100从密闭容器120输送至打印喷嘴130；打印控制器200与载物台110相连，且打印控制器200通过管道220与密闭容器120连通，用于控制喷墨打印；正压发生器210与打印控制器200连通，通过打印控制器200的控制，向密闭容器120提供压力，使电致发光材料墨水100通过输液管140，从打印喷嘴130喷墨打印到基板150上。
需要说明的是，上述打印控制器200与载物台110连接可以是电连接也可以是磁连接等连接方式，该打印控制器200可以控制该载物台110的运动，从而可以控制墨水在基板150上的形状。也可以是控制打印喷嘴130的运动，从而控制墨水在基板150上的形状。另外，该打印控制器2000还可以通过控制正压发生器210的气流，从而控制密闭容器120内的压力，进而控制从打印喷嘴130喷出的墨水的量的多少，以控制基板150上所形成的薄膜的厚度。
在一实施例中，喷墨打印设备还包括支架230，用于固定整个装置。
另外，上述电致发光材料墨水还可以通过其他设备打印或涂布到基板上，不限于上述喷墨打印设备。
一种电致发光器件，包括由上述的电致发光材料墨水制备而成发光层。其可以通过旋涂、刮涂、狭缝涂布、丝网印刷、凸版或凹版印刷，以及喷墨打印等方法制备。在一实施例中，其发光层采用图1所示的打印喷墨设备制备而成。
在一实施例中，如图2所示，电致发光器件20包括：衬底200、第一电极210、第二电极220以及功能层230，功能层230在第一电极210和第二电极220之间，与第一电极210和第二电极220接触，该功能层230依次包括空穴注入层2301、空穴传输层2302、发光层2303以及电子传输层2304，其中，发光层2303由上述的电致发光材料墨水通过喷墨打印制备而成。
需要说明的是，上述器件结构只是示例，根据需要还可以适当增减其他功能层，例如可以增加电子阻挡层、空穴阻挡层、单子注入层、激子阻挡层等。 电致发光器件的具体结构并不限制本发明的发光层墨水应用于电致发光器件的制备。
本发明还包括一种显示或照明装置，该装置包括由上述电致发光器件。
下面结合具体实施例对本发明进行说明。
需要说明的是，本发明未注明具体来源的试剂或仪器，为市场购买的常规试剂或仪器。
实施例一：样本制备
按下述方法制备实施例1-实施例5，以及对比例1和对比例2。
实施例1：
Figure PCTCN2018074172-appb-000003
该实施例的发光层墨水由6-甲基四氢化萘、红光CdSe/ZnS量子点(发光峰值波长625nm)、绿光磷光材料Ir(ppy) 3组成，6-甲基四氢化萘溶剂占墨水的总重量的97％，红光CdSe/ZnS量子点占墨水的总重量的2％，绿光磷光材料Ir(ppy) 3占墨水的总重量的1％。
将以下组分分别添加到大约500mL单口烧瓶中，添加顺序为：2wt％红光CdSe/ZnS量子点，1wt％绿光磷光材料Ir(ppy) 3，97wt％的6-甲基四氢化萘，搅拌混合物60分钟，经过过滤后得到墨水组合物1(实施例1)。
实施例2：
Figure PCTCN2018074172-appb-000004
Figure PCTCN2018074172-appb-000005
该实施例的发光层墨水由5-甲基四氢化萘、红光CdSe/ZnS量子点(发光峰值波长625nm)、绿光磷光材料Ir(ppy) 3组成，5-甲基四氢化萘溶剂占墨水的总重量的97％，红光CdSe/ZnS量子点占墨水的总重量的2％，绿光磷光材料Ir(ppy) 3占墨水的总重量的1％。
将以下组分分别添加到大约500mL单口烧瓶中，添加顺序为：2wt％红光CdSe/ZnS量子点，1wt％绿光磷光材料Ir(ppy) 3，97wt％的5-甲基四氢化萘，搅拌混合物60分钟，经过过滤后得到墨水组合物2(实施例2)。
实施例3：
Figure PCTCN2018074172-appb-000006
该实施例的发光层墨水由1，1，4，4-四甲基-1，2，3，4-四氢萘、红光CdSe/ZnS量子点(发光峰值波长625nm)、蓝光延迟荧光材料CZ-PS组成，1，1，4，4-四甲基-1，2，3，4-四氢萘溶剂占墨水的总重量的97％，红光CdSe/ZnS量子点占墨水的总重量的2％，蓝光延迟荧光材料CZ-PS占墨水的总重量的1％。
将以下组分分别添加到大约500mL单口烧瓶中，添加顺序为：2wt％红光CdSe/ZnS量子点，1wt％蓝光延迟荧光材料CZ-PS，97wt％的1，1，4，4-四甲基-1，2，3，4-四氢萘，搅拌混合物60分钟，经过过滤后得到墨水组合物3(实施例3)。
实施例4：
Figure PCTCN2018074172-appb-000007
该实施例的发光层墨水由1，1，4，4，6-五甲基-1，2，3，4-四氢化萘、红光CdSe/ZnS量子点(发光峰值波长625nm)、蓝光延迟荧光材料CZ-PS组成，1，1，4，4，6-五甲基-1，2，3，4-四氢化萘溶剂占墨水的总重量的97％，红光CdSe/ZnS量子点占墨水的总重量的2％，蓝光延迟荧光材料CZ-PS占墨水的总重量的1％。
将以下组分分别添加到大约500mL单口烧瓶中，添加顺序为：2wt％红光CdSe/ZnS量子点，1wt％蓝光延迟荧光材料CZ-PS，97wt％的1，1，4，4，6-五甲基-1，2，3，4-四氢化萘，搅拌混合物60分钟，经过过滤后得到墨水组合物4(实施例4)。
实施例5：
Figure PCTCN2018074172-appb-000008
Figure PCTCN2018074172-appb-000009
该实施例的发光层墨水包括两种溶剂，由氯苯、1，1，4，4，6-五甲基-1，2，3，4-四氢化萘、红光CdSe/ZnS量子点(发光峰值波长625nm)、蓝光延迟荧光材料CZ-PS组成，氯苯溶剂占墨水的总重量的20％，1，1，4，4，6-五甲基-1，2，3，4-四氢化萘溶剂占墨水的总重量的77％，红光CdSe/ZnS量子点占墨水的总重量的2％，蓝光延迟荧光材料CZ-PS占墨水的总重量的1％。
将以下组分分别添加到大约500mL单口烧瓶中，添加顺序为：2wt％红光CdSe/ZnS量子点，1wt％蓝光延迟荧光材料CZ-PS，20wt％的氯苯，77wt％的1，1，4，4，6-五甲基-1，2，3，4-四氢化萘，搅拌混合物60分钟，经过过滤后得到墨水组合物5(实施例5)。
对比例1：
Figure PCTCN2018074172-appb-000010
该实施例的发光层墨水由四氢化萘、红光CdSe/ZnS量子点(发光峰值波长625nm)、绿光磷光材料Ir(ppy) 3组成，四氢化萘溶剂占墨水的总重量的97％，红光CdSe/ZnS量子点占墨水的总重量的2％，绿光磷光材料Ir(ppy) 3占墨水的总重量的1％。
将以下组分分别添加到大约500mL单口烧瓶中，添加顺序为：2wt％红光CdSe/ZnS量子点，1wt％绿光磷光材料Ir(ppy) 3，97wt％的四氢化萘，搅拌混合 物60分钟，经过过滤后得到墨水组合物6(对比例1)。
对比例2
Figure PCTCN2018074172-appb-000011
该实施例的发光层墨水由四氢化萘、氯苯、红光CdSe/ZnS量子点(发光峰值波长625nm)、绿光磷光材料Ir(ppy) 3组成，四氢化萘溶剂占墨水的总重量的97％，红光CdSe/ZnS量子点占墨水的总重量的2％，绿光磷光材料Ir(ppy) 3占墨水的总重量的1％。
将以下组分分别添加到大约500mL单口烧瓶中，添加顺序为：2wt％红光CdSe/ZnS量子点，1wt％绿光磷光材料Ir(ppy) 3，20wt％的氯苯，77wt％的四氢化萘，搅拌混合物60分钟，经过过滤后得到墨水组合物7(对比例2)。
实施例二：性能测试
将实施例1-实施例5以及对比例1和对比例2的墨水利用喷涂打印的方式进行打印，判断喷嘴的堵塞数目。本实施例中喷头上的喷嘴总数为128个，实验结果如下表1。
表1：
Figure PCTCN2018074172-appb-000012
从表1中可以看出，以烷基四氢化萘作为主要溶剂时，喷嘴堵塞数目少于以四氢化萘作为主要溶剂。
另外，对比实施例3和实施例4可以看出，在烷基四氢化萘中加入氯苯，可以降低喷嘴堵塞的概率。此外，对比实施例1-实施例4和对比例2可以看出，四氢化萘中加入氯苯组成混合溶液后的喷嘴堵塞数目仍多于实施例1-实施例4，即烷基取代四氢化萘的防止喷嘴堵塞的效果优于四氢化萘和氯苯的混合液。
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。

Claims (15)

  1. 一种电致发光材料墨水，其特征在于，包括：量子点材料、有机发光材料以及有机溶剂，所述有机溶剂包括通式(I)所示的第一溶剂：
    Figure PCTCN2018074172-appb-100001
    R 0为C mH 2m+1；
    R 1、R 2、R 3、R 4、R 5以及R 6各自独立地为C nH 2n+1；
    其中，0≤m≤8且0＜n≤8，或者0＜m≤8且0≤n≤8。
  2. 根据权利要求1所述的电致发光材料墨水，其特征在于，0≤m≤4且0＜n≤4，或者0＜m≤4且0≤n≤4。
  3. 根据权利要求1所述的电致发光材料墨水，其特征在于，所述有机溶剂占所述电致发光材料墨水的重量百分含量为80.0％-99.9％。
  4. 根据权利要求1所述的电致发光材料墨水，其特征在于，所述电致发光材料墨水的粘度为2cP-15cP，表面张力为25mN/m-40mN/m。
  5. 根据权利要求1所述的电致发光材料墨水，其特征在于，所述第一溶剂选自：1-甲基-1，2，3，4-四氢化萘、2-甲基-1，2，3，4-四氢化萘、5-甲基-1，2，3，4-四氢化萘、6-甲基-1，2，3，4-四氢化萘、1，5-二甲基-1，2，3，4-四氢萘、1，2，3，4-四氢-6，7-二甲基萘、1，2，3，4-四氢-1，1-二甲基萘、1，2，3，4-四氢-1，4-二甲基萘、1，2，3，4-四氢-1，8-二甲基萘、1，2，3，4-四氢-2，7-二甲基萘、5，8-二甲基-1，2，3，4-四氢萘、1，1，4，4-四甲基-1，2，3，4-四氢萘、6-乙基-1，2，3，4-四氢-1，1，4，4-四甲基萘、1，2，3，4-四氢-1-丙基萘、5-乙基-1，2，3，4-四氢萘、1，1，4，4，6-五甲基-1，2，3，4-四氢化萘中的一种或多种。
  6. 根据权利要求1所述的电致发光材料墨水，其特征在于，所述第一溶剂为6-甲基四氢化萘、5-甲基四氢化萘、1，1，4，4-四甲基-1，2，3，4-四氢萘或1，1，4，4，6-五甲基-1，2，3，4-四氢化萘。
  7. 根据权利要求1-6任一项所述的电致发光材料墨水，其特征在于，所述有机溶剂还包括第二溶剂，所述第二溶剂为卤代芳烃溶剂。
  8. 根据权利要求7所述的电致发光材料墨水，其特征在于，所述第二溶剂 为氯苯。
  9. 根据权利要求1所述的电致发光材料墨水，其特征在于，所述量子点材料包括：II-IV族化合物半导体、III-V族化合物半导体、IV-VI族化合物半导体或I-III-VII族半导体纳米晶；
    所述的有机发光材料包括：磷光材料、延迟荧光材料、稀土配合物材料或激基复合物材料。
  10. 根据权利要求9所述的电致发光材料墨水，其特征在于，所述量子点材料的平均尺寸为2nm-20nm；所述量子点材料为均一混合类型、梯度混合类型、核-壳类型或联合类型。
  11. 根据权利要求9所述的电致发光材料墨水，其特征在于，所述量子点材料为油溶性量子点材料。
  12. 根据权利要求9所述的电致发光材料墨水，其特征在于，所述量子点材料的配体为有机羧酸配体、有机硫醇配体、有机胺配体、有机膦配体、有机氧膦配体、磷脂、软磷脂及聚乙烯基吡啶中的一种或多种。
  13. 根据权利要求12所述的电致发光材料墨水，其特征在于，
    所述有机羧酸为十酸、十一烯酸、十四酸、油酸和硬脂酸中的一种或多种；
    所述有机硫醇配体为八烷基硫醇、十二烷基硫醇和十八烷基硫醇中的一种或多种；
    所述有机胺配体为油胺、十八胺和八胺中的一种或多种；
    所述有机膦配体为三辛基膦；
    所述有机氧膦配体为三辛基氧膦。
  14. 一种电致发光器件，其特征在于，包括由权利要求1-13任一项所述的电致发光材料墨水制备而成发光层。
  15. 一种显示或照明装置，其特征在于，包括权利要求14所述的电致发光器件。
PCT/CN2018/074172 2017-12-18 2018-01-25 电致发光材料墨水及其电致发光器件 WO2019119613A1 (zh)

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