WO2017012275A1 - 量子点墨水 - Google Patents

量子点墨水 Download PDF

Info

Publication number
WO2017012275A1
WO2017012275A1 PCT/CN2015/099337 CN2015099337W WO2017012275A1 WO 2017012275 A1 WO2017012275 A1 WO 2017012275A1 CN 2015099337 W CN2015099337 W CN 2015099337W WO 2017012275 A1 WO2017012275 A1 WO 2017012275A1
Authority
WO
WIPO (PCT)
Prior art keywords
quantum dot
dot ink
layer
surface tension
transport material
Prior art date
Application number
PCT/CN2015/099337
Other languages
English (en)
French (fr)
Inventor
何晓龙
姚琪
刘圣烈
舒适
曹占锋
徐威
Original Assignee
京东方科技集团股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 京东方科技集团股份有限公司 filed Critical 京东方科技集团股份有限公司
Priority to US15/118,234 priority Critical patent/US10311994B2/en
Publication of WO2017012275A1 publication Critical patent/WO2017012275A1/zh

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • 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
    • C09D11/322—Pigment 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
    • C09D11/30—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
    • 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
    • C09D11/52—Electrically conductive 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
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/70—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing phosphorus
    • 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
    • C09K11/74—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing arsenic, antimony or bismuth
    • C09K11/7492—Arsenides; Nitrides; Phosphides
    • 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
    • C09K11/87—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing platina group metals
    • C09K11/873—Chalcogenides
    • C09K11/876—Chalcogenides with zinc or cadmium
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/88—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
    • 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
    • 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
    • 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
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
    • 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
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
    • 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
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
    • 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
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/656—Aromatic compounds comprising a hetero atom comprising two or more different heteroatoms per ring
    • 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
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • 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
    • 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]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers
    • 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]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting 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
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/656—Aromatic compounds comprising a hetero atom comprising two or more different heteroatoms per ring
    • H10K85/6565—Oxadiazole compounds

Definitions

  • Embodiments of the invention relate to quantum dot inks.
  • Quantum Dots Light Emitting Diode Displays are a new type of display technology developed on the basis of organic light-emitting displays. Different from other types of organic light-emitting diodes, the electroluminescent structure is a quantum dot layer, and the principle is that electrons are injected into the quantum dot layer through the electron transport layer, and holes are injected into the quantum dot layer through the hole transport layer, and The holes composite in the quantum dots. Compared with organic light-emitting diode display devices, QLED has the advantages of narrow emission peak, high color saturation and wide color gamut.
  • Quantum dot inks are usually obtained by dispersing quantum dot materials in an organic solvent. Since the quantum dot materials themselves are nanoparticles, it is difficult to obtain high-viscosity quantum dot inks, which causes printing difficulties.
  • Embodiments of the present invention provide a quantum dot ink comprising a non-polar organic solvent, a surface tension modifier, and a hydrophobic quantum dot material, the quantum dot ink further comprising a carrier transport material, the hydrophobic quantum The point material can be phase separated from the carrier transport material.
  • the quantum dot ink has a viscosity of 10-12 cP and a surface tension of 32-42 dynes/cm.
  • the surface tension modifier is a hydrophobic, polar organic having a molecular weight of less than 500.
  • the carrier transport material is an electron transport material or a hole transport material having a molecular weight of less than 500.
  • the non-polar organic solvent is liquid at 25 ° C and often The boiling point is less than 200 ° C.
  • the mass percentage of each component of the quantum dot ink is: 5% to 15% of the carrier transport material, 1% to 5% of the surface tension modifier, and 2% of the hydrophobic quantum dot material. -20%, non-polar organic solvent 60%-92%.
  • the hydrophobic quantum dot material is selected from one or more of the following quantum dot materials: CdS, CdSe, CdTe, ZnO, ZnS, ZnSe, ZnTe, GaAs, GaP, GaSb , HgS, HgSe, HgTe, InAs, InP, InSb, AlAs, AlP, CuInS, CuInSe, AlSb.
  • the carrier transport material is an electron transport material selected from the group consisting of: oxadiazole, thiadiazole, s-triazole, naphthalene, benzoquinone, carbazole, the above Derivatives of substances and combinations thereof.
  • the carrier transport material is a hole transport material selected from the group consisting of: CBP (4,4'-N, N'-dicarbazole-biphenyl) , a-NPD (N'-diphenyl-N,N'-bis(1-naphthyl)-1,1'-biphenyl-4,4"-diamine), TCCA (4,4', 4"-tris(N-oxazolyl)-triphenylamine), DNTPD(N,N'-bis(4-(N,N'-diphenyl-amino)phenyl)-N,N'-diphenyl Aniline) and combinations thereof.
  • CBP 4,4'-N, N'-dicarbazole-biphenyl
  • a-NPD N'-diphenyl-N,N'-bis(1-naphthyl)-1,1'-biphenyl-4,4"-diamine
  • TCCA 4,4', 4"
  • the surface tension modifier is an organic acid, organic ammonia or a mixture thereof.
  • the organic acid is a fatty acid and the organic ammonia is an alkylamine.
  • the fatty acid is selected from the group consisting of caprylic acid, capric acid, oleic acid, lauric acid, and combinations thereof.
  • the alkylamine is selected from the group consisting of dodecylamine, hexadecylamine, stearylamine, oleylamine, and combinations thereof.
  • the non-polar organic solvent is selected from the group consisting of: a chain alkane, a cycloalkane, a halogenated alkane, an aromatic hydrocarbon, a derivative of the above, and combinations thereof.
  • the non-polar organic solvent is selected from the group consisting of: n-pentane, n-hexane, n-heptane, n-octane, cyclopentane, cyclohexane, chloroform, ethyl bromide, tetrachloro Carbon, benzene, toluene and combinations thereof.
  • the mass percentage of each component of the quantum dot ink is:
  • the carrier transport material is 8%-12%
  • the surface tension modifier is 1%-4%
  • the hydrophobic quantum dot material is 5%-18%
  • the non-polar organic solvent is 66%-86%.
  • the mass percentage of each component of the quantum dot ink is: 9%-11% of the carrier transport material, 1%-2% of the surface tension modifier, and 10% of the hydrophobic quantum dot material. -15%, non-polar organic solvent 62%-80%.
  • the surface of the hydrophobic quantum dot material has a trioctylphosphine or a trioctylphosphine oxide ligand.
  • Embodiments of the present invention also provide a method for preparing a quantum dot ink, comprising: mixing a hydrophobic quantum dot material, a carrier transport material, a surface tension modifier, and a non-polar organic solvent to obtain the quantum dot ink.
  • the hydrophobic quantum dot material is capable of phase separation from the carrier transport material.
  • the quantum dot ink has a viscosity of 10-12 cP and a surface tension of 32-42 dynes/cm.
  • the mixing mode is agitation, shaking or ultrasonic dispersion.
  • Embodiments of the present invention also provide a method of fabricating a quantum dot light emitting diode device using the quantum dot ink printing, comprising the steps of:
  • quantum dot ink phase separation forming a hydrophobic quantum dot material layer and a second functional layer, and forming a third functional layer on the second functional layer;
  • the carrier transport material is an electron transport material
  • the first electrode layer is an ITO anode
  • the first functional layer is from the first electrode to the second electrode
  • the hole injection layer and the hole transport layer are sequentially included in the direction
  • the second functional layer is an electron transport layer
  • the third functional layer is an electron injection layer
  • the second electrode layer is a metal cathode.
  • the carrier transport material is a hole transport material
  • the first electrode layer is a metal cathode
  • the first functional layer is from the first electrode to the second
  • the electron injection layer and the electron transport layer are sequentially included in the direction of the electrode
  • the second functional layer is a hole transport layer
  • the third functional layer is a hole injection layer
  • the second electrode layer is an ITO anode.
  • FIG. 1(a)-(e) are schematic views showing a process of preparing a quantum dot light-emitting device according to an embodiment of the present invention
  • FIG. 2 is a schematic structural view of a quantum dot light emitting device according to another embodiment of the present invention.
  • the chemical reagents and chemicals used in the present disclosure are derived from analytically pure/chemically pure commercial products.
  • a polymer is generally used as a carrier transport material.
  • the polymer is easy to agglomerate with the quantum dot material, and the existing quantum dot ink viscosity and surface tension are not suitable for preparing the electroluminescent device by the inkjet printer, and the quantum dot electroluminescent device for inkjet printing is formed greatly. limits.
  • the inventors of the present invention have surprisingly found in research that a non-polar organic solvent, a surface tension modifier and a hydrophobic quantum dot material, and a carrier transport material such as an electron transport material or a hole transport material are mixed.
  • the quantum dot ink is obtained, and the ratio of each component is appropriately adjusted to obtain a quantum dot ink suitable for inkjet printing.
  • the hydrophobic quantum dot material can be phase-separated from the carrier transport material, thereby forming a hydrophobic quantum dot material layer and a carrier transport material layer in one printing.
  • Two-layer structure Not only the quantum dot light-emitting device is prepared by inkjet printing, but also the operation is simplified, and the manufacturing cost of the quantum dot light-emitting device is reduced.
  • the non-polar organic solvent is capable of dispersing a hydrophobic quantum dot material
  • the surface tension modifier is capable of adjusting a surface tension range of the quantum dot ink
  • the hydrophobic quantum dot material is capable of forming a light-emitting layer of the quantum dot light-emitting device
  • the carrier transport material is capable of adjusting the viscosity range of the quantum dot ink and is capable of forming a carrier transport layer after phase separation.
  • the viscosity of the quantum dot ink is controlled to be 10-12 cP and the surface tension is 32-42 dynes/cm, and the viscosity and surface tension of the quantum dot ink are moderate, and the quantum dot ink is inkjet printed. It does not flow out of the ink jet port, nor does it block the ink jet port, so that it is better adapted to inkjet printing. It should be noted that the measured values of viscosity and surface tension are temperature dependent, and it is only required to have a viscosity of 10-12 cP and a surface tension of 32-42 dynes/cm at the temperature of inkjet printing. Better printing results. In the following specific embodiments, both the viscosity and the surface tension are measured at, for example, 25 ° C, which is the most common operating temperature, and the present invention is not limited thereto.
  • the non-polar organic solvent In order to prepare a quantum dot ink having viscosity and surface tension meeting the above requirements, the non-polar organic solvent generally selects an organic substance which is liquid at room temperature at 25 ° C and has a boiling point of less than 200 ° C at normal pressure; the surface tension modifier is generally selected.
  • the non-polar organic solvent selects an organic substance which is liquid at room temperature at 25 ° C and has a boiling point of less than 200 ° C at normal pressure, and can better disperse the hydrophobic quantum dot material;
  • the surface tension modifier generally selects a molecular weight of less than 500
  • Hydrophobic, polar organic material the carrier transport material (such as electron transport material or hole transport material) generally selects organic matter with a molecular weight of less than 500, which can increase the solubility of the above substances and reduce the hydrophobic quantum dot material The risk of reunion is better printed.
  • the quantum dot ink has the following composition: oxadiazole (electron transport material) 5 wt%; hydrophobic quantum dot material CdSe 2 wt%; octanoic acid (surface tension modifier) 1 wt%, non-polar organic solvent N-hexane 92% by weight.
  • the components are prepared in a mass ratio, and the hydrophobic quantum dot material CdS is first uniformly mixed with the non-polar organic solvent n-hexane; then the electron transporting material oxadiazole is added. Mixing uniformly; finally adding the surface tension modifier octanoic acid and mixing well.
  • the above mixing modes include electromagnetic stirring, oscillation, and/or ultrasonic dispersion. The order of mixing is not limited to the above order as long as a uniformly dispersed mixture of hydrophobic quantum dot materials is finally obtained.
  • the above quantum dot ink was tested to have a viscosity of 10 cp (25 ° C) and a surface tension of 32 dynes/cm (25 ° C).
  • the test for viscosity and surface tension can be carried out by methods common in the art.
  • the viscosity measurement can be measured by a capillary viscometer, a rotary viscometer, a vibrating viscometer, etc.
  • the surface tension can be measured by using a rotary drop interface tension meter, a computerized surface tension meter, a static surface tension meter, or the like.
  • the test results of viscosity and surface tension are mainly related to temperature, but have little relevance to the test methods and test instruments used.
  • the viscosity is measured by a digital display rotary viscometer, and the liquid to be tested is injected into the instrument, and the measurement can be started by clicking; in this embodiment, the surface tension is measured by using a rotary drop interface tension meter, using the machine.
  • the video optics tracks the moving droplets and acquires the image through a digital imaging system that calculates the surface tension value by analyzing the droplet image.
  • the above hydrophobic quantum dot material is generally prepared by a high temperature oil phase method in an organic solvent, and the quantum dot material thus prepared has an organic ligand on the surface thereof, and the organic ligand may be, for example, trioctylphosphine, trioctylphosphine oxide or the like. It is advantageous for its dispersion in a non-polar organic solvent.
  • the surface of the hydrophobic quantum dot material is electrically neutral, the hydrophobic quantum dot material and the electron transporting material oxadiazole are not prone to agglomeration.
  • the use of hydrophobic quantum dot materials and non-polar organic solvents solves the problem of quantum dot material dispersion in quantum dot inks, and the problem that quantum dot materials are easily agglomerated with electron transport materials.
  • the inventors of the present invention have found that it is not enough to solve the above problems, and that the viscosity and surface tension of the quantum dot ink need to meet certain requirements, and it is suitable to prepare a quantum dot light-emitting device by inkjet printing.
  • the viscosity of the quantum dot ink is too low and the surface tension is too small, the ink cannot form ink droplets, and the liquid column directly flows out from the ink discharge port, and cannot be printed; if the viscosity is too high and the surface tension is too large, the ink It will block the printer's inkjet port and will not print.
  • the above surface tension modifier octanoic acid mainly acts to increase the surface tension of the quantum dot ink, making it suitable for inkjet printing.
  • the inventors of the present invention found that the ratio range of the electron transporting material, the hydrophobic quantum dot material, the surface tension adjusting agent and the non-polar organic solvent is reasonably adjusted, so that the finally obtained quantum dot ink has a viscosity of 10-12 cP and a surface tension of 32. -42dynes/cm, which is well adapted to the requirements of inkjet printing.
  • the hydrophobic quantum dot material used in this embodiment is a Cds quantum dot material, but the selection of the quantum dot material is not limited thereto, and any quantum dot material which is available in the art can be used, for example, a quantum dot material can also be used.
  • a quantum dot material can also be used.
  • the electron transporting material used in the present embodiment is an oxadiazole, but the selection of the electron transporting material is not limited thereto, and any electron transporting material which is known in the art can satisfy the requirements as long as it is an organic substance having a molecular weight of less than 500. A molecular weight of more than 500 reduces the solubility of the electron transporting material and increases the risk of agglomeration.
  • the electron transporting material may be selected from one or more of the following: oxadiazole, thiadiazole, s-triazole, naphthalene, benzoquinone, carbazole, and derivatives of the above.
  • the non-polar organic solvent used in this embodiment is n-hexane, but the selection of the non-polar organic solvent is not limited thereto, and any non-polar organic solvent which is liquid at room temperature at 25 ° C and has a boiling point of less than 200 ° C at normal pressure. Can meet the requirements.
  • the so-called non-polar organic solvent refers to a type of solvent having a low dielectric constant.
  • the range of the above dielectric constant is not limited herein as long as the hydrophobic quantum dot material can It is sufficient to be dispersed in the non-polar organic solvent within the range used, and stably stored for one week or more, or stably stored for one month or more, or stably stored for three months or more.
  • the non-polar organic solvent may be a mixture of one or more of the following: alkane, cycloalkane, halogenated alkane, aromatic hydrocarbon, and derivatives thereof.
  • the non-polar organic solvent may be a mixture of one or more of the following: n-pentane, n-hexane, n-heptane, n-octane, cyclopentane, cyclohexane, chloroform, bromine Ethane, carbon tetrachloride, benzene, toluene.
  • the surface tension adjusting agent used in the present embodiment is octanoic acid, but the selection of the surface tension adjusting agent is not limited thereto. Any hydrophobic or polar organic substance with a molecular weight of less than 500 can meet the requirements. Hydrophobicity is to ensure its miscibility with non-polar solvents, the polarity is to ensure that it can increase the surface tension of quantum dot ink, and the molecular weight of more than 500 will reduce its solubility and increase the risk of agglomeration.
  • the surface tension modifier may be an organic acid, organic ammonia, or a mixture thereof.
  • the surface tension modifier can be a fatty acid, an alkylamine, or a mixture thereof.
  • the surface tension adjusting agent may be one of or a mixture of octanoic acid, citric acid, oleic acid, and lauric acid; the alkylamine is dodecylamine, hexadecylamine, octadecylamine, and oil. Amine or a mixture thereof.
  • an ITO anode 101 and a pixel defining layer 102 are first prepared on a base substrate 100.
  • the anode 101 is a pixel electrode.
  • three separate pixel electrodes are generally provided, and different pixel electrodes generally emit light of different colors. Taking the full color display as an example, the above three separated pixel electrodes generally emit red light, green light, and blue light, respectively.
  • a hole injecting layer 103 and a hole transporting layer 104 are prepared on the ITO anode 101.
  • a layer of the above quantum dot ink 105 is printed on the hole transport layer 104 by an ink jet printer.
  • the quantum dot ink 105 is printed, it is dried by vacuum or heating.
  • the hydrophobic quantum dot material is separated from the electron transporting material, and is hydrophobic.
  • the quantum dot material is in the lower layer to form the quantum dot light-emitting layer 1051; the electron transporting material is in the upper layer to form the electron transport layer 1052, that is, a two-layer structure is obtained by one printing.
  • the surface tension and viscosity of the quantum dot ink in an appropriate range by adjusting the ratio of each component in the quantum dot ink (the viscosity of the quantum dot ink in this embodiment is 10 cp (25 ° C), surface)
  • the tension is 32 dynes/cm (25 ° C))
  • the thickness of the printed quantum dot luminescent layer and the charge transport layer can be controlled.
  • the electron transport layer 1052 obtained by the above printing has a thickness of 5 nm; and the quantum dot light-emitting layer 1051 has a thickness of 8 nm.
  • the electron injection layer 106 and the metal cathode 107 are continuously formed on the electron transport layer 1052, and the device preparation is completed.
  • the preparation of the above layers can be carried out by inkjet printing except that the ITO anode is generally sputtered and the metal cathode is generally prepared by vacuum evaporation.
  • the quantum dot ink has the following composition: CBP (4,4'-N, N'-dicarbazole-biphenyl) (hole transport material) 5 wt%; hydrophobic quantum dot material CdSe 2 wt%; octanoic acid (surface tension modifier) 1 wt% and non-polar organic solvent n-hexane 92 wt%.
  • CBP 4,4'-N, N'-dicarbazole-biphenyl
  • hole transport material 5 wt%
  • hydrophobic quantum dot material CdSe 2 wt%
  • octanoic acid surface tension modifier
  • the difference from the previous embodiment is that the electron transporting material is replaced with a hole transporting material, and thus the order of preparation of the layers in the quantum dot light emitting device needs to be reversed.
  • a metal cathode 201 and a pixel defining layer 202 are first formed on a base substrate 200.
  • an electron injection layer 203 and an electron transport layer 204 are formed on the metal cathode 201.
  • a layer of the above-described quantum dot ink 205 is printed on the electron transport layer 204 by an ink jet printer (the case after phase separation is shown in the figure).
  • the quantum dot ink 205 After the quantum dot ink 205 is printed, it is dried by vacuuming or heating. In the process, the hydrophobic quantum dot material is phase separated from the hole transport material.
  • the hydrophobic quantum dot material forms a quantum dot light-emitting layer 2051 in the lower layer, and the hole transporting material is in the upper layer to form a hole transport layer 2052, that is, a two-layer structure is obtained by one printing.
  • the quantum dot ink has a viscosity of 10 cp (25 ° C) and a surface tension of 32 dynes/cm (25 ° C), and finally, the thickness of the printed quantum dot light-emitting layer and the charge transport layer can be controlled.
  • the hole transport layer 2052 obtained by the above printing has a thickness of 5 nm; and the quantum dot light-emitting layer 2051 has a thickness of 8 nm.
  • the hole injection layer 206 and the ITO anode 207 are continuously prepared on the electron transport layer 2052, and the device preparation is completed.
  • the quantum dot ink has the following composition: thiadiazole (electron transport material) 5 wt%; hydrophobic quantum dot material ZnO 20 wt%; octadecylamine (surface tension modifier) 1 wt% and non-polar
  • the organic solvent cyclohexane was 74% by weight.
  • the quantum dot ink was configured in the same manner as in Example 1. The above quantum dot ink was tested to have a viscosity of 10.5 cp (25 ° C) and a surface tension of 33 dynes/cm (25 ° C).
  • a quantum dot light-emitting device was prepared in the same manner as in Example 1 to obtain an electron transport layer having a thickness of 5 nm; and a quantum dot material layer having a thickness of 15 nm.
  • the quantum dot ink has the following composition: averax triazole (electron transport material) 5 wt%; hydrophobic quantum dot material GaAs 20 wt%; oleylamine (surface tension modifier) 20 wt% and non-polar organic Solvent benzene 55 wt%.
  • the quantum dot ink was configured in the same manner as in Example 1. The above quantum dot ink was tested to have a viscosity of 11 cp (25 ° C) and a surface tension of 38 dynes/cm (25 ° C).
  • a quantum dot light-emitting device was prepared in the same manner as in Example 1 to obtain an electron transport layer having a thickness of 5 nm; and a quantum dot material layer having a thickness of 15 nm.
  • the quantum dot ink has the following composition: carbazole (electron transport material) 15 wt%; hydrophobic quantum dot material InP 2 wt%; oleic acid (surface tension modifier) 1 wt% and non-polar organic solvent Benzene 82% by weight.
  • the quantum dot ink was configured in the same manner as in Example 1.
  • the above quantum dot ink has been tested to have a viscosity of 11.5 cp (25 ° C) and a surface tension of 35 dynes/cm. (25 ° C).
  • a quantum dot light-emitting device was prepared in the same manner as in Example 1 to obtain an electron transport layer having a thickness of 45 nm; and a quantum dot material layer having a thickness of 10 nm.
  • the quantum dot ink has the following composition: carbazole (electron transport material) 15 wt%; hydrophobic quantum dot material ZnS 20 wt%; oleic acid (surface tension modifier) 1 wt% and non-polar organic solvent Benzene 64 wt%.
  • the quantum dot ink was configured in the same manner as in Example 1. The above quantum dot ink was tested to have a viscosity of 11.5 cp (25 ° C) and a surface tension of 35 dynes/cm (25 ° C).
  • a quantum dot light-emitting device was prepared in the same manner as in Example 1 to obtain an electron transport layer having a thickness of 45 nm; and a quantum dot material layer having a thickness of 28 nm.
  • the quantum dot ink has the following composition: naphthalene (electron transport material) 15 wt%; hydrophobic quantum dot material GaAs 20 wt%; tannic acid (surface tension modifier) 5 wt% and non-polar organic solvent four Carbon chloride 60% by weight.
  • the quantum dot ink was configured in the same manner as in Example 1. The above quantum dot ink was tested to have a viscosity of 12 cp (25 ° C) and a surface tension of 42 dynes/cm (25 ° C).
  • a quantum dot light-emitting device was prepared in the same manner as in Example 1 to obtain an electron transport layer having a thickness of 50 nm; and a quantum dot material layer having a thickness of 40 nm.
  • the quantum dot ink has the following composition: oxadiazole (electron transport material) 10 wt%; hydrophobic quantum dot material CdSe 15 wt%; octanoic acid (surface tension modifier) 1.5 wt% and non-polar organic
  • the solvent n-hexane was 73.5 wt%.
  • the quantum dot ink was disposed in the same manner as in Example 1, and the above quantum dot ink was tested to have a viscosity of 11 cp (25 ° C) and a surface tension of 38 dynes/cm (25 ° C).
  • a quantum dot light-emitting device was prepared in the same manner as in Example 1 to obtain an electron transport layer having a thickness of 30 nm; and a quantum dot material layer having a thickness of 28 nm.
  • the quantum dot ink has the following composition: averax triazole (electron transport material) 8 wt%; hydrophobic quantum dot material GaAs 5 wt%; tannic acid (surface tension modifier) 2 wt% and non-polar organic
  • the solvent n-pentane is 85 wt%.
  • the quantum dot ink was configured in the same manner as in Example 1. The above quantum dot ink was tested to have a viscosity of 11.5 cp (25 ° C) and a surface tension of 40 dynes/cm (25 ° C).
  • a quantum dot light-emitting device was prepared in the same manner as in Example 1 to obtain an electron transport layer having a thickness of 25 nm; and a quantum dot material layer having a thickness of 15 nm.
  • the quantum dot ink has the following composition: oxadiazole (electron transport material) 12 wt%; hydrophobic quantum dot material CdSe 18 wt%; lauric acid (surface tension modifier) 4 wt% and non-polar organic
  • the solvent carbon tetrachloride was 66% by weight.
  • the quantum dot ink was configured in the same manner as in Example 1. The above quantum dot ink was tested to have a viscosity of 12 cp (25 ° C) and a surface tension of 41 dynes/cm (25 ° C).
  • a quantum dot light-emitting device was prepared in the same manner as in Example 1 to obtain an electron transport layer having a thickness of 30 nm; and a quantum dot material layer having a thickness of 20 nm.
  • the quantum dot ink has the following composition: benzoquinone (electron transport material) 9 wt%; hydrophobic quantum dot material CdSe 10 wt%; octanoic acid (surface tension modifier) 2 wt% and non-polar organic solvent
  • the alkane was 79% by weight.
  • the quantum dot ink was configured in the same manner as in Example 1. The above quantum dot ink was tested to have a viscosity of 11 cp (25 ° C) and a surface tension of 39 dynes/cm (25 ° C).
  • a quantum dot light-emitting device was prepared in the same manner as in Example 1 to obtain an electron transport layer having a thickness of 25 nm; and a quantum dot material layer having a thickness of 17 nm.
  • the quantum dot ink has the following composition: naphthalene (electron transport material) 11 wt%; hydrophobic quantum dot material ZnS 13 wt%; dodecylamine (surface tension modifier) 1.5 wt% and a nonpolar organic solvent cyclohexane 74.5 wt%.
  • the quantum dot ink was configured in the same manner as in Example 1. The above quantum dot ink was tested to have a viscosity of 10.5 cp (25 ° C) and a surface tension of 36 dynes/cm (25 ° C).
  • a quantum dot light-emitting device was prepared in the same manner as in Example 1 to obtain an electron transport layer having a thickness of 28 nm; and a quantum dot material layer having a thickness of 19 nm.
  • the quantum dot ink has the following composition: a-NPD (N'-diphenyl-N,N'-bis(1-naphthyl)-1,1'-biphenyl-4, 4"-diamine) (hole transport material) 8 wt%; hydrophobic quantum dot material GaAs 5 wt%; tannic acid (surface tension modifier) 2 wt% and non-polar organic solvent n-pentane 85 wt%.
  • the quantum dot ink was configured in the same manner.
  • the above quantum dot ink was tested to have a viscosity of 11.5 cp (25 ° C) and a surface tension of 40 dynes/cm (25 ° C).
  • a quantum dot light-emitting device was prepared in the same manner as in Example 2 to obtain a hole transport layer having a thickness of 25 nm; and a quantum dot material layer having a thickness of 15 nm.
  • the quantum dot ink has the following composition: TCCA (4,4',4"-tris(N-oxazolyl)-triphenylamine) (hole transport material) 12 wt%; hydrophobic quantum dot material CdSe 18 wt%; lauric acid (surface tension modifier) 4 wt% and non-polar organic solvent n-hexane 66 wt%.
  • the quantum dot ink was configured in the same manner as in Example 2. The viscosity of the above quantum dot ink was tested to be 12 cp ( 25 ° C), surface tension is 41 dynes / cm (25 ° C).
  • a quantum dot light-emitting device was prepared in the same manner as in Example 2 to obtain a hole transport layer having a thickness of 30 nm; and a quantum dot material layer having a thickness of 20 nm.
  • the quantum dot ink has the following composition: DNTPD (N,N'-bis(4-(N,N'-diphenyl-amino)phenyl)-N,N'-diphenyl linkage Aniline) (hole transport material) 9 wt%; hydrophobic quantum dot material CdSe 10 wt%; octanoic acid (surface tension modifier) 2 wt% and nonpolar organic solvent n-heptane 79 wt%.
  • the quantum dot ink was configured in the same manner as in Example 2. The above quantum dot ink was tested to have a viscosity of 11 cp (25 ° C) and a surface tension of 39 dynes/cm (25 ° C).
  • a quantum dot light-emitting device was prepared in the same manner as in Example 2 to obtain a hole transport layer having a thickness of 25 nm; and a quantum dot material layer having a thickness of 17 nm.
  • the quantum dot ink has the following composition: a-NPD (N'-diphenyl-N,N'-bis(1-naphthyl)-1,1'-biphenyl-4, 4"-diamine) (hole transport material) 11 wt%; hydrophobic quantum dot material ZnS 13 wt%; dodecylamine (surface tension modifier) 1.5 wt% and non-polar organic solvent n-pentane 74.5 wt%.
  • the quantum dot ink was disposed in the same manner as in Example 2. The above quantum dot ink was tested to have a viscosity of 10.5 cp (25 ° C) and a surface tension of 36 dynes/cm (25 ° C).
  • a quantum dot light-emitting device was prepared in the same manner as in Example 2 to obtain a hole transport layer having a thickness of 28 nm; and a quantum dot material layer having a thickness of 19 nm.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Dispersion Chemistry (AREA)
  • Electroluminescent Light Sources (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

一种量子点墨水，包括非极性有机溶剂、表面张力调节剂、疏水性量子点材料，和载流子传输材料。使用该量子点墨水喷墨打印完成后，疏水性量子点材料能够与载流子传输材料发生相分离，形成两层结构，便于用喷墨打印的方式制备量子点发光器件。

Description

量子点墨水 技术领域
本发明的实施例涉及量子点墨水。
背景技术
量子点发光二极管显示器(Quantum Dots Light Emitting Diode Displays,QLED)是基于有机发光显示器的基础上发展起来的一种新型显示技术。与其他类型的有机发光二极管不同的是，其电致发光结构为量子点层，且其原理为，电子通过电子传输层注入量子点层，空穴通过空穴传输层注入量子点层，电子和空穴在量子点中复合发光。与有机发光二极管显示器件相比，QLED具有发光峰窄、色彩饱和度高、色域宽等优点。
当前QLED像素化、全彩化存在一定的技术难题，解决的方式有喷墨打印法、转印法、微接触式打印法等。对于喷墨打印法遇到很大的难题在于量子点墨水的制备。量子点墨水通常将量子点材料分散在有机溶剂中而得到，由于量子点材料本身是纳米颗粒，所以很难得到高粘度的量子点墨水，导致打印困难。
发明内容
本发明的实施例提供了一种量子点墨水，包括非极性有机溶剂、表面张力调节剂和疏水性量子点材料，所述量子点墨水还进一步包括载流子传输材料，所述疏水性量子点材料能够与所述载流子传输材料发生相分离。
在本发明的一个实施方式中，所述量子点墨水的粘度为10-12cP，表面张力为32-42dynes/cm。
在本发明的一个实施方式中，所述表面张力调节剂为分子量小于500的疏水性、极性有机物。
在本发明的一个实施方式中，所述载流子传输材料为分子量小于500的电子传输材料或者空穴传输材料。
在本发明的一个实施方式中，所述非极性有机溶剂在25℃下为液体且常 压下沸点小于200℃。
在本发明的一个实施方式中，所述量子点墨水各组分的质量百分比为：载流子传输材料5％-15％，表面张力调节剂1％-5％，疏水性量子点材料2％-20％，非极性有机溶剂60％-92％。
在本发明的一个实施方式中，所述疏水性量子点材料选自下述量子点材料中的一种或多种：CdS、CdSe、CdTe、ZnO、ZnS、ZnSe、ZnTe、GaAs、GaP、GaSb、HgS、HgSe、HgTe、InAs、InP、InSb、AlAs、AlP、CuInS、CuInSe、AlSb。
在本发明的一个实施方式中，所述载流子传输材料为电子传输材料，所述电子传输材料选自：噁二唑、噻二唑、均***、萘、苯醌、咔唑、上述物质的衍生物及其组合。
在本发明的一个实施方式中，所述载流子传输材料为空穴传输材料，所述空穴传输材料选自：CBP(4,4’-N,N’-二咔唑-联苯)、a-NPD(N’-二苯基-N,N’-二(1-萘基)-1,1’-联苯基-4,4”-二胺)、TCCA(4,4’,4”-三(N-唑基)-三苯胺)、DNTPD(N,N’-二(4-(N,N’-二苯基-氨基)苯基)-N,N’-二苯联苯胺)及其组合。
在本发明的一个实施方式中，所述表面张力调节剂为有机酸、有机氨或其混合物。
在本发明的一个实施方式中，所述有机酸为脂肪酸、所述有机氨为烷基氨。
在本发明的一个实施方式中，所述脂肪酸选自：辛酸、癸酸、油酸、月桂酸及其组合。
在本发明的一个实施方式中，所述烷基氨选自：十二胺、十六胺、十八胺、油胺及其组合。
在本发明的一个实施方式中，所述非极性有机溶剂选自：链状烷烃、环烷烃、卤代烷烃、芳香烃、上述物质的衍生物及其组合。
在本发明的一个实施方式中，所述非极性有机溶剂选自：正戊烷、正己烷、正庚烷、正辛烷、环戊烷、环己烷、氯仿、溴乙烷、四氯化碳、苯、甲苯及其组合。
在本发明的一个实施方式中，所述量子点墨水各组分的质量百分比为： 载流子传输材料8％-12％，表面张力调节剂1％-4％，疏水性量子点材料5％-18％，非极性有机溶剂66％-86％。
在本发明的一个实施方式中，所述量子点墨水各组分的质量百分比为：载流子传输材料9％-11％，表面张力调节剂1％-2％，疏水性量子点材料10％-15％，非极性有机溶剂62％-80％。
在本发明的一个实施方式中，所述疏水性量子点材料表面具有三辛基膦或三辛基氧化膦配体。
本发明的实施例还提供一种量子点墨水的制备方法，包括：将疏水性量子点材料、载流子传输材料、表面张力调节剂和非极性有机溶剂混合，以得到所述量子点墨水，所述疏水性量子点材料能够与所述载流子传输材料发生相分离。
在本发明的一个实施方式中，所述量子点墨水的粘度为10-12cP，表面张力为32-42dynes/cm。
在本发明的一个实施方式中，所述混合方式为搅拌、振荡或超声分散。
本发明的实施例还提供一种利用所述的量子点墨水打印制备量子点发光二极管器件的方法，包括如下步骤：
1)在基板上制作第一电极层；
2)在所述第一电极层上制作第一功能层；
3)在所述第一功能层上打印量子点墨水；
4)量子点墨水发生相分离，形成疏水性量子点材料层和第二功能层，在所述第二功能层上制作第三功能层；
5)在所述第三功能层上制作第二电极层。
在本发明的一个实施方式中，所述载流子传输材料为电子传输材料，所述第一电极层为ITO阳极，所述第一功能层在从所述第一电极到所述第二电极的方向上顺次包括空穴注入层和空穴传输层，所述第二功能层为电子传输层，所述第三功能层为电子注入层，所述第二电极层为金属阴极。
在本发明的一个实施方式中，所述载流子传输材料为空穴传输材料，所述第一电极层为金属阴极，所述第一功能层在从所述第一电极到所述第二电极的方向上顺次包括电子注入层和电子传输层，所述第二功能层为空穴传输层，所述第三功能层为空穴注入层，所述第二电极层为ITO阳极。
如何配制适合喷墨打印的量子点墨水是本领域的技术难点，本发明的发明人发现，将非极性有机溶剂、表面张力调节剂和疏水性量子点材料，以及载流子传输材料(例如电子传输材料或空穴传输材料)，混合而得到量子点墨水，适当调整各组分的比例，即可获得适于喷墨打印量子点墨水。使用该量子点墨水喷墨打印完成后，所述疏水性量子点材料能够与所述载流子传输材料发生相分离，从而一次打印即形成疏水性量子点材料层和载流子传输材料层的两层结构，不但实现了用喷墨打印的方式制备量子点发光器件，而且简化了操作，降低了量子点发光器件的制造成本。
附图说明
为了更清楚地说明本发明实施例的技术方案，下面将对实施例的附图作简单地介绍，显而易见地，下面描述中的附图仅仅涉及本发明的一些实施例，而非对本发明的限制。
图1(a)-(e)为本发明一实施方式中量子点发光器件的制备过程示意图；
图2为本发明另一实施方式中量子点发光器件结构示意图。
附图标记：
100-衬底基板、101-ITO阳极、102-像素界定层、103-空穴注入层、104-空穴传输层、105-量子点墨水、1051-量子点发光层、1052-电子传输层、106-电子注入层、107-金属阴极
200-衬底基板、201-金属阴极、202-像素界定层、203-电子注入层、204-电子传输层、2051-量子点发光层、2052-空穴传输层、206-空穴注入层、207-ITO阳极
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚，下面将结合本发明实施例的附图，对本发明实施例的技术方案进行清楚、完整地描述。显然，所描述的实施例是本发明的一部分实施例，而不是全部的实施例。基于所描述的本发明的实施例，本领域普通技术人员在无需创造性劳动的前提下所获得的所有其他实施例，都属于本发明保护的范围。
除非另作定义，本公开所使用的技术术语或者科学术语应当为本发明所 属领域内具有一般技能的人士所理解的通常意义。本发明专利申请说明书以及权利要求书中使用的“第一”、“第二”以及类似的词语并不表示任何顺序、数量或者重要性，而只是用来区分不同的组成部分。同样，“一个”或者“一”等类似词语也不表示数量限制，而是表示存在至少一个。“连接”或者“相连”等类似的词语并非限定于物理的或者机械的连接，而是可以包括电性的连接，不管是直接的还是间接的。
除非另作定义，本公开中百分比均为质量百分比。
除非另作定义，本公开中所使用的化学试剂、化学物质均来自分析纯/化学纯的市售商品。
现有的量子点墨水中一般采用聚合物作为载流子传输材料。但聚合物容易与量子点材料发生团聚，且现有的量子点墨水粘度、表面张力都不适合用喷墨打印机制备电致发光器件，对喷墨打印制备量子点电致发光器件形成了很大的限制。本发明的发明人在研究中惊奇地发现，将非极性有机溶剂、表面张力调节剂和疏水性量子点材料，以及载流子传输材料(例如电子传输材料或空穴传输材料)，混合而得到量子点墨水，适当调整各组分的比例，即可获得适于喷墨打印量子点墨水。使用该量子点墨水喷墨打印完成后，所述疏水性量子点材料能够与所述载流子传输材料发生相分离，从而一次打印即形成疏水性量子点材料层和载流子传输材料层的两层结构。不但实现了用喷墨打印的方式制备量子点发光器件，而且简化了操作，降低了量子点发光器件的制造成本。其中，所述非极性有机溶剂能够分散疏水性量子点材料；所述表面张力调节剂能够调节量子点墨水的表面张力范围；所述疏水性量子点材料能够形成量子点发光器件的发光层；所述载流子传输材料能够调节量子点墨水的粘度范围，并且在相分离之后能够形成载流子传输层。
实际进行打印操作时，控制所述量子点墨水的粘度为10-12cP、表面张力为32-42dynes/cm，则所述量子点墨水的粘度、表面张力适中，喷墨打印时所述量子点墨水既不会从喷墨口流出，也不会堵塞喷墨口，从而更好地适应喷墨打印。需要说明的是，粘度和表面张力的测量数值与温度相关，只需要在喷墨打印的温度下，所述量子点墨水的粘度为10-12cP、表面张力为32-42dynes/cm，即可获得较好的打印效果。在下面具体的实施方式中，粘度和表面张力均在例如25℃下测量，这是最常见的操作温度，本发明并不限于此。
为配制得到粘度和表面张力符合上述要求的量子点墨水，所述非极性有机溶剂一般选择室温25℃下为液体、且常压下沸点小于200℃的有机物；所述表面张力调节剂一般选择分子量小于500的疏水性、极性有机物；所述载流子传输材料(例如电子传输材料或空穴传输材料)一般选择分子量小于500的有机物。所述非极性有机溶剂选择室温25℃下为液体、且常压下沸点小于200℃的有机物，可以更好地分散所述疏水性量子点材料；所述表面张力调节剂一般选择分子量小于500的疏水性、极性有机物，所述载流子传输材料(例如电子传输材料或空穴传输材料)一般选择分子量小于500的有机物，这可以增加上述物质的溶解性并减少与疏水性量子点材料团聚的风险，获得更好地打印效果。
实施例1
在一个具体实施方式中，量子点墨水具有如下的组成：噁二唑(电子传输材料)5wt％；疏水性量子点材料CdSe 2wt％；辛酸(表面张力调节剂)1wt％、非极性有机溶剂正己烷92wt％。
制备上述量子点墨水时，按照质量比例准备好各组分，先将所述疏水性量子点材料CdS与所述非极性有机溶剂正己烷混合均匀；然后加入所述电子传输材料噁二唑，混合均匀；最后加入所述表面张力调节剂辛酸，混合均匀。上述的混合方式包括电磁搅拌、振荡和/或超声分散等。混合顺序不限于上述顺序，只要最终得到均一分散的疏水性量子点材料混合物即可。制备得到量子点墨水之后，经测试，上述量子点墨水的粘度为10cp(25℃)，表面张力为32dynes/cm(25℃)。粘度和表面张力的测试可以用本领域通用的方法。例如，粘度测量可采用毛细管式粘度计、旋转式粘度计、振动式粘度计等测量；表面张力的测量则可采用旋转滴界面张力仪、微机化表面张力仪、静力学表面张力仪等测量。粘度和表面张力的测试结果主要与温度相关，而与采用的测试方法、测试仪器相关度不大。本实施例中粘度的测量用的是数显旋转式粘度计，将待测液体注入仪器中，点击开始测量即可；本实施例中表面张力的测量是采用旋转滴界面张力仪，利用机器的视频光学***追踪移动液滴，并通过数码成像***采集成像，通过对液滴图像进行分析测量计算表面张力值。
上述疏水性量子点材料一般在有机溶剂中通过高温油相法制备，如此制备得到的量子点材料表面具有有机配体，上述有机配体可以为例如三辛基膦，三辛基氧化膦等，有利于其在非极性有机溶剂中分散。此外，由于上述疏水性量子点材料表面呈电中性，疏水性量子点材料与电子传输材料噁二唑也不容易发生团聚。因此，采用疏水性量子点材料和非极性有机溶剂即解决了量子点材料在量子点墨水中分散的问题，以及量子点材料容易与电子传输材料发生团聚的问题。但本发明的发明人发现，只解决上述问题还不够，量子点墨水的粘度和表面张力都需要满足一定的要求，才适合以喷墨打印的方式来制备量子点发光器件。例如，若量子点墨水的粘度过低、表面张力过小，则墨水不能形成墨滴，而会直接形成液柱从喷墨口流出，无法打印；若粘度过高、表面张力过大，则墨水会堵塞打印机喷墨口，同样无法打印。上述表面张力调节剂辛酸的作用主要就在于增加量子点墨水的表面张力，使其适于喷墨打印。本发明的发明人发现，合理调整电子传输材料、疏水性量子点材料、表面张力调节剂和非极性有机溶剂的比例范围，使得最终获得的量子点墨水粘度为10-12cP，表面张力为32-42dynes/cm，即可较好地适应喷墨打印的要求。
本实施例中采用的疏水性量子点材料为Cds量子点材料，但量子点材料材料的选择并不限于此，任何本领域已有的量子点材料材料均可使用，例如量子点材料还可以为以下之一或其混合：CdSe、CdTe、ZnO、ZnS、ZnSe、ZnTe、GaAs、GaP、GaSb、HgS、HgSe、HgTe、InAs、InP、InSb、AlAs、AlP、CuInS、CuInSe、AlSb。
本实施例中采用的电子传输材料为噁二唑，但电子传输材料的选择并不限于此，任何本领域已有的电子传输材料，只要其为分子量小于500的有机物，即可满足要求。分子量超过500会降低电子传输材料的溶解性并增加团聚的风险。例如，所述电子传输材料可以选自下述物质中的一种或多种：噁二唑、噻二唑、均***、萘、苯醌、咔唑及上述物质的衍生物。
本实施例中采用的非极性有机溶剂为正己烷，但非极性有机溶剂的选择并不限于此，任何室温25℃下为液体、且常压下沸点小于200℃的非极性有机溶剂都可满足要求。所谓的非极性有机溶剂，指的是介电常数较低的一类溶剂。但本文并不限定上述介电常数的范围，只要所述疏水性量子点材料能 够在所使用的范围内分散于所述非极性有机溶剂中，并且稳定地存放1周以上，或者稳定地存放1个月以上，或者稳定地存放3个月以上，即可满足要求。例如所述非极性有机溶剂可以为下述物质的一种或多种的混合物：链状烷烃、环烷烃、卤代烷烃、芳香烃及其衍生物。又例如，所述非极性有机溶剂可以为下述物质的一种或多种的混合物：正戊烷、正己烷、正庚烷、正辛烷、环戊烷、环己烷、氯仿、溴乙烷、四氯化碳、苯、甲苯。选择上述具体的非极性溶剂，可以更好地分散所述疏水性量子点材料，形成更稳定的量子点墨水。
本实施例中采用的表面张力调节剂为辛酸，但表面张力调节剂的选择并不限于此。任何分子量小于500的疏水性、极性有机物，都可满足要求。疏水性是为了保证其与非极性溶剂的互溶，极性是保证其能增加量子点墨水的表面张力，而分子量超过500会降低其溶解性并增加团聚的风险。例如，所述表面张力调节剂可以为有机酸、有机氨或其混合物。又例如，所述表面张力调节剂可以为脂肪酸、烷基氨或其混合物。又例如，所述表面张力调节剂可以为下述物质之一或其混合物：辛酸、癸酸、油酸、月桂酸；所述烷基氨为十二胺、十六胺、十八胺、油胺或其混合物。选择上述具体的表面张力调节剂，可以更好地调整所述量子点墨水的表面张力到合适的范围，从而更好地适应喷墨打印的要求。
下面将结合附图1说明利用上述量子点墨水打印制备量子点发光器件的方法。
如图1a所示，首先在衬底基板100上制备ITO阳极101和像素界定层102。阳极101为像素电极，如图1a所示，一般设置3个分离的像素电极，并且不同的像素电极一般发射不同颜色的光。以全彩显示为例，上述3个分离的像素电极一般分别发射红光、绿光和蓝光。
然后，如图1b所示，在ITO阳极101上制备空穴注入层103和空穴传输层104。
如图1c所示，在空穴传输层104上用喷墨打印机打印一层上述量子点墨水105。
如图1d所示，量子点墨水105打印完成后，通过真空或者加热使其干燥，在此过程中，所述疏水性量子点材料与所述电子传输材料发生相分离，疏水 性量子点材料在下层，形成量子点发光层1051；电子传输材料在上层，形成电子传输层1052，即一次打印得到两层结构。如上所述，只需通过调整量子点墨水中各组分的比例，来控制量子点墨水的表面张力和粘度在适当的范围(本实施例中量子点墨水的粘度为10cp(25℃)，表面张力为32dynes/cm(25℃))，最终便能够控制打印得到的量子点发光层和电荷传输层的厚度。本实施例中，上述打印得到的电子传输层1052厚度为5nm；量子点发光层1051厚度为8nm。
如图1e所示，继续在电子传输层1052上制备电子注入层106以及金属阴极107，器件制备完成。
上述各层的制备，除ITO阳极一般采用溅射法、金属阴极一般采用真空蒸镀法制备外，其他各层均可以通过喷墨打印制备。
实施例2
在另一个具体实施方式中，量子点墨水具有如下的组成：CBP(4,4’-N,N’-二咔唑-联苯)(空穴传输材料)5wt％；疏水性量子点材料CdSe 2wt％；辛酸(表面张力调节剂)1wt％及非极性有机溶剂正己烷92wt％。与前述实施方式中相同的内容在此不再重复，下同。
与上一实施方式不同的地方在于，用空穴传输材料替换了电子传输材料，因而量子点发光器件中各层的制备顺序需要颠倒。
下面将结合附图2说明利用上述量子点墨水打印制备量子点发光器件的方法。
如图2所示，首先在衬底基板200上制备金属阴极201和像素界定层202。
然后，在金属阴极201上制备电子注入层203和电子传输层204。
然后，在电子传输层204上用喷墨打印机打印一层上述量子点墨水205(图中展示了相分离之后的情形)。
量子点墨水205打印完成后，通过抽真空或者加热使其干燥。在此过程中，所述疏水性量子点材料与所述空穴传输材料发生相分离。疏水性量子点材料在下层，形成量子点发光层2051；空穴传输材料在上层，形成空穴传输层2052，即一次打印得到两层结构。如上所述，只需通过调整量子点墨水中各组分的比例，来控制量子点墨水的表面张力和粘度在适当的范围(本实施 例中量子点墨水的粘度为10cp(25℃)，表面张力为32dynes/cm(25℃))，最终便能够控制打印得到的量子点发光层和电荷传输层的厚度。本实施例中，上述打印得到的空穴传输层2052厚度为5nm；量子点发光层2051厚度为8nm。
最后，继续在电子传输层2052上制备空穴注入层206以及ITO阳极207，器件制备完成。
实施例3
在一个具体实施方式中，量子点墨水具有如下的组成：噻二唑(电子传输材料)5wt％；疏水性量子点材料ZnO 20wt％；十八胺(表面张力调节剂)1wt％及非极性有机溶剂环己烷74wt％。按照与实施例1相同的方式配置量子点墨水。经测试，上述量子点墨水的粘度为10.5cp(25℃)，表面张力为33dynes/cm(25℃)。
按照与实施例1相同的方式制备量子点发光器件，得到电子传输层厚5nm；量子点材料层厚15nm。
实施例4
在一个具体实施方式中，量子点墨水具有如下的组成：均***(电子传输材料)5wt％；疏水性量子点材料GaAs 20wt％；油胺(表面张力调节剂)20wt％及非极性有机溶剂苯55wt％。按照与实施例1相同的方式配置量子点墨水。经测试，上述量子点墨水的粘度为11cp(25℃)，表面张力为38dynes/cm(25℃)。
按照与实施例1相同的方式制备量子点发光器件，得到电子传输层厚5nm；量子点材料层厚15nm。
实施例5
在一个具体实施方式中，量子点墨水具有如下的组成：咔唑(电子传输材料)15wt％；疏水性量子点材料InP 2wt％；油酸(表面张力调节剂)1wt％及非极性有机溶剂苯82wt％。按照与实施例1相同的方式配置量子点墨水。经测试，上述量子点墨水的粘度为11.5cp(25℃)，表面张力为35dynes/cm (25℃)。
按照与实施例1相同的方式制备量子点发光器件，得到电子传输层厚45nm；量子点材料层厚10nm。
实施例6
在一个具体实施方式中，量子点墨水具有如下的组成：咔唑(电子传输材料)15wt％；疏水性量子点材料ZnS 20wt％；油酸(表面张力调节剂)1wt％及非极性有机溶剂苯64wt％。按照与实施例1相同的方式配置量子点墨水。经测试，上述量子点墨水的粘度为11.5cp(25℃)，表面张力为35dynes/cm(25℃)。
按照与实施例1相同的方式制备量子点发光器件，得到电子传输层厚45nm；量子点材料层厚28nm。
实施例7
在一个具体实施方式中，量子点墨水具有如下的组成：萘(电子传输材料)15wt％；疏水性量子点材料GaAs 20wt％；癸酸(表面张力调节剂)5wt％及非极性有机溶剂四氯化碳60wt％。按照与实施例1相同的方式配置量子点墨水。经测试，上述量子点墨水的粘度为12cp(25℃)，表面张力为42dynes/cm(25℃)。
按照与实施例1相同的方式制备量子点发光器件，得到电子传输层厚50nm；量子点材料层厚40nm。
实施例8
在一个具体实施方式中，量子点墨水具有如下的组成：噁二唑(电子传输材料)10wt％；疏水性量子点材料CdSe 15wt％；辛酸(表面张力调节剂)1.5wt％及非极性有机溶剂正己烷73.5wt％。按照与实施例1相同的方式配置量子点墨水，经测试，上述量子点墨水的粘度为11cp(25℃)，表面张力为38dynes/cm(25℃)。
按照与实施例1相同的方式制备量子点发光器件，得到电子传输层厚30nm；量子点材料层厚28nm。
实施例9
在一个具体实施方式中，量子点墨水具有如下的组成：均***(电子传输材料)8wt％；疏水性量子点材料GaAs 5wt％；癸酸(表面张力调节剂)2wt％及非极性有机溶剂正戊烷85wt％。按照与实施例1相同的方式配置量子点墨水。经测试，上述量子点墨水的粘度为11.5cp(25℃)，表面张力为40dynes/cm(25℃)。
按照与实施例1相同的方式制备量子点发光器件，得到电子传输层厚25nm；量子点材料层厚15nm。
实施例10
在一个具体实施方式中，量子点墨水具有如下的组成：噁二唑(电子传输材料)12wt％；疏水性量子点材料CdSe 18wt％；月桂酸(表面张力调节剂)4wt％及非极性有机溶剂四氯化碳66wt％。按照与实施例1相同的方式配置量子点墨水。经测试，上述量子点墨水的粘度为12cp(25℃)，表面张力为41dynes/cm(25℃)。
按照与实施例1相同的方式制备量子点发光器件，得到电子传输层厚30nm；量子点材料层厚20nm。
实施例11
在一个具体实施方式中，量子点墨水具有如下的组成：苯醌(电子传输材料)9wt％；疏水性量子点材料CdSe 10wt％；辛酸(表面张力调节剂)2wt％及非极性有机溶剂正己烷79wt％。按照与实施例1相同的方式配置量子点墨水。经测试，上述量子点墨水的粘度为11cp(25℃)，表面张力为39dynes/cm(25℃)。
按照与实施例1相同的方式制备量子点发光器件，得到电子传输层厚25nm；量子点材料层厚17nm。
实施例12
在一个具体实施方式中，量子点墨水具有如下的组成：萘(电子传输材料)11wt％；疏水性量子点材料ZnS 13wt％；十二胺(表面张力调节剂) 1.5wt％及非极性有机溶剂环己烷74.5wt％。按照与实施例1相同的方式配置量子点墨水。经测试，上述量子点墨水的粘度为10.5cp(25℃)，表面张力为36dynes/cm(25℃)。
按照与实施例1相同的方式制备量子点发光器件，得到电子传输层厚28nm；量子点材料层厚19nm。
实施例13
在一个具体实施方式中，量子点墨水具有如下的组成：a-NPD(N’-二苯基-N,N’-二(1-萘基)-1,1’-联苯基-4,4”-二胺)(空穴传输材料)8wt％；疏水性量子点材料GaAs 5wt％；癸酸(表面张力调节剂)2wt％及非极性有机溶剂正戊烷85wt％。按照与实施例2相同的方式配置量子点墨水。经测试，上述量子点墨水的粘度为11.5cp(25℃)，表面张力为40dynes/cm(25℃)。
按照与实施例2相同的方式制备量子点发光器件，得到空穴传输层厚25nm；量子点材料层厚15nm。
实施例14
在一个具体实施方式中，量子点墨水具有如下的组成：TCCA(4,4’,4”-三(N-唑基)-三苯胺)(空穴传输材料)12wt％；疏水性量子点材料CdSe 18wt％；月桂酸(表面张力调节剂)4wt％及非极性有机溶剂正己烷66wt％。按照与实施例2相同的方式配置量子点墨水。经测试，上述量子点墨水的粘度为12cp(25℃)，表面张力为41dynes/cm(25℃)。
按照与实施例2相同的方式制备量子点发光器件，得到空穴传输层厚30nm；量子点材料层厚20nm。
实施例15
在一个具体实施方式中，量子点墨水具有如下的组成：DNTPD(N,N’-二(4-(N,N’-二苯基-氨基)苯基)-N,N’-二苯联苯胺)(空穴传输材料)9wt％；疏水性量子点材料CdSe 10wt％；辛酸(表面张力调节剂)2wt％及非极性有机溶剂正庚烷79wt％。按照与实施例2相同的方式配置量子点墨水。经测试，上述量子点墨水的粘度为11cp(25℃)，表面张力为39dynes/cm(25℃)。
按照与实施例2相同的方式制备量子点发光器件，得到空穴传输层厚25nm；量子点材料层厚17nm。
实施例16
在一个具体实施方式中，量子点墨水具有如下的组成：a-NPD(N’-二苯基-N,N’-二(1-萘基)-1,1’-联苯基-4,4”-二胺)(空穴传输材料)11wt％；疏水性量子点材料ZnS 13wt％；十二胺(表面张力调节剂)1.5wt％及非极性有机溶剂正戊烷74.5wt％。按照与实施例2相同的方式配置量子点墨水。经测试，上述量子点墨水的粘度为10.5cp(25℃)，表面张力为36dynes/cm(25℃)。
按照与实施例2相同的方式制备量子点发光器件，得到空穴传输层厚28nm；量子点材料层厚19nm。
以上所述仅是本发明的示范性实施方式，而非用于限制本发明的保护范围，本发明的保护范围由所附的权利要求确定。
本申请要求于2015年7月21日递交的中国专利申请第201510431537.8号的优先权，在此全文引用上述中国专利申请公开的内容以作为本申请的一部分。

Claims (24)

  1. 一种量子点墨水，包括非极性有机溶剂、表面张力调节剂和疏水性量子点材料，所述量子点墨水还包括载流子传输材料，所述疏水性量子点材料能够与所述载流子传输材料发生相分离。
  2. 根据权利要求1所述的量子点墨水，其中所述量子点墨水的粘度为10-12cP，表面张力为32-42dynes/cm。
  3. 根据权利要求1所述的量子点墨水，其中所述表面张力调节剂为分子量小于500的疏水性、极性有机物。
  4. 根据权利要求1所述的量子点墨水，其中所述载流子传输材料为分子量小于500的电子传输材料或者空穴传输材料。
  5. 根据权利要求1所述的量子点墨水，其中所述非极性有机溶剂在25℃下为液体且常压下沸点小于200℃。
  6. 根据权利要求1所述的量子点墨水，其中各组分的质量百分比为：载流子传输材料5％-15％，表面张力调节剂1％-5％，疏水性量子点材料2％-20％，非极性有机溶剂60％-92％。
  7. 根据权利要求1-6的任一项所述的量子点墨水，其中，所述疏水性量子点材料选自下述量子点材料中的一种或多种：CdS、CdSe、CdTe、ZnO、ZnS、ZnSe、ZnTe、GaAs、GaP、GaSb、HgS、HgSe、HgTe、InAs、InP、InSb、AlAs、AlP、CuInS、CuInSe、AlSb。
  8. 根据权利要求1-6的任一项所述的量子点墨水，其中，所述载流子传输材料为电子传输材料，所述电子传输材料选自：噁二唑、噻二唑、均***、萘、苯醌、咔唑、上述物质的衍生物及其组合。
  9. 根据权利要求1-6的任一项所述的量子点墨水，其中，所述载流子传输材料为空穴传输材料，所述空穴传输材料选自：CBP(4,4’-N,N’-二咔唑-联苯)、a-NPD(N’-二苯基-N,N’-二(1-萘基)-1,1’-联苯基-4,4”-二胺)、TCCA(4,4’,4”-三(N-唑基)-三苯胺)、DNTPD(N,N’-二(4-(N,N’-二苯基-氨基)苯基)-N,N’-二苯联苯胺)及其组合。
  10. 根据权利要求1-6的任一项所述的量子点墨水，其中，所述表面张力调节剂为有机酸、有机氨或其混合物。
  11. 根据权利要求10所述的量子点墨水，其中，所述有机酸为脂肪酸、所述有机氨为烷基氨。
  12. 根据权利要求11所述的量子点墨水，其中，所述脂肪酸选自：辛酸、癸酸、油酸、月桂酸及其组合。
  13. 根据权利要求12所述的量子点墨水，其中，所述烷基氨选自：十二胺、十六胺、十八胺、油胺及其组合。
  14. 根据权利要求1-6的任一项所述的量子点墨水，其中，所述非极性有机溶剂选自：链状烷烃、环烷烃、卤代烷烃、芳香烃、上述物质的衍生物及其组合。
  15. 根据权利要求14所述的量子点墨水，其中，所述非极性有机溶剂选自：正戊烷、正己烷、正庚烷、正辛烷、环戊烷、环己烷、氯仿、溴乙烷、四氯化碳、苯、甲苯及其组合。
  16. 根据权利要求1-6的任一项所述的量子点墨水，其中，各组分的质量百分比为：载流子传输材料8％-12％，表面张力调节剂1％-4％，疏水性量子点材料5％-18％，非极性有机溶剂66％-86％。
  17. 根据权利要求1-6的任一项所述的量子点墨水，其中，各组分的质量百分比为：载流子传输材料9％-11％，表面张力调节剂1％-2％，疏水性量子点材料10％-15％，非极性有机溶剂62％-80％。
  18. 根据权利要求1-6的任一项所述的量子点墨水，其中，所述疏水性量子点材料表面具有三辛基膦或三辛基氧化膦配体。
  19. 一种量子点墨水的制备方法，包括：
    将疏水性量子点材料、载流子传输材料、表面张力调节剂和非极性有机溶剂混合，以得到所述量子点墨水，其中，调节上述各组分的比例，使得所述疏水性量子点材料能够与所述载流子传输材料发生相分离。
  20. 根据权利要求19所述的方法，其中，所述量子点墨水的粘度为10-12cP，表面张力为32-42dynes/cm。
  21. 根据权利要求19或20所述的方法，其中，所述混合方式为搅拌、振荡或超声分散。
  22. 一种利用权利要求1-18的任一项所述的量子点墨水打印制备量子点发光二极管器件的方法，包括如下步骤：
    1)在基板上制作第一电极层；
    2)在所述第一电极层上制作第一功能层；
    3)在所述第一功能层上打印量子点墨水；
    4)量子点墨水发生相分离，形成疏水性量子点材料层和第二功能层，在所述第二功能层上制作第三功能层；
    5)在所述第三功能层上制作第二电极层。
  23. 根据权利要求22所述的方法，其中，所述载流子传输材料为电子传输材料，所述第一电极层为ITO阳极，所述第一功能层在从所述第一电极到所述第二电极的方向上顺次包括空穴注入层和空穴传输层，所述第二功能层为电子传输层，所述第三功能层为电子注入层，所述第二电极层为金属阴极。
  24. 根据权利要求22所述的方法，其中，所述载流子传输材料为空穴传输材料，所述第一电极层为金属阴极，所述第一功能层在从所述第一电极到所述第二电极的方向上顺次包括电子注入层和电子传输层，所述第二功能层为空穴传输层，所述第三功能层为空穴注入层，所述第二电极层为ITO阳极。
PCT/CN2015/099337 2015-07-21 2015-12-29 量子点墨水 WO2017012275A1 (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US15/118,234 US10311994B2 (en) 2015-07-21 2015-12-29 Quantum dot ink

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201510431537.8A CN105153807B (zh) 2015-07-21 2015-07-21 量子点墨水
CN201510431537.8 2015-07-21

Publications (1)

Publication Number Publication Date
WO2017012275A1 true WO2017012275A1 (zh) 2017-01-26

Family

ID=54794873

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2015/099337 WO2017012275A1 (zh) 2015-07-21 2015-12-29 量子点墨水

Country Status (3)

Country Link
US (1) US10311994B2 (zh)
CN (1) CN105153807B (zh)
WO (1) WO2017012275A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111117357A (zh) * 2019-12-24 2020-05-08 阜阳欣奕华材料科技有限公司 一种量子点墨水、电致发光器件

Families Citing this family (40)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105153807B (zh) 2015-07-21 2016-10-19 京东方科技集团股份有限公司 量子点墨水
CN105820663A (zh) * 2016-05-04 2016-08-03 Tcl集团股份有限公司 一种量子点墨水及其制备方法
CN106206871A (zh) * 2016-08-03 2016-12-07 纳晶科技股份有限公司 发光器件的制备方法与发光器件
CN106634205A (zh) * 2016-09-21 2017-05-10 Tcl集团股份有限公司 一种提高量子点墨水利用率的方法
CN106356386B (zh) * 2016-09-30 2019-06-07 福州大学 一种基于Micro-LED阵列背光源的喷墨打印量子点显示装置
CN106519799A (zh) * 2016-10-10 2017-03-22 Tcl集团股份有限公司 一种量子点墨水及其制备方法
CN106531895B (zh) * 2016-12-12 2019-09-10 Tcl集团股份有限公司 量子点发光二极管及其制备方法与发光模组、显示装置
CN106711283B (zh) * 2016-12-27 2019-05-24 南京理工大学 一种全印刷氧化锌纳米晶基紫外光电探测器制备方法
CN106952826A (zh) * 2017-03-30 2017-07-14 深圳市华星光电技术有限公司 一种场效应晶体管及其制备方法
EP3406455A1 (en) 2017-05-23 2018-11-28 Omya International AG Method for producing water-insoluble quantum dot patterns
CN107400414B (zh) * 2017-07-03 2021-06-29 苏州星烁纳米科技有限公司 量子点油墨及电致发光器件
CN109181414B (zh) * 2017-07-14 2022-04-15 苏州星烁纳米科技有限公司 量子点墨水以及发光二极管
CN109306207A (zh) * 2017-07-26 2019-02-05 Tcl集团股份有限公司 量子点墨水
CN107502065A (zh) * 2017-10-18 2017-12-22 福州大学 一种基于喷墨打印的量子点墨水
CN109932405B (zh) * 2017-12-15 2021-08-10 Tcl科技集团股份有限公司 量子点表面配体含量的测定方法及量子点墨水的配制方法
CN108254950B (zh) * 2018-02-09 2021-01-08 京东方科技集团股份有限公司 一种量子点小球喷洒设备
WO2019180881A1 (ja) * 2018-03-22 2019-09-26 シャープ株式会社 表示デバイスおよびその製造方法
KR20190123694A (ko) * 2018-04-24 2019-11-01 삼성전자주식회사 발광막, 그 제조 방법, 및 이를 포함하는 발광 소자
CN110408266A (zh) * 2018-04-27 2019-11-05 Tcl集团股份有限公司 无机纳米材料印刷油墨及其制备方法和应用
CN110085748B (zh) * 2018-05-25 2021-06-29 广东聚华印刷显示技术有限公司 量子点墨水及其制备方法和量子点发光器件
CN111218157A (zh) * 2018-11-23 2020-06-02 广东聚华印刷显示技术有限公司 量子点电子墨水及其制备方法
CN111384308B (zh) * 2018-12-29 2021-05-28 Tcl科技集团股份有限公司 量子点发光二极管的制备方法
CN109749742A (zh) * 2019-01-22 2019-05-14 深圳扑浪创新科技有限公司 一种氧化锌包覆量子点的制备方法
KR20210025159A (ko) 2019-08-26 2021-03-09 삼성디스플레이 주식회사 양자점 조성물, 발광 소자 및 이의 제조 방법
CN112442300B (zh) * 2019-09-04 2022-06-07 Tcl科技集团股份有限公司 量子点墨水和量子点发光二极管的制备方法
US11555149B2 (en) 2019-09-11 2023-01-17 Nanosys, Inc. Nanostructure ink compositions for inkjet printing
CN111876021A (zh) * 2019-09-16 2020-11-03 广东聚华印刷显示技术有限公司 墨水组合物及其制备方法、量子点发光器件
CN110982347A (zh) * 2019-12-16 2020-04-10 深圳市华星光电半导体显示技术有限公司 用于喷墨打印有机发光二极管的墨水组合物及其制造方法
US11441045B2 (en) 2019-12-16 2022-09-13 Shenzhen China Star Optoelectronics Semiconductor Display Technology Co., Ltd. Ink composition for inkjet printing organic light-emitting diodes and method of manufacturing the same
WO2021152790A1 (ja) * 2020-01-30 2021-08-05 シャープ株式会社 表示装置、および表示装置の製造方法
CN111534151A (zh) * 2020-05-14 2020-08-14 深圳市华星光电半导体显示技术有限公司 量子点墨水、显示面板及其制作方法
US20230180496A1 (en) * 2020-05-21 2023-06-08 Sharp Kabushiki Kaisha Display device and display device production method
CN111599931B (zh) * 2020-05-29 2022-09-20 合肥福纳科技有限公司 一种图像显示装置、量子点发光二极管及其制作方法
CN111592788B (zh) * 2020-05-29 2022-09-16 合肥福纳科技有限公司 量子点发光二极管、量子点墨水及其制作方法
US11492547B2 (en) 2020-06-04 2022-11-08 UbiQD, Inc. Low-PH nanoparticles and ligands
KR20220043997A (ko) 2020-09-28 2022-04-06 삼성디스플레이 주식회사 양자점 조성물 및 이를 이용한 발광 소자의 제조 방법
CN114686203B (zh) * 2020-12-28 2023-12-26 Tcl科技集团股份有限公司 一种量子点分散液及量子点保存方法
CN112736209B (zh) * 2020-12-30 2023-02-07 广东聚华印刷显示技术有限公司 量子点发光二极管及其制备方法、以及显示面板
TWI792259B (zh) * 2021-04-09 2023-02-11 財團法人工業技術研究院 分散液與墨水
CN115537072B (zh) * 2021-06-29 2024-04-02 广东聚华印刷显示技术有限公司 量子点墨水、量子点发光二极管及其制备方法、显示装置

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090286338A1 (en) * 2006-06-24 2009-11-19 Seth Coe-Sullivan Methods for depositing nanomaterial, methods for fabricating a device, methods for fabricating an array of devices and compositions
CN101810054A (zh) * 2007-09-28 2010-08-18 大日本印刷株式会社 电致发光元件
US8043793B2 (en) * 2007-09-28 2011-10-25 Dai Nippon Printing Co., Ltd. Method for manufacturing electroluminescence element
US8535758B2 (en) * 2002-11-07 2013-09-17 Massachusetts Institute Of Technology Materials including semiconductor nanocrystals
CN105153807A (zh) * 2015-07-21 2015-12-16 京东方科技集团股份有限公司 量子点墨水
CN105161635A (zh) * 2015-07-01 2015-12-16 Tcl集团股份有限公司 一种具有自组装电子传输层的qled器件及其制备方法

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060159838A1 (en) * 2005-01-14 2006-07-20 Cabot Corporation Controlling ink migration during the formation of printable electronic features
US7850943B2 (en) * 2004-05-28 2010-12-14 Samsung Electronics Co., Ltd. Method of preparing cadmium sulfide nanocrystals emitting light at multiple wavelengths, and cadmium sulfide nanocrystals prepared by the method
EP1666562B1 (en) * 2004-11-11 2018-03-07 Samsung Electronics Co., Ltd. Interfused nanocrystals and method of preparing the same
US8563348B2 (en) 2007-04-18 2013-10-22 Nanoco Technologies Ltd. Fabrication of electrically active films based on multiple layers
JP5407241B2 (ja) * 2007-09-28 2014-02-05 大日本印刷株式会社 エレクトロルミネッセンス素子
EP3671865B1 (en) * 2007-11-30 2023-07-19 Nanoco Technologies, Ltd. Preparation of nanoparticle material
KR101475520B1 (ko) * 2008-01-14 2014-12-23 삼성전자주식회사 잉크젯 프린트용 양자점 잉크 조성물 및 그를 이용한전자소자
KR101995370B1 (ko) 2008-04-03 2019-07-02 삼성 리서치 아메리카 인코포레이티드 양자점들을 포함하는 발광 소자
KR101462658B1 (ko) * 2008-12-19 2014-11-17 삼성전자 주식회사 반도체 나노 결정 및 그 제조 방법
US20100264371A1 (en) * 2009-03-19 2010-10-21 Nick Robert J Composition including quantum dots, uses of the foregoing, and methods
US8062555B2 (en) 2009-04-16 2011-11-22 Rhodia Operations Co-assembly method and co-assembled structures made thereby
JP2011040486A (ja) * 2009-08-07 2011-02-24 Sharp Corp 発光装置および画像表示装置
GB0916700D0 (en) 2009-09-23 2009-11-04 Nanoco Technologies Ltd Semiconductor nanoparticle-based materials
GB0916699D0 (en) * 2009-09-23 2009-11-04 Nanoco Technologies Ltd Semiconductor nanoparticle-based materials
KR101305119B1 (ko) * 2010-11-05 2013-09-12 현대자동차주식회사 잉크젯 인쇄용 반도체 산화물 잉크 조성물과 이의 제조방법 및 이를 이용한 광전변환 소자의 제조방법

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8535758B2 (en) * 2002-11-07 2013-09-17 Massachusetts Institute Of Technology Materials including semiconductor nanocrystals
US20090286338A1 (en) * 2006-06-24 2009-11-19 Seth Coe-Sullivan Methods for depositing nanomaterial, methods for fabricating a device, methods for fabricating an array of devices and compositions
CN101810054A (zh) * 2007-09-28 2010-08-18 大日本印刷株式会社 电致发光元件
US8043793B2 (en) * 2007-09-28 2011-10-25 Dai Nippon Printing Co., Ltd. Method for manufacturing electroluminescence element
CN105161635A (zh) * 2015-07-01 2015-12-16 Tcl集团股份有限公司 一种具有自组装电子传输层的qled器件及其制备方法
CN105153807A (zh) * 2015-07-21 2015-12-16 京东方科技集团股份有限公司 量子点墨水

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111117357A (zh) * 2019-12-24 2020-05-08 阜阳欣奕华材料科技有限公司 一种量子点墨水、电致发光器件
CN111117357B (zh) * 2019-12-24 2022-08-19 阜阳欣奕华材料科技有限公司 一种量子点墨水、电致发光器件

Also Published As

Publication number Publication date
US10311994B2 (en) 2019-06-04
CN105153807A (zh) 2015-12-16
US20170174921A1 (en) 2017-06-22
CN105153807B (zh) 2016-10-19

Similar Documents

Publication Publication Date Title
WO2017012275A1 (zh) 量子点墨水
US11866598B2 (en) Compositions and methods including depositing nanomaterial
US10770619B2 (en) Light-emitting devices and displays with improved performance
Yang et al. High‐resolution inkjet printing of quantum dot light‐emitting microdiode arrays
US9096425B2 (en) Methods for depositing nanomaterial, methods for fabricating a device, methods for fabricating an array of devices and compositions
US20090280586A1 (en) Methods for depositing nanomaterial, methods for fabricating a device, and methods for fabricating an array of devices
Xiong et al. Realizing 17.0% external quantum efficiency in red quantum dot light-emitting diodes by pursuing the ideal inkjet-printed film and interface
US20160293875A1 (en) Method for manufacturing quantum dot light-emitting element and display device using quantum dot
JP2008227330A (ja) 発光素子
CN105810851A (zh) 量子点发光二极管显示器的制作方法及量子点发光二极管显示器
CN102484207B (zh) 有机el元件、有机el元件的制造方法和有机el显示装置
CN111393908B (zh) 量子点墨水及其制备方法
Zheng et al. High-brightness perovskite quantum dot light-emitting devices using inkjet printing
US11637257B2 (en) Electroluminescent material ink and electroluminescent device thereof
Nguyen et al. Electrohydrodynamic jet-sprayed quantum dots for solution-processed light-emitting-diodes
Qian et al. 6‐2: Invited paper: Key challenges towards the commercialization of quantum‐dot light‐emitting diodes
Kaçar et al. A review of high-end display technologies focusing on inkjet printed manufacturing
US20240215353A1 (en) Display device and method of manufacturing the same
JP2019108244A (ja) 半導体微粒子組成物、量子ドット、それらを含有する塗工液、インキ組成物、およびそれらの用途。
Jung et al. 83‐1: Improved performance of EL‐QD display through surface modified QDs and inorganic nanoink
JP2008218241A (ja) 有機エレクトロルミネッセンスディスプレイの製造方法及び有機エレクトロルミネッセンスディスプレイ

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 15118234

Country of ref document: US

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15898831

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 15898831

Country of ref document: EP

Kind code of ref document: A1

122 Ep: pct application non-entry in european phase

Ref document number: 15898831

Country of ref document: EP

Kind code of ref document: A1

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205A DATED 27.08.2018)

122 Ep: pct application non-entry in european phase

Ref document number: 15898831

Country of ref document: EP

Kind code of ref document: A1