WO2023051317A1 - Nanomatériau d'oxyde de tungstène et son procédé de préparation et dispositif optoélectronique - Google Patents

Nanomatériau d'oxyde de tungstène et son procédé de préparation et dispositif optoélectronique Download PDF

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WO2023051317A1
WO2023051317A1 PCT/CN2022/119906 CN2022119906W WO2023051317A1 WO 2023051317 A1 WO2023051317 A1 WO 2023051317A1 CN 2022119906 W CN2022119906 W CN 2022119906W WO 2023051317 A1 WO2023051317 A1 WO 2023051317A1
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tungsten oxide
halogenated
zns
acid
preparation
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PCT/CN2022/119906
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Chinese (zh)
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徐威
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Tcl科技集团股份有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G41/00—Compounds of tungsten
    • C01G41/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/34—Halogenated alcohols
    • C07C31/36—Halogenated alcohols the halogen not being fluorine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/41—Preparation of salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
    • C07C53/15—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen containing halogen
    • C07C53/16—Halogenated acetic acids
    • 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]
    • H10K50/17—Carrier injection layers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the present application relates to the field of display technology, and in particular to a preparation method of tungsten oxide nanomaterials, tungsten oxide nanomaterials prepared by the preparation method, and photoelectric devices.
  • Optoelectronic devices refer to devices made according to the photoelectric effect, which have a wide range of applications in new energy, sensing, communication, display, lighting and other fields, such as solar cells, photodetectors, electroluminescent devices, etc.
  • the light-emitting elements of the display panels of electronic products such as computers and mobile phones are mainly electroluminescent devices.
  • the existing widely used electroluminescent devices are mainly organic electroluminescent devices (OLEDs) and quantum dot electroluminescent devices (QLEDs).
  • the structure of a traditional electroluminescent device mainly includes an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer and a cathode. Under the action of the electric field, the holes generated by the anode of the electroluminescent device and the electrons generated by the cathode move, inject into the hole transport layer and the electron transport layer respectively, and finally migrate to the light-emitting layer. When the two meet in the light-emitting layer , to generate energy excitons, thereby exciting the luminescent molecules and finally producing visible light.
  • electroluminescent devices can effectively improve the efficiency and lifetime of electroluminescent devices.
  • existing electroluminescent devices have poor hole injection and/or transport capabilities due to various reasons, resulting in an unbalanced electron-hole injection of the electroluminescent device.
  • top-emitting electroluminescent devices are generally used.
  • top-emitting electroluminescent devices usually requires increasing the thickness of the hole injection layer of the electroluminescent device to optimize the cavity length of the device, and the increase in the thickness of the hole injection layer of the electroluminescent device will lead to The hole injection capability of the electroluminescent device is reduced, which makes the electron-hole injection in the electroluminescent device unbalanced, resulting in low efficiency and life of the electroluminescent device.
  • inorganic materials can effectively solve the problem of device performance degradation due to water absorption in organic materials
  • hole injection materials and hole transport materials has become a relatively popular technology in the preparation of electroluminescent devices.
  • tungsten oxide (WO 3 ) with a band gap of 2.6-2.8eV, can absorb blue light in sunlight, and has good chemical stability, adjustable W/O stoichiometry, adjustable energy level structure, and Due to its high mobility and low price, it is used as a hole injection material or a hole transport material.
  • the hole injection performance of WO 3 prepared by the existing preparation method is poor, so that the electron-hole injection in the electroluminescent device is unbalanced, resulting in low efficiency and life of the electroluminescent device.
  • the present application provides a tungsten oxide nanomaterial, a preparation method thereof, and a photoelectric device.
  • the embodiment of the present application provides a method for preparing tungsten oxide nanomaterials, which includes the following steps:
  • the tungstic acid is mixed with a halogenated compound, wherein the halogenated compound is selected from one or more of halogenated acids and halogenated alcohols, and heated to react to obtain tungsten oxide nanomaterials, and the tungsten oxide nanomaterials It includes tungsten oxide nanoparticles and ligands connected on the surface of the tungsten oxide nanoparticles, and the ligands include one or more of haloacid ligands and halohydrin ligands.
  • the temperature range of the heating reaction is 40-80°C, and the heating reaction time is 48-72h.
  • the range of the mass ratio of the tungstic acid to the halogenated compound is (1.0:1)-(9.1:1).
  • the preparation method of the tungstic acid is as follows: mixing tungstate and acid to react to obtain tungstic acid.
  • the tungstate is selected from one or more of sodium tungstate, titanium tungstate, nickel tungstate and magnesium tungstate.
  • the tungstate includes one or more of titanium tungstate, nickel tungstate and magnesium tungstate, and the tungsten oxide nanoparticles are doped with doping metal elements, and the doping metal elements are selected from One or more of Ti, Ni and Mg.
  • the molar amount of the doping metal element is 1-20% of the molar amount of the tungsten oxide.
  • a step of adding a weak base is also included.
  • the weak base is selected from one or more of K 2 CO 3 , KHCO 3 , Na 2 CO 3 and NaHCO 3 .
  • the range of the molar ratio of the tungstic acid to the weak base is (1:1.1)-(1:1.5).
  • the halogenated acid is halogenated acetic acid
  • the halogenated alcohol is halogenated alcohol
  • the halogenated acetic acid is selected from one or more of monochlorinated acetic acid, dichlorinated acetic acid and trichloroacetic acid
  • the described halogenated alcohol is selected from monochlorinated ethanol, dichlorinated ethanol and trichloroacetic acid
  • chloroethanols One or more of chloroethanols.
  • the present application also provides a tungsten oxide nanomaterial, wherein the tungsten oxide nanomaterial includes tungsten oxide nanoparticles and ligands attached to the surface of the tungsten oxide nanoparticles, and the ligands include halogenated acid ligands.
  • the ligands include halogenated acid ligands.
  • the content of the ligand is in the range of 10-50wt%.
  • the tungsten oxide nanoparticles are doped with doping metal elements.
  • the doping metal element is selected from one or more of Ti, Ni and Mg.
  • the molar amount of the doping metal element is 1-20% of the molar amount of the tungsten oxide.
  • the average particle diameter of the tungsten oxide nanoparticles is 8-15nm.
  • the haloacid in the haloacid ligand is haloacetic acid
  • the halohydrin in the halohydrin ligand is haloethanol
  • the halogenated acetic acid is selected from one or more of monochlorinated acetic acid, dichlorinated acetic acid and trichloroacetic acid
  • the described halogenated alcohol is selected from monochlorinated ethanol, dichlorinated ethanol and trichloroacetic acid
  • chloroethanols One or more of chloroethanols.
  • the present application also provides a photoelectric device, including a stacked anode, a hole functional layer, a light-emitting layer, and a cathode, wherein the hole functional layer includes the aforementioned tungsten oxide nanomaterial.
  • the anode is selected from doped metal oxide electrodes or composite electrodes
  • the doped metal oxide electrodes are selected from indium-doped tin oxide, fluorine-doped tin oxide, antimony-doped tin oxide, aluminum-doped tin oxide
  • the composite electrode is selected from AZO/Ag/AZO, AZO/Al/AZO , ITO/Ag/ITO, ITO/Al/ITO, ZnO/Ag/ZnO, ZnO/Al/ZnO, TiO 2 /Ag/TiO 2 , TiO 2 /Al/TiO 2 , ZnS/Ag/ZnS or ZnS/Al /ZnS;
  • the light-emitting layer is an organic light-emitting layer or a quantum dot light-emitting layer
  • the material of the organic light-emitting layer is selected from 4,4'-bis(N-carbazole)-1,1'-biphenyl:tri[2-(p Tolyl)pyridine-C2,N)Iridium(III), 4,4',4"-tri(carbazol-9-yl)triphenylamine: Tris[2-(p-tolyl)pyridine-C2,N)
  • iridium(III) diarylanthracene derivatives, stilbene aromatic derivatives, pyrene derivatives, fluorene derivatives, TBPe fluorescent materials, TTPA fluorescent materials, TBRb fluorescent materials, and DBP fluorescent materials multiple
  • the material of the quantum dot light-emitting layer is selected from one or more of single-structure quantum dots and core-shell structure quantum dots
  • the single-structure quantum dots are selected from II-VI group compounds and III-V group compounds
  • the cathode is selected from one or more of Ag electrodes, Al electrodes, Au electrodes, Pt electrodes, Ag/IZO electrodes, IZO electrodes or alloy electrodes.
  • the tungsten oxide nanomaterial prepared by the preparation method of the tungsten oxide nanomaterial of the present application includes tungsten oxide nanoparticles and one or more of the haloacid ligands and the halohydrin ligands attached to the surface of the tungsten oxide nanoparticles. kind.
  • the haloacid ligand and the halohydrin ligand can effectively passivate the defect state luminescence of tungsten oxide nanoparticles, improve the dispersibility and stability of tungsten oxide nanoparticles in solvents, and improve the
  • the hole mobility of the hole functional layer can improve the hole injection and transport capabilities of optoelectronic devices, thereby improving the charge balance in optoelectronic devices, thereby improving the external quantum efficiency and life of optoelectronic devices.
  • Fig. 1 is a flow chart of a preparation method of a tungsten oxide nanomaterial provided in an embodiment of the present application
  • Fig. 2 is a schematic structural diagram of an optoelectronic device provided by an embodiment of the present application
  • Fig. 3 is a schematic structural diagram of another optoelectronic device provided by the embodiment of the present application.
  • Fig. 4 is a schematic structural diagram of another optoelectronic device provided by an embodiment of the present application.
  • Embodiments of the present application provide a tungsten oxide nanomaterial, a preparation method thereof, and an optoelectronic device. Each will be described in detail below. It should be noted that the description sequence of the following embodiments is not intended to limit the preferred sequence of the embodiments. In addition, in the description of the present application, the term “including” means “including but not limited to”.
  • expressions such as “one or more” refer to one or more of the listed items, and “multiple” refers to any combination of two or more of these items, including single items (species) ) or any combination of plural items (species), for example, "at least one (species) of a, b, or c" or "at least one (species) of a, b, and c" can mean: a ,b,c,a-b (that is, a and b),a-c,b-c, or a-b-c, where a,b,c can be single or multiple.
  • the embodiment of this application provides a preparation method of tungsten oxide nanomaterials, including the following steps:
  • Step S11 providing tungstic acid
  • Step S12 Mix tungstic acid with a halogenated compound, the halogenated compound includes one or more of halogenated acid and halogenated alcohol; heat the reaction to obtain tungsten oxide nanomaterials, and the tungsten oxide nanomaterials include oxidized Tungsten nanoparticles and ligands connected to the surface of the tungsten oxide nanoparticles, the ligands include one or more of haloacid ligands and halohydrin ligands.
  • the tungstic acid may be selected from but not limited to one or more of white tungstic acid, yellow tungstic acid and metatungstic acid.
  • the tungstic acid is produced by the following method: mixing tungstate with acid and reacting to obtain tungstic acid.
  • the tungstate can be selected from but not limited to sodium tungstate (Na 2 WO 4 ), titanium tungstate (TiW 2 O 5 ), nickel tungstate (NiW 2 O 5 ) and magnesium tungstate (MgWO 4 ). one or more.
  • the sodium tungstate can be sodium tungstate dihydrate (Na 2 WO 4 ⁇ 2H 2 O)
  • the titanium tungstate can be titanium tungstate hexahydrate (TiW 2 O 5 ⁇ 2H 2 O)
  • the tungstate The nickel may be nickel tungstate hexahydrate (NiW 2 O 5 ⁇ 2H 2 O), and the magnesium tungstate may be magnesium tungstate dihydrate (MgWO 4 ⁇ 2H 2 O).
  • the prepared tungstate will contain one or more of metal elements such as Ti, Ni and Mg.
  • metal elements such as Ti, Ni and Mg.
  • the tungsten oxide nanoparticles in the tungsten oxide nanomaterials prepared in step S14 are metal element-doped tungsten oxide nanoparticles, and the tungsten oxide nanomaterials include metal element-doped tungsten oxide nanoparticles and connecting haloacid ligands and/or halohydrin ligands on the surface of the tungsten oxide nanoparticles.
  • the doping metal elements include but not limited to one or more of Ti, Ni and Mg.
  • the acid is an acid commonly used in the preparation of tungstic acid, for example, it can be selected from but not limited to one or more of nitric acid and hydrochloric acid. In one embodiment, the acid is 10% nitric acid in water.
  • the preparation method of white tungstic acid further includes the step of cleaning the tungstic acid with a cleaning agent.
  • the cleaning agent can be isopropanol, cyclohexane, ethanol, etc. that are conventionally used for cleaning tungstic acid.
  • the halogenated acid refers to a compound containing both a halogen atom and a carboxyl group in the molecule.
  • the halogen atom may be selected from but not limited to one or more of fluorine (F), chlorine (Cl), bromine (Br) and iodine (I).
  • the haloacid is the haloacetic acid.
  • the haloacid is selected from monochlorinated acetic acid (CH 2 ClCOOH), dichlorinated acetic acid (CHCl 2 COOH) and trichloroacetic acid.
  • acetic acid CCl 3 COOH.
  • the halogenated alcohol refers to a compound containing both a halogen atom and a -CH 2 -OH group in the molecule.
  • the halogen atom may be selected from but not limited to one or more of fluorine (F), chlorine (Cl), bromine (Br) and iodine (I).
  • the halogenated alcohol is the halogenated alcohol.
  • the halogenated alcohol is selected from monochlorinated ethanol (CH 2 ClCH 2 OH), dichlorinated alcohol (CHCl 2 CH 2 OH ) and one or more of trichloroethanol (CCl 3 CH 2 OH).
  • the mass ratio of the tungstic acid to the haloacid and/or halohydrin ranges from (1.0:1) to (9.1:1).
  • the method of mixing tungstic acid and halogenated compound is ultrasonic, so that tungstic acid is uniformly dispersed in the halogenated acid and/or halogenated alcohol.
  • a weak base needs to be added to adjust the pH value of the solution to 6-8, thereby promoting the reaction between the tungstic acid and the halogenated compound. Form a coordination bond.
  • the weak base may be selected from but not limited to one or more of K 2 CO 3 , KHCO 3 , Na 2 CO 3 and NaHCO 3 .
  • the weak base is an aqueous solution of a weak base, and the content of the weak base in the aqueous solution of the weak base is 10-30 wt%.
  • the molar ratio of the tungstic acid to the weak base is in the range of (1:1.1)-(1:1.5).
  • the temperature range of the heating is 40-80°C.
  • the reaction time is 48-72h. It can be understood that, in order to make the reaction proceed quickly and fully, the reaction can be carried out under stirring.
  • the content of the ligand is in the range of 10-50wt%. If the ligand content is too low, the defect state luminescence of the tungsten oxide nanoparticles cannot be effectively passivated; if the ligand content is too high, the conductivity of the tungsten oxide nanomaterials will be too low.
  • the average particle diameter of the tungsten oxide nanoparticles is 8-15nm. If the particle size of the tungsten oxide nanoparticles is too small, the electrical conductivity is poor and unstable; The energy level mismatch will cause difficulty in carrier injection.
  • the tungsten oxide nanoparticles may be doped with doping metal elements, in other words, the tungsten oxide nanoparticles are tungsten oxide nanoparticles doped with metal elements.
  • the doping metal element may be selected from but not limited to one or more of Ti, Ni and Mg. The metal element doping can effectively improve the hole concentration and hole mobility of the tungsten oxide nanomaterial.
  • the molar amount of the doping metal element is 1-20% of that of the tungsten oxide. If the content of the doping metal element is too low, there will be no doping effect, and if the content is too high, the doping metal element will be crystallized separately.
  • the tungsten oxide nanomaterial prepared by the preparation method of the tungsten oxide nanomaterial comprises tungsten oxide nanoparticles and one or more of halogenated acid ligands and halogenated alcohol ligands attached to the surface of the tungsten oxide nanoparticles .
  • the haloacid ligand and the halohydrin ligand can effectively passivate the defect state luminescence of tungsten oxide nanoparticles, improve the dispersibility and stability of tungsten oxide nanoparticles in solvents, and improve the
  • the hole mobility of the hole functional layer can improve the hole injection and transport capabilities of optoelectronic devices, thereby improving the charge balance in optoelectronic devices, thereby improving the external quantum efficiency and life of optoelectronic devices.
  • the embodiment of the present application also provides a hole-functional thin film, and the hole-functional thin film may be a hole injection thin film or a hole transport thin film.
  • the hole function thin film includes the tungsten oxide nanomaterial.
  • the embodiment of the present application also provides a method for preparing the hole function thin film, comprising the following steps:
  • Step S21 providing the tungsten oxide nanomaterial
  • Step S22 disposing the tungsten oxide nanomaterial on the substrate to form a thin film of the tungsten oxide nanomaterial, that is, to obtain a hole-energy film.
  • the type of the substrate is not limited.
  • the substrate is an anode substrate, and the substrate may be a conventionally used substrate such as glass, and the tungsten oxide nanomaterial is disposed on the anode.
  • the substrate includes a stacked cathode and a light-emitting layer, and the tungsten oxide nanomaterial is disposed on the light-emitting layer.
  • the method of disposing the tungsten oxide nanomaterial on the substrate may be a chemical method or a physical method.
  • the chemical method can be chemical vapor deposition method, continuous ion layer adsorption and reaction method, anodic oxidation method, electrolytic deposition method and co-precipitation method, etc.
  • the physical method can be physical coating method or solution processing method, and the physical coating method can be thermal evaporation coating method CVD, electron beam evaporation coating method, magnetron sputtering method, multi-arc ion coating method, physical vapor deposition method PVD, atomic layer deposition method and pulse laser deposition method, etc.; the solution processing method can be spin coating method, printing method, inkjet printing method, scraping method, printing method, dipping and pulling method, soaking method, spraying method, roller coating method, casting method, Slot coating method and strip coating method, etc.
  • the method of disposing the tungsten oxide nanomaterial on the substrate is a solution method, at this time, the tungsten oxide nanomaterial needs to be dispersed with a dispersant to obtain a tungsten oxide nanomaterial dispersion, Then the tungsten oxide nanomaterial dispersion is disposed on the substrate by a solution method.
  • the dispersant may be selected from but not limited to one or more of methanol, ethanol, butanol and pentanol. In one embodiment, the concentration range of the dispersion is 5-40 mg/mL.
  • the embodiment of the present application also provides an optoelectronic device 100 , and the optoelectronic device 100 may be a solar cell, a photodetector, an organic optoelectronic device (OLED) or a quantum dot optoelectronic device (QLED).
  • the optoelectronic device 100 includes an anode 10 , a hole functional layer 20 , a light emitting layer 30 and a cathode 40 which are sequentially stacked.
  • the hole functional layer 20 includes one or more of a hole injection layer 21 and a hole transport layer 22 .
  • the hole injection layer 21 and/or the hole transport layer 22 is the hole energy film, in other words, the hole injection layer 21 and/or the hole transport layer 22 includes the oxide Tungsten nanomaterials.
  • the optoelectronic device 100 includes an anode 10 , a hole injection layer 21 , a light emitting layer 30 and a cathode 40 which are sequentially stacked.
  • the hole injection layer 21 includes the tungsten oxide nanomaterial.
  • the optoelectronic device 100 includes an anode 10 , a hole transport layer 22 , a light emitting layer 30 and a cathode 40 which are sequentially stacked.
  • the hole transport layer 22 includes the tungsten oxide nanomaterial.
  • the optoelectronic device 100 includes an anode 10 , a hole injection layer 21 , a hole transport layer 22 , a light emitting layer 30 and a cathode 40 which are sequentially stacked.
  • the hole injection layer 21 and/or the hole transport layer 22 includes the tungsten oxide nanomaterial.
  • the material of the anode 10 is known in the art for anode materials, for example, can be selected from but not limited to doped metal oxide electrodes, composite electrodes and the like.
  • the doped metal oxide electrode may be selected from but not limited to indium doped tin oxide (ITO), fluorine doped tin oxide (FTO), antimony doped tin oxide (ATO), aluminum doped zinc oxide (AZO), One or more of gallium-doped zinc oxide (GZO), indium-doped zinc oxide (IZO), magnesium-doped zinc oxide (MZO) and aluminum-doped magnesium oxide (AMO).
  • the composite electrode is a composite electrode with a metal layer sandwiched between doped or non-doped transparent metal oxide layers, such as AZO/Ag/AZO, AZO/Al/AZO, ITO/Ag/ITO, ITO/Al/ ITO, ZnO/Ag/ZnO, ZnO/Al/ZnO, TiO 2 /Ag/TiO 2 , TiO 2 /Al/TiO 2 , ZnS/Ag/ZnS, ZnS/Al/ZnS, etc.
  • "/" indicates a laminated structure
  • AZO/Ag/AZO indicates a composite electrode with a laminated structure formed by sequentially laminating an AZO layer, an Ag layer and an AZO layer.
  • the light emitting layer 30 may be an organic light emitting layer or a quantum dot light emitting layer.
  • the optoelectronic device 100 may be an organic optoelectronic device.
  • the optoelectronic device 100 may be a quantum dot optoelectronic device.
  • the material of the organic light-emitting layer is a material known in the art for the organic light-emitting layer of optoelectronic devices, for example, can be selected from but not limited to CBP:Ir(mppy)3(4,4'-bis(N-carbazole )-1,1'-biphenyl: Tris[2-(p-tolyl)pyridine-C2,N) iridium(III)), TCTA:Ir(mmpy)(4,4',4"-tri(carba Azol-9-yl)triphenylamine: tris[2-(p-tolyl)pyridine-C2,N)iridium(III)), diarylanthracene derivatives, stilbene aromatic derivatives, pyrene derivatives or One or more of fluorene derivatives, TBPe fluorescent material emitting blue light, TTPA fluorescent material emitting green light, TBRb fluorescent material emitting orange light, and DBP fluorescent material emitting red light.
  • the material of the quantum dot light-emitting layer is a quantum dot material known in the art for the quantum dot light-emitting layer of an optoelectronic device, for example, it can be selected from but not limited to one or more of a single-structure quantum dot and a core-shell structure quantum dot Various.
  • the single-structure quantum dots may be selected from, but not limited to, one or more of II-VI compounds, III-V compounds, and I-III-VI compounds.
  • the II-VI group compound can be selected from but not limited to CdSe, CdS, CdTe, ZnSe, ZnS, CdTe, ZnTe, CdZnS, CdZnSe, CdZnTe, ZnSeS, ZnSeTe, ZnTeS, CdSeS, CdSeTe, CdTeS, CdZnSeTe and One or more of CdZnSTe;
  • the III-V compound can be selected from but not limited to one or Various;
  • the I-III-VI compound may be selected from but not limited to one or more of CuInS 2 , CuInSe 2 and AgInS 2 .
  • the quantum dots of the core-shell structure can be selected from but not limited to CdSe/ZnS, CdSe/ZnSe/ZnS, ZnCdSe/ZnSe/ZnS, ZnSe/ZnS, ZnSeTe/ZnS, CdSe/CdZnSeS/ZnS, InP/ZnSe/ZnS and One or more of InP/ZnSeS/ZnS.
  • the cathode 40 is a cathode known in the art for optoelectronic devices, for example, can be selected from but not limited to Ag electrodes, Al electrodes, Au electrodes, Pt electrodes, Ag/IZO electrodes, IZO electrodes or alloy electrodes or one of them.
  • the Ag/IZO electrode refers to a composite electrode having a laminated structure formed by laminating an Ag layer and an IZO layer.
  • the optoelectronic device 100 further includes an electron transport layer, and the electron transport layer is connected between the light emitting layer 30 and the cathode 40 .
  • the material of the electron transport layer is a material known in the art for the electron transport layer, for example, can be selected from but not limited to ZnO, TiO 2 , ZrO 2 , HfO 2 , Ca, Ba, CsF, LiF, CsCO 3 , One or more of ZnMgO, PBD (2-(4-biphenyl)-5-phenyloxadiazole), 8-hydroxyquinoline aluminum (Alq3) and graphene.
  • the material of the hole transport layer 22 can be known in the art.
  • Known materials for the hole transport layer can be selected from but not limited to poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA), 2,2' ,7,7'-tetra[N,N-bis(4-methoxyphenyl)amino]-9,9'-spirobifluorene (spiro-omeTAD), 4,4'-cyclohexylbis[N, N-bis(4-methylphenyl)aniline](TAPC), N,N'-bis(1-naphthyl)-N,N'-diphenyl-1,1'-diphenyl-4, 4'-diamine (NPB), 4,4'-bis(N-carbazole)-1,1'-
  • the material of the hole injection layer 21 is known in the art
  • the material used for the hole injection layer can be selected from but not limited to 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene One or more of (HAT-CN), PEDOT:PSS and its derivative doped with s-MoO 3 (PEDOT:PSS:s-MoO 3 ).
  • the optoelectronic device 100 can also add some functional layers that are conventionally used in optoelectronic devices to help improve the performance of optoelectronic devices, such as electron blocking layers, hole blocking layers, electron injection layers and Interface modification layer, etc.
  • each layer of the optoelectronic device 100 can be adjusted according to the light emission requirement of the optoelectronic device 100 .
  • the optoelectronic device 100 may be a positive optoelectronic device or an inverted optoelectronic device.
  • the embodiment of the present application also provides a method for preparing the optoelectronic device 100, including the following steps:
  • Step S31 providing the anode 10
  • Step S32 providing the tungsten oxide nanomaterial, and disposing the tungsten oxide nanomaterial on the anode 10 to obtain a hole functional layer 20;
  • Step S33 sequentially forming a laminated light-emitting layer 30 and a cathode 40 on the hole functional layer 20 .
  • the step S33 is: sequentially forming a stacked light emitting layer 30 , an electron transport layer and a cathode 40 on the hole functional layer 20 .
  • the embodiment of the present application also provides another method for preparing the optoelectronic device 100, which includes the following steps:
  • Step S41 providing a cathode 40, and forming a light-emitting layer 30 on the cathode 40;
  • Step S42 providing the tungsten oxide nanomaterial, and disposing the tungsten oxide nanomaterial on the light-emitting layer 30 to obtain the hole functional layer 20;
  • Step S43 forming the anode 10 on the hole functional layer 20 .
  • the step S41 is: providing a cathode 40 , and sequentially forming a laminated electron transport layer and a light emitting layer 30 on the cathode 40 .
  • the method for forming the anode 10, the light-emitting layer 30, the electron transport layer and the cathode 40 can be realized by conventional techniques in the art, such as chemical or physical methods.
  • the chemical method or physical method can be referred to above, and will not be repeated here.
  • the preparation method of the photoelectric device 100 also includes forming the functional layer layer steps.
  • An ITO/Ag/ITO composite anode 10 is provided, and the thicknesses of the ITO layer, the Ag layer and the ITO layer stacked in the ITO/Ag/ITO composite anode 10 are respectively 10nm, 100nm, and 10nm;
  • PEDOT:PSS model AI4083
  • tungsten oxide nanomaterial dispersion Disperse the tungsten oxide nanomaterial in cyclohexane to obtain a tungsten oxide nanomaterial dispersion with a concentration of 20 mg/mL, spin-coat the tungsten oxide nanomaterial dispersion on the hole injection layer 21, and then Heat treatment at 100° C. for 30 minutes to obtain a hole transport layer 22 with a thickness of 24 nm;
  • the NPB material was vapor-deposited on the cathode 40 to obtain a covering layer with a thickness of 60 nm, and the photoelectric device 100 was obtained.
  • the optoelectronic device 100 of this embodiment is a quantum dot optoelectronic device.
  • This example is basically the same as Example 1, the difference is that in this example, 8mmol Na 2 WO 4 2H 2 O and 1mmol TiW 2 O 5 6H 2 O were dissolved in 100ml deionized water, correspondingly, the obtained oxidation
  • the tungsten nano material comprises Ti-doped tungsten oxide nanoparticles and monochlorinated acetic acid ligands connected on the surface of the tungsten oxide nanoparticles.
  • the molar amount of Ti is 10% of the molar amount of W.
  • This example is basically the same as Example 1, the difference is that in this example, 8mmol Na 2 WO 4 2H 2 O and 1mmol NiW 2 O 5 6H 2 O were dissolved in 100ml deionized water, correspondingly, the obtained oxidation
  • the tungsten nano material comprises Ni-doped tungsten oxide nanoparticles and monochlorinated acetic acid ligands connected on the surface of the tungsten oxide nanoparticles.
  • the molar amount of Ni is 10% of the molar amount of W.
  • This example is basically the same as Example 1, the difference is that in this example, 8mmol Na 2 WO 4 2H 2 O and 2mmol MgWO 4 2H 2 O were dissolved in 100ml deionized water, correspondingly, the obtained tungsten oxide nano
  • the materials include Mg-doped tungsten oxide nanoparticles and monochlorinated acetic acid ligands connected on the surface of the tungsten oxide nanoparticles.
  • the molar amount of Mg is 20% of the molar amount of W.
  • This example is basically the same as Example 1, except that 8.5mmol Na 2 WO 4 2H 2 O, 0.5mmol NiW 2 O 5 6H 2 O and 0.5mmol MgWO 4 2H 2 O were dissolved in In 100ml of deionized water, correspondingly, the obtained tungsten oxide nanomaterials include Ni and Mg doped tungsten oxide nanoparticles and acetic acid monochloride ligands attached to the surface of the tungsten oxide nanoparticles.
  • the molar amount of Ni is 5% of the molar amount of W
  • the molar amount of Mg is 5% of the molar amount of W.
  • This example is basically the same as Example 1, the difference is that in this example, 8.5mmol Na 2 WO 4 ⁇ 2H 2 O, 0.5mmol TiW 2 O 5 ⁇ 6H 2 O and 0.5mmol MgWO 4 ⁇ 2H 2 O were dissolved in 100ml of deionized water, correspondingly, the obtained tungsten oxide nanomaterials include Ti and Mg doped tungsten oxide nanoparticles and acetic acid monochloride ligands attached to the surface of the tungsten oxide nanoparticles.
  • the molar weight of Ti is 5% of the molar weight of W
  • the molar weight of Mg is 5% of the molar weight of W.
  • This example is basically the same as Example 1, the difference is that the H 2 WO 4 precipitate is dissolved in 150 mL of dichlorinated ethanol, and correspondingly, the obtained tungsten oxide nanomaterials include tungsten oxide nanoparticles and tungsten oxide nanoparticles connected to the Ethanol dichloride ligands on the surface of tungsten oxide nanoparticles.
  • An ITO/Ag/ITO composite anode 10 is provided, and the thicknesses of the ITO layer, the Ag layer and the ITO layer stacked in the ITO/Ag/ITO composite anode 10 are respectively 10nm, 100nm, and 10nm;
  • the NPB material was vapor-deposited on the cathode 40 to obtain a covering layer with a thickness of 60 nm, and the photoelectric device 100 was obtained.
  • the optoelectronic device 100 of this embodiment is an organic optoelectronic device.
  • This comparative example is basically the same as Example 1, except that the material of the hole transport 22 in this comparative example is TFB.
  • This comparative example is basically the same as Example 8, except that the material of the hole injection layer 21 in this comparative example is PEDOT:PSS (model: AI4083).
  • the external quantum efficiency EQE and lifetime T95_1knit tests were performed on the optoelectronic devices of Examples 1-8 and Comparative Examples 1-2. Among them, the external quantum efficiency EQE is measured by EQE optical testing equipment, and the life test is carried out through the life test box.
  • the life time T95_1knit refers to the time for the quantum dot light-emitting diode to decay to 95% of the initial brightness of 1knit.
  • the test results are shown in Table 1 below.
  • Example 1 15 12000 Example 2 16 13000 Example 3 15 12000 Example 4 17 13000 Example 5 14 11000 Example 6 15 14000 Example 7 16 15000 Example 8 15 10000 Comparative example 1 10 2000 Comparative example 2 5 3000
  • the external quantum efficiency and the lifespan of the quantum dot optoelectronic device of embodiment 1-7 are obviously higher than the external quantum efficiency and the life of the quantum dot optoelectronic device of comparative example 1, the external quantum efficiency of the organic optoelectronic device of embodiment 8
  • the external quantum efficiency and the lifetime of the organic optoelectronic device of Comparative Example 2 are obviously higher than that of the organic optoelectronic device.

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Abstract

L'invention concerne un procédé de préparation d'un nanomatériau d'oxyde de tungstène, un nanomatériau d'oxyde de tungstène et un dispositif optoélectronique. Le procédé de préparation consiste à : fournir de l'acide tungstique ; et mélanger l'acide tungstique avec un composé halogéné, le composé halogéné étant choisi parmi un ou plusieurs acides halogénés et alcools halogénés, puis chauffer et faire réagir ceux-ci pour obtenir un nanomatériau d'oxyde de tungstène. Le nanomatériau d'oxyde de tungstène comprend des nanoparticules d'oxyde de tungstène et des ligands connectés à des surfaces des nanoparticules d'oxyde de tungstène et les ligands comprennent un ou plusieurs ligands d'haloacide et ligands d'halohydrine. Le dispositif optoélectronique comprend : une anode, une couche à fonction de trou, une couche électroluminescente et une cathode qui sont empilées, la couche à fonction de trou comprenant le nanomatériau d'oxyde de tungstène. Le nanomatériau d'oxyde de tungstène a une mobilité de trous élevée, ce qui peut améliorer les capacités d'injection et de transport de trous du dispositif optoélectronique, améliorant ainsi l'équilibre de charge dans le dispositif optoélectronique et améliorant ainsi l'efficacité quantique externe et la durée de vie du dispositif optoélectronique.
PCT/CN2022/119906 2021-09-30 2022-09-20 Nanomatériau d'oxyde de tungstène et son procédé de préparation et dispositif optoélectronique WO2023051317A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101318703A (zh) * 2008-07-08 2008-12-10 清华大学 一种氧化钨纳米线及氧化钨纳米线氨敏传感器的制备方法
US20120165563A1 (en) * 2007-03-20 2012-06-28 R.T. Vanderbilt Company, Inc. Organic tungsten complexes
CN103011293A (zh) * 2013-01-05 2013-04-03 吉林大学 一种三氧化钨的合成方法
JP2015140261A (ja) * 2014-01-27 2015-08-03 株式会社Kri 酸化タングステン粒子の製造方法
US20160178804A1 (en) * 2013-08-05 2016-06-23 Beijing University Of Chemical Technology Preparation Methods and Uses of Doped VIB Group Metal Oxide Nanoparticles or Dispersions Thereof
CN106299159A (zh) * 2016-08-25 2017-01-04 纳晶科技股份有限公司 金属氧化物纳米颗粒的制备方法及量子点电致发光器件

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120165563A1 (en) * 2007-03-20 2012-06-28 R.T. Vanderbilt Company, Inc. Organic tungsten complexes
CN101318703A (zh) * 2008-07-08 2008-12-10 清华大学 一种氧化钨纳米线及氧化钨纳米线氨敏传感器的制备方法
CN103011293A (zh) * 2013-01-05 2013-04-03 吉林大学 一种三氧化钨的合成方法
US20160178804A1 (en) * 2013-08-05 2016-06-23 Beijing University Of Chemical Technology Preparation Methods and Uses of Doped VIB Group Metal Oxide Nanoparticles or Dispersions Thereof
JP2015140261A (ja) * 2014-01-27 2015-08-03 株式会社Kri 酸化タングステン粒子の製造方法
CN106299159A (zh) * 2016-08-25 2017-01-04 纳晶科技股份有限公司 金属氧化物纳米颗粒的制备方法及量子点电致发光器件

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