WO2023051461A1 - Nanomatériau d'oxyde de molybdène, son procédé de préparation et dispositif photoélectrique - Google Patents

Nanomatériau d'oxyde de molybdène, son procédé de préparation et dispositif photoélectrique Download PDF

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WO2023051461A1
WO2023051461A1 PCT/CN2022/121354 CN2022121354W WO2023051461A1 WO 2023051461 A1 WO2023051461 A1 WO 2023051461A1 CN 2022121354 W CN2022121354 W CN 2022121354W WO 2023051461 A1 WO2023051461 A1 WO 2023051461A1
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molybdenum oxide
halogenated
preparation
nanomaterial
zns
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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
    • 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
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K99/00—Subject matter not provided for in other groups of this subclass
    • 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, in particular to a method for preparing a molybdenum oxide nanomaterial, a molybdenum oxide nanomaterial prepared by the preparation method, and a photoelectric device.
  • 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 structure of a traditional optoelectronic device mainly includes an anode, a hole injection layer, a hole transport layer, a light emitting layer and a cathode.
  • the holes generated by the anode and the electrons generated by the cathode of the electroluminescent device move and are respectively injected into the light-emitting layer.
  • energy excitons are generated, thereby exciting the light-emitting molecules and finally producing visible light.
  • the electron-hole injection balance of optoelectronic devices can effectively improve the performance of optoelectronic devices such as efficiency and lifetime.
  • top-emitting electroluminescent devices are generally used.
  • the optical design of 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.
  • Molybdenum oxide (MoO x ) is a non-toxic, N-type semiconductor material with high work function and high conductivity. Molybdenum oxide is used as a hole functional layer material in photoelectric devices, which can effectively improve hole transport efficiency.
  • the molybdenum oxide material prepared by the existing molybdenum oxide preparation method has low hole mobility.
  • the present application provides a molybdenum oxide nanomaterial, a preparation method, and a photoelectric device.
  • the embodiment of the present application provides a method for preparing molybdenum oxide nanomaterials, comprising the following steps:
  • Molybdenum oxide, solvent, and halogenated compound are provided and mixed to obtain a mixed solution, wherein the halogenated compound includes one or both of halogenated acid and halogenated alcohol;
  • the molybdenum oxide nanomaterials include molybdenum oxide nanoparticles and halogenated ligands connected to the surface of the molybdenum oxide nanoparticles.
  • the halogenated ligands include halogenated acid ligands and halogenated ligands. One or both of the substituted alcohol ligands.
  • the molar ratio of the molybdenum oxide to the halogenated compound is (1:1)-(1:6).
  • the mixing temperature is 70-100° C.
  • the mixing time is 2-4 hours.
  • the temperature of the evaporative crystallization is 100-200° C.
  • the time of the evaporative crystallization is 0.5-1 h.
  • 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 One or more of trichloroethanol.
  • the concentration of the halogenated compound is 0.25-6 mmol/mL, and the concentration of the molybdenum oxide is 0.04-1 mmol/mL.
  • the concentration of the halogenated compound is 0.25-1 mmol/mL, and the concentration of the molybdenum oxide is 0.04-0.4 mmol/mL.
  • hydrogen peroxide is also added to the mixed solution.
  • the volume ratio of the hydrogen peroxide to the solvent ranges from (1:2) to (1:3).
  • the average particle diameter of the molybdenum oxide nanoparticles is 2-9 nm.
  • the preparation method further includes: adding the molybdenum oxide nanomaterials into an alcoholic solvent for washing at 50-80°C.
  • the alcohol solvent is selected from one or more of isopropanol IPA, butanol and tert-butanol.
  • the present application also provides a molybdenum oxide nanomaterial, wherein the molybdenum oxide nanomaterial includes molybdenum oxide nanoparticles and haloacid ligands and halohydrin ligands connected on the surface of the molybdenum oxide nanoparticles one or both.
  • the content of the halogenated ligand is in the range of 32-87wt%.
  • the haloacid in the haloacid ligand is selected from haloacetic acid
  • the halohydrin in the halohydrin ligand is selected from haloethanol
  • the haloacetic acid is selected from One or more of monochlorinated acetic acid, dichlorinated acetic acid and trichloroacetic acid
  • the halogenated alcohol is selected from one or more of monochlorinated ethanol, dichlorinated ethanol and trichloroethanol .
  • the average particle diameter of the molybdenum oxide nanoparticles is 2-9 nm.
  • the present application also provides a photoelectric device, comprising a stacked anode, a hole functional layer, a light-emitting layer and a cathode, wherein the hole functional layer includes the above-mentioned molybdenum oxide nanomaterial.
  • the hole functional layer is a hole injection layer, and the average particle size of oxide nanoparticles in the molybdenum oxide nanomaterial is 3.5-9 nm.
  • the hole functional layer is a hole transport layer, and the average particle diameter of oxide nanoparticles in the molybdenum oxide nanomaterial is 2-3.5 nm.
  • 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: three [2-(p-tolyl)pyridine- C2, N) Iridium (III), diaryl anthracene derivatives, stilbene aromatic derivatives, pyrene derivatives, fluorene derivatives, TBPe fluorescent materials, TTPA fluorescent materials, TBRb fluorescent materials, and DBP fluorescent materials
  • 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, and the single-structure quantum dots are selected from II-VI group compounds, III -One or more of the V group
  • the molybdenum oxide nanomaterial prepared by the preparation method of the molybdenum oxide nanomaterial of the present application includes molybdenum oxide nanoparticles and one or more of the haloacid ligands and halohydrin ligands attached to the surface of the molybdenum oxide nanoparticle two kinds.
  • the haloacid ligand and the halohydrin ligand can effectively passivate the defect state luminescence of the molybdenum oxide nanoparticles, improve the dispersibility and stability of the molybdenum oxide nanoparticles in solvents, and improve the molybdenum oxide nanomaterials.
  • Hole mobility improves the hole injection and transport capabilities of optoelectronic devices, thereby improving the charge balance in optoelectronic devices, thereby improving the luminous efficiency and life of optoelectronic devices.
  • Fig. 1 is the flow chart of the preparation method of a kind of molybdenum oxide nanomaterial provided by the 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 molybdenum oxide nanomaterial, a preparation method, and a photoelectric 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 the present application provides a method for preparing molybdenum oxide nanomaterials, including the following steps:
  • Step S11 Provide molybdenum oxide, a solvent and a halogenated compound, mix them to obtain a mixed solution, the halogenated compound includes one or both of halogenated acid and halogenated alcohol, and molybdenum oxide particles are dispersed in the mixed solution ;
  • Step S12 evaporating and crystallizing, recrystallizing the molybdenum oxide particles with the volatilization of the solvent to form molybdenum oxide nanoparticles, and bonding the halogenated compound to the surface of the molybdenum oxide nanoparticles to obtain molybdenum oxide nanomaterials
  • the Molybdenum oxide nanomaterials include molybdenum oxide nanoparticles and halogenated ligands attached to the surface of the molybdenum oxide nanoparticles
  • the halogenated ligands include one or both of halogenated acid ligands and halogenated alcohol ligands .
  • the chemical formula of the molybdenum oxide is MoO x , wherein x is a value of 1-3.
  • the MoO x may be selected from but not limited to MoO 1/2 , MoO 4/11 , MoO 17/47 , MoO 5/14 , MoO 8/23 , MoO 9/26 , MoO 1/3 and MoO 2 One or more of /3 .
  • 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 haloacetic acid, which can be selected from but not limited to monochlorinated acetic acid (CH 2 ClCOOH), dichlorinated acetic acid (CHCl 2 COOH) and trichloroacetic acid One or more of 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 a halogenated alcohol, and the halogenated alcohol can be selected from but not limited to 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 solvent may be selected from but not limited to one or more of methanol, ethanol and water.
  • the molar ratio of the molybdenum oxide to the halogenated compound ranges from (1:1) to (1:6).
  • the concentration range of the halogenated compound in the mixed solution is 0.25-6 mmol/mL. In at least one preferred embodiment, the concentration range of the halogenated compound is 0.25-1 mmol/mL.
  • the molybdenum oxide concentration ranges from 0.04-1 mmol/mL in the mixed solution. In at least one preferred embodiment, the concentration range of the molybdenum oxide is 0.04-0.4 mmol/mL.
  • the mixing method is heating at 70-100° C. for 2-4 hours.
  • hydrogen peroxide H 2 O 2
  • the hydrogen peroxide can promote the dispersion of molybdenum oxide.
  • the volume ratio of the hydrogen peroxide to the solvent ranges from (1:2) to (1:3). Within the above range, molybdenum oxide can be fully dispersed, and too large or too small may cause insufficient dispersion of molybdenum oxide.
  • the method for evaporative crystallization is: heating the mixed solution.
  • the temperature range of the heating is 100-200° C., and the time range is 0.5-1 h.
  • the preparation method further includes the step of cleaning the molybdenum oxide nanomaterials, specifically: adding the molybdenum oxide nanomaterials into a less polar alcohol solvent, at a temperature of 50-80°C Stir for 2-5 hours to fully disperse the molybdenum oxide nanomaterials, then wash with a cleaning agent, and centrifugally precipitate to obtain molybdenum oxide nanomaterials with higher purity.
  • the less polar alcohol solvent may be selected from but not limited to one or more of isopropanol IPA, butanol and tert-butanol.
  • the cleaning agent is a commonly used cleaning agent, such as one or more selected from but not limited to cyclohexane and ethanol.
  • the content range of the halogenated ligand is 32-87wt%. If the ligand content is too low, the defect state luminescence of the molybdenum oxide nanoparticles cannot be effectively passivated; if the ligand content is too high, the conductivity of the molybdenum oxide nanomaterials will be too low.
  • the average particle diameter of the molybdenum oxide nanoparticles is 2-9nm. Within the particle size range, the dispersibility and stability of the molybdenum oxide nanomaterials can be effectively improved.
  • the prepared molybdenum oxide nanoparticles have an average particle diameter of 3.5-9 nm, and the stirring time at a temperature of 50-80° C. is 4-5 h when cleaning the molybdenum oxide nano-materials.
  • the prepared molybdenum oxide nanoparticles have an average particle diameter of 2-3.5 nm, and the stirring time at a temperature of 50-80° C. is 2-5 h when cleaning the molybdenum oxide nano-materials.
  • haloacids and haloalcohols are described above, and will not be repeated here.
  • the molybdenum oxide nanomaterial prepared by the preparation method of the molybdenum oxide nanomaterial comprises molybdenum oxide nanoparticles and one or both of haloacid ligands and halohydrin ligands connected to the surface of the molybdenum oxide nanoparticle. kind.
  • the haloacid ligand and the halohydrin ligand can effectively passivate the defect state luminescence of the molybdenum oxide nanoparticles, improve the dispersibility and stability of the molybdenum oxide nanoparticles in solvents, and improve the molybdenum oxide nanomaterials.
  • Hole mobility improves the hole injection and transport capabilities of optoelectronic devices, thereby improving the charge balance in optoelectronic devices, thereby improving the luminous efficiency and life of optoelectronic devices.
  • the embodiment of the present application also provides a hole function thin film, which is mainly used in the photoelectric device 100 .
  • the molybdenum oxide nanomaterial is included in the hole function thin film.
  • the hole functional thin film may be a hole injection thin film or a hole transport thin film.
  • 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 molybdenum oxide nanomaterial
  • Step S22 disposing the molybdenum oxide nanomaterial on the substrate to form a molybdenum oxide nanomaterial thin film, 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 molybdenum oxide nanomaterial is disposed on the anode.
  • the substrate includes a stacked cathode and a light-emitting layer, and the molybdenum oxide nanomaterial is disposed on the light-emitting layer.
  • the method of disposing the molybdenum 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 method, soaking method, spraying method, roller coating method, casting method, Slot coating method and strip coating method, etc.
  • 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 method, soaking method, spraying method, roller coating method, casting method
  • the method of disposing the molybdenum oxide nanomaterials on the substrate is a solution method.
  • the molybdenum oxide nanomaterials need to be dispersed with a dispersant to obtain a molybdenum oxide nanomaterial dispersion.
  • the molybdenum oxide nanomaterial dispersion is disposed on the substrate by a solution method.
  • the dispersant may be selected from but not limited to methanol, ethanol, butanol, amyl alcohol 2-(trifluoromethyl)-3-2 ethoxydodecafluorohexane (C 9 H 5 F 15 O), methyl Oxy-nonafluorobutane (C 4 F 9 OCH 3 ), 1-chloro-4-methoxybutane (C 5 H 11 ClO), 2-bromo-1,1-diethoxyethane One or more of (C 6 H 13 BrO 2 ).
  • optoelectronic device 100 can be solar cell, photodetector, organic electroluminescent device (OLED) or quantum dot electroluminescent device (QLED) ).
  • OLED organic electroluminescent device
  • QLED quantum dot electroluminescent device
  • 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 both of a hole injection layer 21 and a hole transport layer 22 .
  • the hole functional layer 20 includes the aforementioned hole functional thin film, in other words, the hole injection layer 21 and/or the hole transport layer 22 is the aforementioned hole functional thin film.
  • the hole injection layer 21 includes the molybdenum oxide nanomaterial, and at this time, the particle size range of the molybdenum oxide nanoparticle in the molybdenum oxide nanomaterial is 3.5-9 nm, and in the particle
  • the energy level of the molybdenum oxide nanoparticles within the diameter range matches the energy level of the material of the anode 10 conventionally used in the optoelectronic device 100, so that the energy level between the anode 10 and the hole injection layer 21 in the optoelectronic device 100 can be improved
  • Matching reduces the potential barrier between the anode 10 and the hole injection layer 21 , improves the hole injection capability of the photoelectric device 100 , improves the charge balance in the photoelectric device 100 , and then improves the luminous efficiency and life of the photoelectric device 100 .
  • the hole transport layer 22 includes the molybdenum oxide nanomaterial, and at this time, the particle size range of the molybdenum oxide nanoparticle in the molybdenum oxide nanomaterial is 2-3.5nm.
  • the energy level of the molybdenum oxide nanoparticles in the above particle size range matches the energy level of the materials conventionally used in the light-emitting layer 30 of the photoelectric device 100, so that the light-emitting layer 30 and the hole transport layer 22 in the photoelectric device 100 can be improved.
  • the energy level matching between them reduces the potential barrier between the hole transport layer 22 and the light-emitting layer 30, improves the hole transport capability of the optoelectronic device 100, improves the charge balance in the optoelectronic device 100, and then improves the luminous efficiency of the optoelectronic device 100 and longevity.
  • 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 is the hole injection film, in other words, the hole injection layer 21 includes the molybdenum oxide nanomaterial.
  • the particle size range of the molybdenum oxide nano particles in the molybdenum oxide nano material is 3.5-9nm.
  • 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 is the hole transport film, in other words, the hole transport layer 22 includes the molybdenum oxide nanomaterial.
  • the particle size range of the molybdenum oxide nano particles in the molybdenum oxide nano material is 2-3.5nm.
  • 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 is the hole transport film, in other words, the hole injection layer 21 and/or the hole transport layer 22 includes the molybdenum oxide Nanomaterials, the average particle diameter of the molybdenum oxide nanoparticles in the molybdenum oxide nanomaterials in the hole injection layer 21 is 3.5-9nm, and the molybdenum oxide nanoparticles in the molybdenum oxide nanomaterials in the hole transport layer 22 The average particle size is 2-3.5nm.
  • 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 metal sandwiched between doped or non-doped transparent metal oxides, 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), diarylanthracene derivatives, stilbene aromatic derivatives, pyrene derivatives, fluorene derivatives , TBPe fluorescent material, TTPA fluorescent material, TBRb fluorescent material, and one or more of DBP fluorescent materials.
  • 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 quantum dot 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, may be selected from but not limited to one or more of Ag electrodes, Al electrodes, Au electrodes, Pt electrodes, IZO electrodes and alloy electrodes.
  • 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, 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 molybdenum oxide nanomaterial, and disposing the molybdenum 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 molybdenum oxide nanomaterial, and disposing the molybdenum 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.
  • PEDOT:PSS model AI4083
  • the molybdenum oxide nanomaterials include molybdenum oxide nanoparticles and molybdenum oxide nanoparticles connected to the molybdenum oxide nanoparticles
  • Dichlorinated acetic acid ligands on the surface the particle diameter of the molybdenum oxide nanoparticles is 3.5nm, and the content of the dichlorinated acetic acid ligands is 50wt%;
  • the NPB material was vapor-deposited on the cathode 40 to obtain a covering layer with a thickness of 65 nm, and the photoelectric device 100 was obtained.
  • the optoelectronic device 100 of this embodiment is a quantum dot electroluminescent device.
  • Example 2 This example is basically the same as Example 1, the difference is that this example uses monochlorinated ethanol to replace the dichloroacetic acid in Example 1, and correspondingly, the molybdenum oxide nanomaterials obtained in this example include molybdenum oxide nanoparticles and Ethanol monochloride ligands attached to the surface of the molybdenum oxide nanoparticles.
  • This example is basically the same as Example 1, the difference is that this example uses 20mmol of monochlorinated ethanol and 30mmol of trichloroacetic acid to replace the 50mmol of dichlorinated acetic acid in Example 1, correspondingly, this example obtains
  • the molybdenum oxide nanometer material comprises molybdenum oxide nanoparticle and monochlorinated ethanol ligand and trichloroacetic acid ligand connected on the surface of the molybdenum oxide nanoparticle.
  • This embodiment is basically the same as Embodiment 1, the difference is that the hole injection layer 21 and the hole transport layer 22 of this embodiment are prepared by the following method:
  • the molybdenum oxide nanomaterials include molybdenum oxide nanoparticles and are connected to Dichloroacetic acid ligands on the surface of the molybdenum oxide nanoparticles, the particle diameter of the molybdenum oxide nanoparticles is 4-9nm, and the content of the dichloroacetic acid ligands is 30wt%;
  • the molybdenum oxide nanomaterial was dispersed in methoxy-nonafluorobutane to obtain a molybdenum oxide nanomaterial dispersion with a concentration of 25 mg/mL, and the molybdenum oxide nanomaterial dispersion was spin-coated on the anode 10 and heat treatment at 150° C. for 20 minutes to obtain a hole injection layer 21 with a thickness of 35 nm;
  • the NPB material was spin-coated on the hole injection layer 21, and then heat-treated at 150° C. for 15 minutes to obtain a hole transport layer 22 with a thickness of 20 nm.
  • This embodiment is basically the same as Embodiment 1, the difference is that the hole injection layer 21 of this embodiment is prepared by the following method:
  • the molybdenum oxide nanomaterials include molybdenum oxide nanoparticles and are connected to Dichloroacetic acid ligands on the surface of the molybdenum oxide nanoparticles, the particle diameter of the molybdenum oxide nanoparticles is 4-9nm, and the content of the dichloroacetic acid ligands is 30wt%;
  • the molybdenum oxide nanomaterial was dispersed in methoxy-nonafluorobutane to obtain a molybdenum oxide nanomaterial dispersion with a concentration of 25 mg/mL, and the molybdenum oxide nanomaterial dispersion was spin-coated on the anode 10 and heat treatment at 150° C. for 20 minutes to obtain a hole injection layer 21 with a thickness of 35 nm;
  • the molybdenum oxide nanomaterials include molybdenum oxide nanoparticles and are connected to Dichlorinated acetic acid ligands on the surface of the molybdenum oxide nanoparticles, the particle diameter of the molybdenum oxide nanoparticles is 2-3.5nm, and the content of the dichlorinated acetic acid ligands is 70wt%;
  • the molybdenum oxide nanomaterial was dispersed in methoxy-nonafluorobutane to obtain a molybdenum oxide nanomaterial dispersion with a concentration of 25 mg/mL, and the molybdenum oxide nanomaterial dispersion was spin-coated on the anode 10 and heat treatment at 150° C. for 20 minutes to obtain a hole injection layer 21 with a thickness of 35 nm;
  • Ag is sequentially vapor-deposited on the electron transport layer to obtain a cathode 40 with a thickness of 50 nm;
  • the NPB material was vapor-deposited on the cathode 40 to obtain a covering layer with a thickness of 65 nm, and the photoelectric device 100 was obtained.
  • the optoelectronic device 100 of this embodiment is an organic electroluminescent device.
  • This embodiment is basically the same as Embodiment 6, the difference is that the preparation method of the hole transport layer 22 of this embodiment is:
  • the molybdenum oxide nanomaterials include molybdenum oxide nanoparticles and are connected to The dichloride ethanol ligand on the surface of the molybdenum oxide nanoparticle, the particle diameter of the molybdenum oxide nanoparticle is 2-3.5nm, and the content of the dichloride ethanol ligand is 50wt%;
  • the molybdenum oxide nanomaterial was dispersed in methoxy-nonafluorobutane to obtain a molybdenum oxide nanomaterial dispersion with a concentration of 25 mg/mL, and the molybdenum oxide nanomaterial dispersion was spin-coated on the anode 10 and heat treatment at 150° C. for 20 minutes to obtain a hole transport layer 22 with a thickness of 20 nm.
  • 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 6, 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 1-7 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.
  • the external quantum efficiency and the life-span of the quantum dot electroluminescent device of embodiment 1-5 are obviously higher than the external quantum efficiency and the life-span of the quantum dot electroluminescent device of comparative example 1, and embodiment 6-7 has The external quantum efficiency and lifetime of the electroluminescent device are significantly higher than those of the organic electroluminescent device of Comparative Example 2.

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Abstract

La présente demande concerne un nanomatériau d'oxyde de molybdène, son procédé de préparation et un dispositif photoélectrique. Le nanomatériau d'oxyde de molybdène préparé par le procédé de préparation comprend des nanoparticules d'oxyde de molybdène et l'un ou les deux parmi un ligand d'haloacide et un ligand d'halohydrine lié à la surface des nanoparticules d'oxyde de molybdène, et présente une dispersibilité et une stabilité relativement élevées, de telle sorte qu'une couche fonctionnelle de trou comprenant celui-ci présente une mobilité de trou relativement élevée, ce qui permet d'améliorer l'efficacité lumineuse et la durée de vie du dispositif photoélectrique.
PCT/CN2022/121354 2021-09-30 2022-09-26 Nanomatériau d'oxyde de molybdène, son procédé de préparation et dispositif photoélectrique WO2023051461A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103107289A (zh) * 2008-04-28 2013-05-15 大日本印刷株式会社 用于形成空穴注入传输层的含过渡金属的纳米粒子及其制造方法
CN103154010A (zh) * 2010-09-14 2013-06-12 科学与工业研究委员会 有机金属钼炔化物二氧配合物及其制备方法
WO2013129042A1 (fr) * 2012-02-29 2013-09-06 日本精機株式会社 Élément électroluminescent organique
CN105374953A (zh) * 2015-12-24 2016-03-02 Tcl集团股份有限公司 一种量子点发光二极管及制备方法、发光模组与显示装置
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

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103107289A (zh) * 2008-04-28 2013-05-15 大日本印刷株式会社 用于形成空穴注入传输层的含过渡金属的纳米粒子及其制造方法
CN103154010A (zh) * 2010-09-14 2013-06-12 科学与工业研究委员会 有机金属钼炔化物二氧配合物及其制备方法
WO2013129042A1 (fr) * 2012-02-29 2013-09-06 日本精機株式会社 Élément électroluminescent organique
CN105374953A (zh) * 2015-12-24 2016-03-02 Tcl集团股份有限公司 一种量子点发光二极管及制备方法、发光模组与显示装置
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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