WO2023051317A1 - Tungsten oxide nanomaterial and preparation method therefor, and optoelectronic device - Google Patents
Tungsten oxide nanomaterial and preparation method therefor, and optoelectronic device Download PDFInfo
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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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- WIPO (PCT)
- Prior art keywords
- tungsten oxide
- halogenated
- zns
- acid
- preparation
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- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 title claims abstract description 139
- 229910001930 tungsten oxide Inorganic materials 0.000 title claims abstract description 139
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 230000005693 optoelectronics Effects 0.000 title abstract description 57
- 239000003446 ligand Substances 0.000 claims abstract description 54
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- 150000001875 compounds Chemical class 0.000 claims abstract description 34
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims abstract description 33
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- 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
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- 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
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- 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
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/15—Hole transporting layers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/17—Carrier injection layers
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- 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
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- 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
Provided are a preparation method for a tungsten oxide nanomaterial, a tungsten oxide nanomaterial and an optoelectronic device. The preparation method comprises: providing tungstic acid; and mixing tungstic acid with a halogenated compound, the halogenated compound being selected from one or more among halogenated acids and halogenated alcohols, and heating and reacting same to obtain a tungsten oxide nanomaterial. The tungsten oxide nanomaterial comprises tungsten oxide nanoparticles and ligands connected to surfaces of the tungsten oxide nanoparticles, and the ligands comprise one or more among haloacid ligands and halohydrin ligands. The optoelectronic device comprises: an anode, a hole function layer, a light emitting layer and a cathode which are stacked, wherein the hole function layer comprises the tungsten oxide nanomaterial. The tungsten oxide nanomaterial has high hole mobility, which may improve the hole injection and transport capabilities of the optoelectronic device, thereby improving the charge balance in the optoelectronic device, and thus improving the external quantum efficiency and service life of the optoelectronic device.
Description
本申请要求于2021年09月30日在中国专利局提交的、申请号为202111160505.0、申请名称为“氧化钨纳米材料及其制备方法、空穴功能薄膜及光电器件”的中国专利申请的优先权,其全部内容通过引用结合在本申请中。This application claims the priority of the Chinese patent application with the application number 202111160505.0 and the application name "tungsten oxide nanomaterial and its preparation method, hole function thin film and optoelectronic device" filed at the China Patent Office on September 30, 2021 , the entire contents of which are incorporated in this application by reference.
本申请涉及显示技术领域,尤其涉及一种氧化钨纳米材料的制备方法、由所述制备方法制得的氧化钨纳米材料、及光电器件。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.
光电器件是指根据光电效应制作的器件,其在新能源、传感、通信、显示、照明等领域具有广泛的应用,如太阳能电池、光电探测器、电致发光器件等。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.
目前电脑、手机等电子产品的显示面板的发光元件主要为电致发光器件。现有的广泛使用的电致发光器件主要为有机电致发光器件(OLED)和量子点电致发光器件(QLED)。传统的电致发光器件的结构主要包括阳极、空穴注入层、空穴传输层、发光层、电子传输层、电子注入层及阴极。在电场的作用下,电致发光器件的阳极产生的空穴和阴极产生的电子发生移动,分别向空穴传输层和电子传输层注入,最终迁移到发光层,当二者在发光层相遇时,产生能量激子,从而激发发光分子最终产生可见光。At present, 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.
众所周知,电致发光器件的电子-空穴注入平衡可以有效地提升电致发光器件的效率及寿命等性能。然而,现有的电致发光器件因为各种原因会导致空穴注入和/或传输的能力较差,使得电致发光器件的电子-空穴注入不平衡。例如,为了增加显示面板的开口率,通常采用顶发射电致发光器件。而顶发射电致发光器件的光学设计,通常需要增加电致发光器件的空穴注入层厚度来优化器件的腔长,而电致发光器件的空穴注入层的厚度增加会导致电致发光器件的空穴注入能力降低,使得电致发光器件中的电子-空穴注入不平衡,而导致电致发光器件的效率和寿命较低。It is well known that the electron-hole injection balance of electroluminescent devices can effectively improve the efficiency and lifetime of electroluminescent devices. However, 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. For example, in order to increase the aperture ratio of the display panel, 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.
由于无机材料能够有效解决有机材料所存在的由于吸水而导致器件性能 降低的问题,近年来,采用无机半导体材料作为空穴注入材料和空穴传输材料,成为了电致发光器件的制备技术中比较热门的研究内容之一。其中,氧化钨(WO
3),禁带宽度为2.6-2.8eV,能够吸收太阳光中的蓝光,且具有化学稳定性好、W/O化学计量可调控、能级结构可调控、载流子迁移率高、价格低廉等优点,而被用作空穴注入材料或空穴传输材料。
Since inorganic materials can effectively solve the problem of device performance degradation due to water absorption in organic materials, in recent years, the use of inorganic semiconductor materials as hole injection materials and hole transport materials has become a relatively popular technology in the preparation of electroluminescent devices. One of the most popular research topics. Among them, 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.
现有的制备方法制得的WO
3的空穴注入性能较差,使得电致发光器件中的电子-空穴注入不平衡,而导致电致发光器件的效率和寿命较低。
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.
因此,本申请提供一种氧化钨纳米材料及其制备方法、光电器件。Therefore, the present application provides a tungsten oxide nanomaterial, a preparation method thereof, and a photoelectric device.
本申请实施例提供一种氧化钨纳米材料的制备方法,其中,包括如下步骤:The embodiment of the present application provides a method for preparing tungsten oxide nanomaterials, which includes the following steps:
提供钨酸;Provide tungstic acid;
将所述钨酸与卤代化合物混合,其中,所述卤代化合物选自卤代酸和卤代醇中的一种或多种,加热反应,得到氧化钨纳米材料,所述氧化钨纳米材料包括氧化钨纳米颗粒及连接在所述氧化钨纳米颗粒表面的配体,所述配体包括卤代酸配体和卤代醇配体中的一种或多种。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.
优选的,所述加热反应的温度范围为40-80℃,所述加热反应时间为48-72h。Preferably, the temperature range of the heating reaction is 40-80°C, and the heating reaction time is 48-72h.
优选的,所述钨酸与所述卤代化合物的质量比的范围为(1.0:1)-(9.1:1)。Preferably, the range of the mass ratio of the tungstic acid to the halogenated compound is (1.0:1)-(9.1:1).
优选的,所述钨酸的制备方法为:将钨酸盐与酸混合,反应,得到钨酸。Preferably, the preparation method of the tungstic acid is as follows: mixing tungstate and acid to react to obtain tungstic acid.
优选的,所述钨酸盐选自钨酸钠、钨酸钛、钨酸镍及钨酸镁中的一种或多种。Preferably, the tungstate is selected from one or more of sodium tungstate, titanium tungstate, nickel tungstate and magnesium tungstate.
优选的,所述钨酸盐包括钨酸钛、钨酸镍及钨酸镁中的一种或多种,所述氧化钨纳米颗粒中掺杂有掺杂金属元素,所述掺杂金属元素选自Ti、Ni及Mg中的一种或多种。Preferably, 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.
优选的,所述掺杂金属元素的摩尔量为所述氧化钨的摩尔量的1-20%。Preferably, the molar amount of the doping metal element is 1-20% of the molar amount of the tungsten oxide.
优选的,所述钨酸与所述卤代化合物混合后,还包括加入弱碱的步骤。Preferably, after the tungstic acid is mixed with the halogenated compound, a step of adding a weak base is also included.
优选的,所述弱碱选自K
2CO
3、KHCO
3、Na
2CO
3及NaHCO
3中的一种或多种。
Preferably, the weak base is selected from one or more of K 2 CO 3 , KHCO 3 , Na 2 CO 3 and NaHCO 3 .
优选的,所述钨酸与所述弱碱的摩尔比的范围为(1:1.1)-(1:1.5)。Preferably, the range of the molar ratio of the tungstic acid to the weak base is (1:1.1)-(1:1.5).
优选的,所述卤代酸为卤代乙酸,所述卤代醇为卤代乙醇。Preferably, the halogenated acid is halogenated acetic acid, and the halogenated alcohol is halogenated alcohol.
优选的,所述卤代乙酸选自一氯化乙酸、二氯化乙酸及三氯代乙酸中的一种或多种,所述卤代乙醇选自一氯化乙醇、二氯化乙醇及三氯代乙醇中的一种或多种。Preferably, the halogenated acetic acid is selected from one or more of monochlorinated acetic acid, dichlorinated acetic acid and trichloroacetic acid, and the described halogenated alcohol is selected from monochlorinated ethanol, dichlorinated ethanol and trichloroacetic acid One or more of chloroethanols.
相应的,本申请还提供一种氧化钨纳米材料,其中,所述氧化钨纳米材料包括氧化钨纳米颗粒及连接在所述氧化钨纳米颗粒表面的配体,所述配体包括卤代酸配体和卤代醇配体中的一种或多种。Correspondingly, 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. One or more of ligands and halohydrin ligands.
优选的,所述氧化钨纳米材料中,所述配体的含量范围为10-50wt%。Preferably, in the tungsten oxide nanomaterial, the content of the ligand is in the range of 10-50wt%.
优选的,所述氧化钨纳米颗粒中掺杂有掺杂金属元素。Preferably, the tungsten oxide nanoparticles are doped with doping metal elements.
优选的,所述掺杂金属元素选自Ti、Ni及Mg中的一种或多种。Preferably, the doping metal element is selected from one or more of Ti, Ni and Mg.
优选的,所述掺杂金属元素的摩尔量为所述氧化钨的摩尔量的1-20%。Preferably, the molar amount of the doping metal element is 1-20% of the molar amount of the tungsten oxide.
优选的,所述氧化钨纳米颗粒的平均粒径为8-15nm。Preferably, the average particle diameter of the tungsten oxide nanoparticles is 8-15nm.
优选的,所述卤代酸配体中的卤代酸为卤代乙酸,所述卤代醇配体中的卤代醇为卤代乙醇。Preferably, the haloacid in the haloacid ligand is haloacetic acid, and the halohydrin in the halohydrin ligand is haloethanol.
优选的,所述卤代乙酸选自一氯化乙酸、二氯化乙酸及三氯代乙酸中的一种或多种,所述卤代乙醇选自一氯化乙醇、二氯化乙醇及三氯代乙醇中的一种或多种。Preferably, the halogenated acetic acid is selected from one or more of monochlorinated acetic acid, dichlorinated acetic acid and trichloroacetic acid, and the described halogenated alcohol is selected from monochlorinated ethanol, dichlorinated ethanol and trichloroacetic acid One or more of chloroethanols.
相应的,本申请还提供一种光电器件,包括层叠的阳极、空穴功能层、发光层及阴极,其中,所述空穴功能层中包括前文所述的氧化钨纳米材料。Correspondingly, 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.
优选的,所述阳极选自掺杂金属氧化物电极或复合电极,所述掺杂金属氧化物电极选自铟掺杂氧化锡、氟掺杂氧化锡、锑掺杂氧化锡、铝掺杂氧化锌、镓掺杂氧化锌、铟掺杂氧化锌、镁掺杂氧化锌及铝掺杂氧化镁中的一种或多种,所述复合电极选自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或ZnS/Al/ZnS;
Preferably, the anode is selected from doped metal oxide electrodes or composite electrodes, and the doped metal oxide electrodes are selected from indium-doped tin oxide, fluorine-doped tin oxide, antimony-doped tin oxide, aluminum-doped tin oxide One or more of zinc, gallium doped zinc oxide, indium doped zinc oxide, magnesium doped zinc oxide and aluminum doped magnesium 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;
所述发光层为有机发光层或量子点发光层,所述有机发光层的材料选自4,4'-双(N-咔唑)-1,1'-联苯:三[2-(对甲苯基)吡啶-C2,N)合铱(III)、4,4',4”-三(咔唑-9-基)三苯胺:三[2-(对甲苯基)吡啶-C2,N)合铱(III)、二芳香基蒽衍生物、二苯乙烯芳香族衍生物、芘衍生物、芴衍生物、TBPe荧光材料、TTPA荧光材料、TBRb荧光材料、及DBP荧光材料中的一种或多种,所述量子点发光层的材料选自单一结构量子点及核壳结构量子点中的一种或多种,所述单一结构量子点选自II-VI族化合物、III-V族化合物和I-III-VI族化合物中的一种或多种,所述II-VI族化合物选自CdSe、CdS、CdTe、ZnSe、ZnS、CdTe、ZnTe、CdZnS、CdZnSe、CdZnTe、ZnSeS、ZnSeTe、ZnTeS、CdSeS、CdSeTe、CdTeS、CdZnSeTe及CdZnSTe中的一种或多种,所述III-V族化合物选自InP、InAs、GaP、GaAs、GaSb、AlN、AlP、InAsP、InNP、InNSb、GaAlNP及InAlNP中的一种或多种,所述I-III-VI族化合物选自CuInS
2、CuInSe
2及AgInS
2中的一种或多种,所述核壳结构的量子点选自CdSe/ZnS、CdSe/ZnSe/ZnS、ZnCdSe/ZnSe/ZnS、ZnSe/ZnS、ZnSeTe/ZnS、CdSe/CdZnSeS/ZnS、InP/ZnSe/ZnS及InP/ZnSeS/ZnS中的一种或多种;
The light-emitting layer is an organic light-emitting layer or a quantum dot light-emitting layer, and 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) One or more of 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, and the single-structure quantum dots are selected from II-VI group compounds and III-V group compounds And one or more of I-III-VI group compounds, the II-VI group compound is selected from CdSe, CdS, CdTe, ZnSe, ZnS, CdTe, ZnTe, CdZnS, CdZnSe, CdZnTe, ZnSeS, ZnSeTe, ZnTeS , CdSeS, CdSeTe, CdTeS, CdZnSeTe and CdZnSTe one or more, the III-V compound is selected from InP, InAs, GaP, GaAs, GaSb, AlN, AlP, InAsP, InNP, InNSb, GaAlNP and InAlNP One or more of them, the I-III-VI group compound is selected from one or more of CuInS 2 , CuInSe 2 and AgInS 2 , and the quantum dots of the core-shell structure are selected from CdSe/ZnS, CdSe One or more of /ZnSe/ZnS, ZnCdSe/ZnSe/ZnS, ZnSe/ZnS, ZnSeTe/ZnS, CdSe/CdZnSeS/ZnS, InP/ZnSe/ZnS and InP/ZnSeS/ZnS;
所述阴极选自Ag电极、Al电极、Au电极、Pt电极、Ag/IZO电极、IZO电极或合金电极的一种或多种。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.
本申请的氧化钨纳米材料的制备方法制得的氧化钨纳米材料包括氧化钨纳米颗粒及连接在所述氧化钨纳米颗粒表面的卤代酸配体和卤代醇配体中的一种或多种。所述卤代酸配体和卤代醇配体可以有效地钝化氧化钨纳米颗粒的缺陷态发光,提高氧化钨纳米颗粒在溶剂中的分散性和稳定性,提高包括所述氧化钨纳米材料的空穴功能层的空穴迁移率,提高光电器件的空穴注入及传输能力,从而改善光电器件中的电荷平衡,进而提升光电器件的外量子效率和寿命。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.
为了更清楚地说明本申请实施例中的技术方案,下面将对实施例描述中所 需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本申请的一些实施例,对于本领域技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他的附图。In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings that need to be used in the description of the embodiments will be briefly introduced below. Obviously, the drawings in the following description are only some embodiments of the present application. For those skilled in the art, other drawings can also be obtained based on these drawings without any creative effort.
图1是本申请实施例提供的一种氧化钨纳米材料的制备方法流程图;Fig. 1 is a flow chart of a preparation method of a tungsten oxide nanomaterial provided in an embodiment of the present application;
图2是本申请实施例提供的一种光电器件的结构示意图;Fig. 2 is a schematic structural diagram of an optoelectronic device provided by an embodiment of the present application;
图3是本申请实施例提供的另一种光电器件的结构示意图;Fig. 3 is a schematic structural diagram of another optoelectronic device provided by the embodiment of the present application;
图4是本申请实施例提供的又一种光电器件的结构示意图。Fig. 4 is a schematic structural diagram of another optoelectronic device provided by an embodiment of the present application.
本申请的实施方式Embodiment of this application
下面将结合本申请实施例中的附图,对本申请实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本申请一部分实施例,而不是全部的实施例。基于本申请中的实施例,本领域技术人员在没有做出创造性劳动前提下所获得的所有其它实施例,都属于本申请保护的范围。The following will clearly and completely describe the technical solutions in the embodiments of the application with reference to the drawings in the embodiments of the application. Apparently, the described embodiments are only some of the embodiments of the application, not all of them. Based on the embodiments in this application, all other embodiments obtained by those skilled in the art without making creative efforts belong to the scope of protection of this application.
本申请实施例提供一种氧化钨纳米材料及其制备方法、光电器件。以下分别进行详细说明。需说明的是,以下实施例的描述顺序不作为对实施例优选顺序的限定。另外,在本申请的描述中,术语“包括”是指“包括但不限于”。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".
本申请中“一种或多种”等表述,是指所列举多项中的一种或者多种,“多种”是指这些项中两种或两种以上的任意组合,包括单项(种)或复数项(种)的任意组合,例如,“a、b或c中的至少一项(种)”或“a、b和c中的至少一项(种)”,均可以表示:a,b,c,a-b(即a和b),a-c,b-c,或a-b-c,其中a,b,c分别可以是单个,也可以是多个。In this application, 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.
本申请的各种实施例可以以一个范围的型式存在;应当理解,以一范围型式的描述仅仅是因为方便及简洁,不应理解为对本申请范围的硬性限制;因此,应当认为所述的范围描述已经具体公开所有可能的子范围以及该范围内的单一数值。例如,应当认为从1到6的范围描述已经具体公开子范围,例如从1到3,从1到4,从1到5,从2到4,从2到6,从3到6等,以及所述范围内的单一数字,例如1、2、3、4、5及6,此不管范围为何皆适用。另外,每当在本文中指出数值范围,是指包括所指范围内的任何引用的数字(分数或整数)。Various embodiments of the present application may exist in the form of a range; it should be understood that the description in the form of a range is only for convenience and brevity, and should not be construed as a rigid limitation on the scope of the application; therefore, the described range should be regarded as The description has specifically disclosed all possible subranges as well as individual values within that range. For example, a description of a range from 1 to 6 should be considered to have specifically disclosed subranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., and Single numbers within the stated ranges, eg 1, 2, 3, 4, 5 and 6, apply regardless of the range. Additionally, whenever a numerical range is indicated herein, it is meant to include any cited numeral (fractional or integral) within the indicated range.
请参阅图1,本申请实施例提供一种氧化钨纳米材料的制备方法,包括如下步骤:Please refer to Figure 1, the embodiment of this application provides a preparation method of tungsten oxide nanomaterials, including the following steps:
步骤S11:提供钨酸;Step S11: providing tungstic acid;
步骤S12:将钨酸与卤代化合物混合,所述卤代化合物包括卤代酸和卤代醇中的一种或多种;加热反应,得到氧化钨纳米材料,所述氧化钨纳米材料包括氧化钨纳米颗粒及连接在所述氧化钨纳米颗粒表面的配体,所述配体包括卤代酸配体和卤代醇配体中的一种或多种。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.
所述步骤S11中:In the step S11:
所述钨酸可以选自但不限于白钨酸、黄钨酸及偏钨酸中的一种或多种。The tungstic acid may be selected from but not limited to one or more of white tungstic acid, yellow tungstic acid and metatungstic acid.
在一实施例中,所述钨酸通过以下方法制得:将钨酸盐与酸混合,反应,得到钨酸。In one embodiment, the tungstic acid is produced by the following method: mixing tungstate with acid and reacting to obtain tungstic acid.
所述钨酸盐可以选自但不限于钨酸钠(Na
2WO
4)、钨酸钛(TiW
2O
5)、钨酸镍(NiW
2O
5)及钨酸镁(MgWO
4)中的一种或多种。所述钨酸钠可以为二水合钨酸钠(Na
2WO
4·2H
2O),所述钨酸钛可以为六水合钨酸钛(TiW
2O
5·2H
2O),所述钨酸镍可以为六水合钨酸镍(NiW
2O
5·2H
2O),所述钨酸镁可以为二水合钨酸镁(MgWO
4·2H
2O)。
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).
在所述钨酸盐包括钨酸钛、钨酸镍及钨酸镁中的一种或多种时,所述制得的钨酸中会含有Ti、Ni及Mg等金属元素中的一种或多种。对应的,所述步骤S14所制得的氧化钨纳米材料中的氧化钨纳米颗粒为掺杂金属元素的氧化钨纳米颗粒,所述氧化钨纳米材料包括掺杂金属元素的氧化钨纳米颗粒及连接在所述氧化钨纳米颗粒表面的卤代酸配体和/或卤代醇配体。所述掺杂金属元素包括但不限于Ti、Ni及Mg中的一种或多种。When the tungstate includes one or more of titanium tungstate, nickel tungstate and magnesium tungstate, the prepared tungstate will contain one or more of metal elements such as Ti, Ni and Mg. Various. Correspondingly, 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.
所述酸为常规用于制备钨酸的酸,例如,可以选自但不限于硝酸及盐酸中的一种或多种。在一实施例中,所述酸为10%的硝酸的水溶液。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.
在一些实施例中,所述白钨酸的制备方法还包括使用清洗剂对所述钨酸进行清洗的步骤。可以理解,所述清洗剂可以为常规用于清洗钨酸的异丙醇、环己烷、乙醇等。In some embodiments, the preparation method of white tungstic acid further includes the step of cleaning the tungstic acid with a cleaning agent. It can be understood that the cleaning agent can be isopropanol, cyclohexane, ethanol, etc. that are conventionally used for cleaning tungstic acid.
所述步骤S12中:In the step S12:
所述卤代酸是指分子中同时含有卤素原子和羧基的化合物。所述卤素原子可以选自但不限于氟(F)、氯(Cl)、溴(Br)及碘(I)中的一种或多种。在一些实施例中,所述卤代酸为所述卤代乙酸,作为示例,所述卤代酸选自一氯化乙酸(CH
2ClCOOH)、二氯化乙酸(CHCl
2COOH)及三氯代乙酸(CCl
3COOH)中的一种或多种。
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). In some embodiments, the haloacid is the haloacetic acid. As an example, the haloacid is selected from monochlorinated acetic acid (CH 2 ClCOOH), dichlorinated acetic acid (CHCl 2 COOH) and trichloroacetic acid. One or more of acetic acid (CCl 3 COOH).
所述卤代醇是指分子中同时含有卤素原子和-CH
2-OH基的化合物。所述卤素原子可以选自但不限于氟(F)、氯(Cl)、溴(Br)及碘(I)中的一种或多种。在一些实施例中,所述卤代醇为所述卤代乙醇,作为示例,所述卤代醇选自一氯化乙醇(CH
2ClCH
2OH)、二氯化乙醇(CHCl
2CH
2OH)及三氯代乙醇(CCl
3CH
2OH)中的一种或多种。
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). In some embodiments, the halogenated alcohol is the halogenated alcohol. As an example, 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).
在一些实施例中,所述钨酸与所述卤代酸和/或卤代醇的质量比的范围为(1.0:1)-(9.1:1)。In some embodiments, the mass ratio of the tungstic acid to the haloacid and/or halohydrin ranges from (1.0:1) to (9.1:1).
在一些实施例中,所述将钨酸与卤代化合物混合的方法为超声,以使钨酸均匀分散在所述卤代酸和/或卤代醇中。In some embodiments, 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.
在一些实施例中,所述钨酸与卤代酸和/或卤代醇混合后,还需要加入弱碱,以调解溶液的pH值至6-8,从而促进钨酸与卤代化合物之间形成配位键。所述弱碱可以选自但不限于K
2CO
3、KHCO
3、Na
2CO
3及NaHCO
3中的一种或多种。在一实施例中,所述弱碱为弱碱的水溶液,所述弱碱水溶液中弱碱的含量范围为10-30wt%。
In some embodiments, after the tungstic acid is mixed with the halogenated acid and/or the 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 . In one embodiment, 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%.
在一些实施例中,所述钨酸与所述弱碱的摩尔比的范围为(1:1.1)-(1:1.5)。In some embodiments, the molar ratio of the tungstic acid to the weak base is in the range of (1:1.1)-(1:1.5).
在一些实施例中,所述加热的温度范围为40-80℃。反应时间为48-72h。可以理解,为使所述反应快速充分的进行,所述反应可以在搅拌下进行。In some embodiments, 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.
在一些实施例中,所述氧化钨纳米材料中,所述配体的含量范围为10-50wt%。所述配体含量过低,则不能有效地钝化氧化钨纳米颗粒的缺陷态发光,所述配体含量过高,则会导致氧化钨纳米材料的导电性过低。In some embodiments, in the tungsten oxide nanomaterial, 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.
所述氧化钨纳米颗粒的平均粒径为8-15nm。所述氧化钨纳米颗粒的粒径过小,导电性差且不稳定;所述氧化钨纳米颗粒的粒径过大,由所述氧化钨纳米材料制备的空穴空能层与光电器件的发光层的能级不匹配,会造成载流子注入困难。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.
在一些实施例中,所述氧化钨纳米颗粒中可以掺杂有掺杂金属元素,换言之,所述氧化钨纳米颗粒为掺杂金属元素的氧化钨纳米颗粒。所述掺杂金属元素可以选自但不限于Ti、Ni及Mg中的一种或多种。所述掺杂金属元素可以有效地提高氧化钨纳米材料的空穴浓度及空穴迁移率。In some embodiments, 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.
所述氧化钨纳米材料中,所述掺杂金属元素的摩尔量为氧化钨的摩尔量的1-20%。所述掺杂金属元素的含量过低则无掺杂效果,含量过高则掺杂金属元素将单独结晶析出。In 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.
所述氧化钨纳米材料的制备方法制得的氧化钨纳米材料包括氧化钨纳米颗粒及连接在所述氧化钨纳米颗粒表面的卤代酸配体和卤代醇配体中的一种或多种。所述卤代酸配体和卤代醇配体可以有效地钝化氧化钨纳米颗粒的缺陷态发光,提高氧化钨纳米颗粒在溶剂中的分散性和稳定性,提高包括所述氧化钨纳米材料的空穴功能层的空穴迁移率,提高光电器件的空穴注入及传输能力,从而改善光电器件中的电荷平衡,进而提升光电器件的外量子效率和寿命。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.
本申请实施例还提供一种空穴功能薄膜,所述空穴功能薄膜可以为空穴注入薄膜或空穴传输薄膜。所述空穴功能薄膜中包括所述氧化钨纳米材料。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.
本申请实施例还提供一种所述空穴功能薄膜的制备方法,包括如下步骤:The embodiment of the present application also provides a method for preparing the hole function thin film, comprising the following steps:
步骤S21:提供所述氧化钨纳米材料;Step S21: providing the tungsten oxide nanomaterial;
步骤S22:将所述氧化钨纳米材料设置在基板上,形成氧化钨纳米材料薄膜,即得到空穴空能膜。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.
可以理解,所述基板的种类没有限制。在一实施例中,所述基板为阳极衬底,所述衬底可以为玻璃等常规使用的衬底,所述氧化钨纳米材料设置在所述阳极上。在又一实施例中,所述基板包括层叠的阴极及发光层,所述氧化钨纳米材料设置在所述发光层上。It can be understood that the type of the substrate is not limited. In an embodiment, 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. In yet another embodiment, the substrate includes a stacked cathode and a light-emitting layer, and the tungsten oxide nanomaterial is disposed on the light-emitting layer.
所述步骤S22中,将所述氧化钨纳米材料设置在所述基板上的方法可以为化学法或物理法。其中,化学法可以为化学气相沉积法、连续离子层吸附与反应法、阳极氧化法、电解沉积法及共沉淀法等。物理法可以为物理镀膜法或溶液加工法,物理镀膜法可以为热蒸发镀膜法CVD、电子束蒸发镀膜法、磁控溅射法、多弧离子镀膜法、物理气相沉积法PVD、原子层沉积法及脉冲激光沉积法等;溶液加工法可以为旋涂法、印刷法、喷墨打印法、刮涂法、打印法、 浸渍提拉法、浸泡法、喷涂法、滚涂法、浇铸法、狭缝式涂布法及条状涂布法等。In the step S22, the method of disposing the tungsten oxide nanomaterial on the substrate may be a chemical method or a physical method. Among them, 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.
在一实施例中,将所述氧化钨纳米材料设置在所述基板上的方法为溶液法,此时,需要先将所述氧化钨纳米材料使用分散剂分散,得到氧化钨纳米材料分散液,然后将氧化钨纳米材料分散液通过溶液法设置在所述基板上。所述分散剂可以选自但不限于甲醇、乙醇、丁醇及戊醇中的一种或多种。在一实施例中,所述分散液的浓度范围为5-40mg/mL。In one embodiment, 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.
请参阅图2-4,本申请实施例还提供一种光电器件100,所述光电器件100可以为太阳能电池、光电探测器、有机光电器件(OLED)或量子点光电器件(QLED)。所述光电器件100包括依次层叠设置的阳极10、空穴功能层20、发光层30及阴极40。所述空穴功能层20包括空穴注入层21及空穴传输层22中的一种或多种。所述空穴注入层21和/或所述空穴传输层22为所述空穴空能膜,换言之,所述空穴注入层21和/或所述空穴传输层22中包括所述氧化钨纳米材料。Referring to FIGS. 2-4 , 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.
请参阅图2,在一实施例中,所述光电器件100包括依次层叠设置的阳极10、空穴注入层21、发光层30及阴极40。所述空穴注入层21中包括所述氧化钨纳米材料。Referring to FIG. 2 , in one embodiment, 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.
请参阅图3,在另一实施例中,所述光电器件100包括依次层叠设置的阳极10、空穴传输层22、发光层30及阴极40。所述空穴传输层22中包括所述氧化钨纳米材料。Please refer to FIG. 3 , in another embodiment, 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.
请参阅图4,在又一实施例中,所述光电器件100包括依次层叠设置的阳极10、空穴注入层21、空穴传输层22、发光层30及阴极40。所述空穴注入层21和/或所述空穴传输层22中包括所述氧化钨纳米材料。Please refer to FIG. 4 , in yet another embodiment, 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.
所述阳极10的材料为本领域已知用于阳极的材料,例如,可以选自但不限于掺杂金属氧化物电极、复合电极等。所述掺杂金属氧化物电极可以选自但不限于铟掺杂氧化锡(ITO)、氟掺杂氧化锡(FTO)、锑掺杂氧化锡(ATO)、铝掺杂氧化锌(AZO)、镓掺杂氧化锌(GZO)、铟掺杂氧化锌(IZO)、镁掺杂氧化锌(MZO)及铝掺杂氧化镁(AMO)中的一种或多种。所述复合电极为掺杂或非掺杂的透明金属氧化物层之间夹着金属层的复合电极,如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等。其中,“/”表示叠层结构,例如,AZO/Ag/AZO表示由AZO层、Ag层和AZO层依次层叠形成的具有层叠结构的复合电极。
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. Wherein, "/" indicates a laminated structure, for example, 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.
所述发光层30可以为有机发光层或量子点发光层。当所述发光层30为有机发光层时,所述光电器件100可以为有机光电器件。当所述发光层30为量子点发光层时,所述光电器件100可以为量子点光电器件。The light emitting layer 30 may be an organic light emitting layer or a quantum dot light emitting layer. When the light emitting layer 30 is an organic light emitting layer, the optoelectronic device 100 may be an organic optoelectronic device. When the light emitting layer 30 is a quantum dot light emitting layer, the optoelectronic device 100 may be a quantum dot optoelectronic device.
所述有机发光层的材料为本领域已知用于光电器件的有机发光层的材料,例如,可以选自但不限于CBP:Ir(mppy)3(4,4'-双(N-咔唑)-1,1'-联苯:三[2-(对甲苯基)吡啶-C2,N)合铱(III))、TCTA:Ir(mmpy)(4,4',4”-三(咔唑-9-基)三苯胺:三[2-(对甲苯基)吡啶-C2,N)合铱(III))、二芳香基蒽衍生物、二苯乙烯芳香族衍生物、芘衍生物或芴衍生物、发蓝色光的TBPe荧光材料、发绿色光的TTPA荧光材料、发橙色光的TBRb荧光材料、及发红色光的DBP荧光材料中的一种或多种。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.
所述量子点发光层的材料为本领域已知用于光电器件的量子点发光层的量子点材料,例如,可以选自但不限于单一结构量子点及核壳结构量子点中的一种或多种。例如,所述单一结构量子点可以选自但不限于II-VI族化合物、III-V族化合物和I-III-VI族化合物中的一种或多种。作为举例,所述II-VI族化合物可以选自但不限于CdSe、CdS、CdTe、ZnSe、ZnS、CdTe、ZnTe、CdZnS、CdZnSe、CdZnTe、ZnSeS、ZnSeTe、ZnTeS、CdSeS、CdSeTe、CdTeS、CdZnSeTe及CdZnSTe中的一种或多种;所述III-V族化合物可以选自但不限于InP、InAs、GaP、GaAs、GaSb、AlN、AlP、InAsP、InNP、InNSb、GaAlNP及InAlNP中的一种或多种;所述I-III-VI族化合物可以选自但不限于CuInS
2、CuInSe
2及AgInS
2中的一种或多种。所述核壳结构的量子点可以选自但不限于CdSe/ZnS、CdSe/ZnSe/ZnS、ZnCdSe/ZnSe/ZnS、ZnSe/ZnS、ZnSeTe/ZnS、CdSe/CdZnSeS/ZnS、InP/ZnSe/ZnS及InP/ZnSeS/ZnS中的一种或多种。
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. For example, 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. As an example, 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.
所述阴极40为本领域已知用于光电器件的阴极,例如,可以选自但不限于Ag电极、Al电极、Au电极、Pt电极、Ag/IZO电极,IZO电极或合金电极 的一种或多种。其中,Ag/IZO电极表示由Ag层和IZO层层叠形成的具有层叠结构的复合电极。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. Various. Among them, the Ag/IZO electrode refers to a composite electrode having a laminated structure formed by laminating an Ag layer and an IZO layer.
在一实施例中,所述光电器件100还包括电子传输层,所述电子传输层连接在所述发光层30与所述阴极40之间。In one embodiment, 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 .
所述电子传输层的材料为本领域已知用于电子传输层的材料,例如,可以选自但不限于ZnO、TiO
2、ZrO
2、HfO
2、Ca、Ba、CsF、LiF、CsCO
3、ZnMgO、PBD(2-(4-联苯基)-5-苯基恶二唑)、8-羟基喹啉铝(Alq3)及石墨烯中的一种或多种。
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.
在所述光电器件100同时包括空穴注入层21及空穴传输层22,且仅空穴注入层21包括所述氧化钨纳米材料时,所述空穴传输层22的材料可以为本领域已知用于空穴传输层的材料,例如,可以选自但不限于聚[双(4-苯基)(2,4,6-三甲基苯基)胺](PTAA)、2,2',7,7'-四[N,N-二(4-甲氧基苯基)氨基]-9,9'-螺二芴(spiro-omeTAD)、4,4'-环己基二[N,N-二(4-甲基苯基)苯胺](TAPC)、N,N′-双(1-奈基)-N,N′-二苯基-1,1′-二苯基-4,4′-二胺(NPB)、4,4'-双(N-咔唑)-1,1'-联苯(CBP)、聚[(9,9-二辛基芴基-2,7-二基)-co-(4,4'-(N-(对丁基苯基))二苯胺)](TFB)、聚(9-乙烯基咔唑)(PVK)、聚三苯胺(Poly-TPD)、聚(3,4-亚乙二氧基噻吩)-聚(苯乙烯磺酸)(PEDOT:PSS)及4,4',4”-三(咔唑-9-基)三苯胺(TCTA)中的一种或多种。When the photoelectric device 100 includes a hole injection layer 21 and a hole transport layer 22 at the same time, and only the hole injection layer 21 includes the tungsten oxide nanomaterial, the material of the hole transport layer 22 can be known in the art. Known materials for the hole transport layer, for example, 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'-biphenyl (CBP), poly[(9,9-dioctylfluorenyl-2,7- Diyl)-co-(4,4'-(N-(p-butylphenyl))diphenylamine)] (TFB), poly(9-vinylcarbazole) (PVK), polytriphenylamine (Poly- TPD), poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonic acid) (PEDOT:PSS) and 4,4',4"-tris(carbazol-9-yl)triphenylamine ( TCTA) in one or more.
在所述光电器件100同时包括空穴注入层21及空穴传输层22,且仅空穴传输层22包括所述氧化钨纳米材料时,所述空穴注入层21的材料为本领域已知用于空穴注入层的材料,例如可以选自但不限于2,3,6,7,10,11-六氰基-1,4,5,8,9,12-六氮杂苯并菲(HAT-CN)、PEDOT:PSS及其掺有s-MoO
3的衍生物(PEDOT:PSS:s-MoO
3)中的一种或多种。
When the photoelectric device 100 includes a hole injection layer 21 and a hole transport layer 22 at the same time, and only the hole transport layer 22 includes the tungsten oxide nanomaterial, the material of the hole injection layer 21 is known in the art The material used for the hole injection layer, for example, 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 ).
可以理解,所述光电器件100除上述各功能层外,还可以增设一些常规用于光电器件的有助于提升光电器件性能的功能层,例如电子阻挡层、空穴阻挡层、电子注入层及界面修饰层等。It can be understood that, in addition to the above-mentioned functional layers, 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.
可以理解,所述光电器件100的各层的材料可以依据光电器件100的发光需求进行调整。It can be understood that the material of each layer of the optoelectronic device 100 can be adjusted according to the light emission requirement of the optoelectronic device 100 .
可以理解,所述光电器件100可以为正置光电器件或倒置光电器件。It can be understood that the optoelectronic device 100 may be a positive optoelectronic device or an inverted optoelectronic device.
本申请实施例还提供一种所述光电器件100的制备方法,包括如下步骤:The embodiment of the present application also provides a method for preparing the optoelectronic device 100, including the following steps:
步骤S31:提供阳极10;Step S31: providing the anode 10;
步骤S32:提供所述氧化钨纳米材料,将所述氧化钨纳米材料设置在所述阳极10上,得到空穴功能层20;Step S32: providing the tungsten oxide nanomaterial, and disposing the tungsten oxide nanomaterial on the anode 10 to obtain a hole functional layer 20;
步骤S33:在所述空穴功能层20上依次形成层叠的发光层30及阴极40。Step S33 : sequentially forming a laminated light-emitting layer 30 and a cathode 40 on the hole functional layer 20 .
可以理解,在所述光电器件100还包括电子传输层时,所述步骤S33为:在所述空穴功能层20上依次形成层叠的发光层30、电子传输层及阴极40。It can be understood that when the optoelectronic device 100 further includes an electron transport layer, 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 .
本申请实施例还提供另一种所述光电器件100的制备方法,包括如下步骤:The embodiment of the present application also provides another method for preparing the optoelectronic device 100, which includes the following steps:
步骤S41:提供阴极40,在所述阴极40上形成发光层30;Step S41: providing a cathode 40, and forming a light-emitting layer 30 on the cathode 40;
步骤S42:提供所述氧化钨纳米材料,将所述氧化钨纳米材料设置在所述发光层30上,得到空穴功能层20;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;
步骤S43:在所述空穴功能层20上形成阳极10。Step S43 : forming the anode 10 on the hole functional layer 20 .
可以理解,在所述光电器件100还包括电子传输层时,所述步骤S41为:提供阴极40,在所述阴极40上依次形成层叠的电子传输层及发光层30。It can be understood that when the optoelectronic device 100 further includes an electron transport layer, 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 .
以上两种制备方法中:In the above two preparation methods:
所述形成阳极10、发光层30、电子传输层及阴极40的方法可采用本领域常规技术实现,例如可以为化学法或物理法。所述化学法或物理法参上文所述,在此不再赘述。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.
可以理解,在所述光电器件100还包括电子阻挡层、空穴阻挡层、电子注入层和/或界面修饰层等其它功能层时,所述光电器件100的制备方法还包括形成所述各功能层的步骤。It can be understood that when the photoelectric device 100 further includes other functional layers such as an electron blocking layer, a hole blocking layer, an electron injection layer and/or an interface modification layer, the preparation method of the photoelectric device 100 also includes forming the functional layer layer steps.
下面通过具体实施例来对本申请进行具体说明,以下实施例仅是本申请的部分实施例,不是对本申请的限定。The present application will be described in detail through specific examples below, and the following examples are only part of the examples of the present application, and are not intended to limit the present application.
实施例1Example 1
提供ITO/Ag/ITO复合阳极10,所述ITO/Ag/ITO复合阳极10中层叠的ITO层、Ag层及ITO层的厚度分别为10nm、100nm、10nm;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;
在所述阳极10上旋涂PEDOT:PSS(型号AI4083)材料,然后150℃热处理15min,得到厚度为24nm的空穴注入层21;Spin-coat PEDOT:PSS (model AI4083) material on the anode 10, and then heat-treat at 150° C. for 15 minutes to obtain a hole injection layer 21 with a thickness of 24 nm;
将10mmol Na
2WO
4·2H
2O溶解在100ml去离子水中,加入10%的HNO
3水溶液,剧烈搅拌,得到米白色的H
2WO
4沉淀,然后用异丙醇清洗所述H
2WO
4沉淀;将所述H
2WO
4沉淀溶于150mL的一氯化乙酸中,超声分散,加入10ml质量浓度为10wt%的K
2CO
3水溶液,剧烈搅拌60min,在50℃下搅拌2天后用去离子水和乙醇离心清洗,得到氧化钨纳米材料,所述氧化钨纳米材料包括氧化钨纳米颗粒及连接在所述氧化钨纳米颗粒表面的一氯化乙酸配体,所述一氯化乙酸配体的含量为20wt%;
Dissolve 10mmol Na 2 WO 4 2H 2 O in 100ml deionized water, add 10% HNO 3 aqueous solution, stir vigorously to obtain off-white H 2 WO 4 precipitate, then wash the H 2 WO 4 with isopropanol Precipitation: Dissolve the H 2 WO 4 precipitate in 150 mL of monochlorinated acetic acid, ultrasonically disperse, add 10 ml of K 2 CO 3 aqueous solution with a mass concentration of 10 wt%, stir vigorously for 60 min, and use it after stirring at 50°C for 2 days Centrifugal cleaning with ion water and ethanol to obtain tungsten oxide nanomaterials, the tungsten oxide nanomaterials include tungsten oxide nanoparticles and monochlorinated acetic acid ligands connected to the surface of the tungsten oxide nanoparticles, the monochlorinated acetic acid ligands The content is 20wt%;
将所述氧化钨纳米材料分散在环己烷中,得到浓度为20mg/mL的氧化钨纳米材料分散液,将所述氧化钨纳米材料分散液旋涂在所述空穴注入层21上,然后100℃热处理30min,得到厚度为24nm的空穴传输层22;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;
在所述空穴传输层22上旋涂CdSe/CdZnSeS/ZnS量子点发光材料,得到厚度为29nm的发光层30;Spin-coat CdSe/CdZnSeS/ZnS quantum dot luminescent material on the hole transport layer 22 to obtain a luminescent layer 30 with a thickness of 29 nm;
在所述发光层30上旋涂ZnMgO材料,其中ZnMgO材料中Mg的含量为15wt%,氮气气氛及100℃下热处理20min,得到厚度为50nm的电子传输层;Spin-coat ZnMgO material on the light-emitting layer 30, wherein the content of Mg in the ZnMgO material is 15wt%, heat treatment at 100° C. for 20 minutes in a nitrogen atmosphere, and obtain an electron transport layer with a thickness of 50 nm;
在所述电子传输层上蒸镀Ag,得到厚度为40nm的阴极40;Evaporating Ag on the electron transport layer to obtain a cathode 40 with a thickness of 40 nm;
在所述阴极40上蒸镀NPB材料,得到厚度为60nm的覆盖层,得到光电器件100。本实施例的光电器件100为量子点光电器件。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.
实施例2Example 2
本实施例与实施例1基本相同,区别在于,本实施例为将8mmol Na
2WO
4·2H
2O和1mmol TiW
2O
5·6H
2O溶解在100ml去离子水中,对应的,得到的氧化钨纳米材料包括Ti掺杂氧化钨纳米颗粒及连接在所述氧化钨纳米颗粒表面的一氯化乙酸配体。其中,Ti的摩尔量为W的摩尔量的10%。
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. Wherein, the molar amount of Ti is 10% of the molar amount of W.
实施例3Example 3
本实施例与实施例1基本相同,区别在于,本实施例为将8mmol Na
2WO
4·2H
2O和1mmol NiW
2O
5·6H
2O溶解在100ml去离子水中,对应的,得到的氧化钨纳米材料包括Ni掺杂氧化钨纳米颗粒及连接在所述氧化钨纳米颗粒表面的一氯化乙酸配体。其中,Ni的摩尔量为W的摩尔量的10%。
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. Wherein, the molar amount of Ni is 10% of the molar amount of W.
实施例4Example 4
本实施例与实施例1基本相同,区别在于,本实施例为将8mmol Na
2WO
4·2H
2O和2mmol MgWO
4·2H
2O溶解在100ml去离子水中,对应的,得到的氧化钨纳米材料包括Mg掺杂氧化钨纳米颗粒及连接在所述氧化钨纳米颗粒表面的一氯化乙酸配体。其中,Mg的摩尔量为W的摩尔量的20%。
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. Wherein, the molar amount of Mg is 20% of the molar amount of W.
实施例5Example 5
本实施例与实施例1基本相同,区别在于,本实施例为将8.5mmol Na
2WO
4·2H
2O、0.5mmol NiW
2O
5·6H
2O及0.5mmol MgWO
4·2H
2O溶解在100ml去离子水中,对应的,得到的氧化钨纳米材料包括Ni和Mg掺杂氧化钨纳米颗粒及连接在所述氧化钨纳米颗粒表面的一氯化乙酸配体。其中,Ni的摩尔量为W的摩尔量的5%,Mg的摩尔量为W的摩尔量的5%。
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. Wherein, the molar amount of Ni is 5% of the molar amount of W, and the molar amount of Mg is 5% of the molar amount of W.
实施例6Example 6
本实施例与实施例1基本相同,区别在于,本实施例为将8.5mmol Na
2WO
4·2H
2O、0.5mmol TiW
2O
5·6H
2O和0.5mmol MgWO
4·2H
2O溶解在100ml去离子水中,对应的,得到的氧化钨纳米材料包括Ti和Mg掺杂氧化钨纳米颗粒及连接在所述氧化钨纳米颗粒表面的一氯化乙酸配体。其中,Ti的摩尔量为W的摩尔量的5%,Mg的摩尔量为W的摩尔量的5%。
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. Wherein, the molar weight of Ti is 5% of the molar weight of W, and the molar weight of Mg is 5% of the molar weight of W.
实施例7Example 7
本实施例与实施例1基本相同,区别在于,将所述H
2WO
4沉淀溶于150mL的二氯化乙醇中,对应的,得到的氧化钨纳米材料包括氧化钨纳米颗粒及连接在所述氧化钨纳米颗粒表面的二氯化乙醇配体。
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.
实施例8Example 8
提供ITO/Ag/ITO复合阳极10,所述ITO/Ag/ITO复合阳极10中层叠的ITO层、Ag层及ITO层的厚度分别为10nm、100nm、10nm;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;
将10mmol Na
2WO
4·2H
2O溶解在100ml去离子水中,加入10%的HNO
3水溶液,剧烈搅拌,得到米白色的H
2WO
4沉淀,然后用异丙醇清洗所述H
2WO
4沉淀;将所述H
2WO
4沉淀溶于150mL的三氯代乙酸中,超声分散,加入10ml质量浓度为10wt%的K
2CO
3水溶液,剧烈搅拌60min,在50℃下搅拌2天后用去离子水和乙醇离心清洗,得到氧化钨纳米材料,所述氧化钨纳米材料包括 氧化钨纳米颗粒及连接在所述氧化钨纳米颗粒表面的三氯代乙酸配体,所述三氯代乙酸配体的含量为60wt%;
Dissolve 10mmol Na 2 WO 4 2H 2 O in 100ml deionized water, add 10% HNO 3 aqueous solution, stir vigorously to obtain off-white H 2 WO 4 precipitate, then wash the H 2 WO 4 with isopropanol Precipitation: Dissolve the H 2 WO 4 precipitate in 150 mL of trichloroacetic acid, ultrasonically disperse, add 10 ml of K 2 CO 3 aqueous solution with a mass concentration of 10 wt%, stir vigorously for 60 min, and use it after stirring at 50°C for 2 days Centrifugal cleaning with ion water and ethanol to obtain tungsten oxide nanomaterials, the tungsten oxide nanomaterials include tungsten oxide nanoparticles and trichloroacetic acid ligands connected to the surface of the tungsten oxide nanoparticles, the trichloroacetic acid ligands The content is 60wt%;
将所述氧化钨纳米材料分散在环己烷中,得到浓度为20mg/mL的氧化钨纳米材料分散液,将所述氧化钨纳米材料分散液旋涂在所述阳极10上,然后100℃热处理30min,得到厚度为24nm的空穴注入层21;Dispersing the tungsten oxide nanomaterial in cyclohexane to obtain a tungsten oxide nanomaterial dispersion with a concentration of 20 mg/mL, spin-coating the tungsten oxide nanomaterial dispersion on the anode 10, and then heat-treating at 100°C 30min to obtain a hole injection layer 21 with a thickness of 24nm;
在所述空穴注入层21上旋涂TFB材料,得到厚度为24nm的空穴传输层22;Spin-coat TFB material on the hole injection layer 21 to obtain a hole transport layer 22 with a thickness of 24 nm;
在所述空穴传输层22上旋涂CBP:Ir(mppy)3材料,得到厚度为29nm的发光层30;Spin-coat CBP:Ir(mppy)3 material on the hole transport layer 22 to obtain a light-emitting layer 30 with a thickness of 29nm;
在所述发光层30上旋涂PBD材料,氮气气氛及150℃下热处理30min,得到厚度为50nm的电子传输层;Spin-coat PBD material on the light-emitting layer 30, and heat-treat at 150° C. for 30 minutes in a nitrogen atmosphere to obtain an electron transport layer with a thickness of 50 nm;
在所述电子传输层上依次蒸镀Ag及IZO,得到厚度为40nm的Ag/IZO阴极40;Evaporating Ag and IZO sequentially on the electron transport layer to obtain an Ag/IZO cathode 40 with a thickness of 40 nm;
在所述阴极40上蒸镀NPB材料,得到厚度为60nm的覆盖层,得到光电器件100。本实施例的光电器件100为有机光电器件。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.
对比例1Comparative example 1
本对比例与实施例1基本相同,区别在于,本对比例的空穴传输22的材料为TFB。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.
对比例2Comparative example 2
本对比例与实施例8基本相同,区别在于,本对比例的空穴注入层21的材料为PEDOT:PSS(型号:AI4083)。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).
对所述实施例1-8及对比例1-2的光电器件进行外量子效率EQE及寿命T95_1knit测试。其中,外量子效率EQE及采用EQE光学测试仪器测定,寿命测试通过寿命测试盒进行,寿命T95_1knit是指量子点发光二极管在1knit特起始亮度下,亮度衰减至95%的时间。检测结果参下表一。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.
表一:Table I:
the | 外量子效率(EQE)/%External Quantum Efficiency (EQE)/% | T95_1knit寿命/hT95_1knit service life/h |
实施例1Example 1 | 1515 | 1200012000 |
实施例2Example 2 | 1616 | 1300013000 |
实施例3Example 3 | 1515 | 1200012000 |
实施例4Example 4 | 1717 | 1300013000 |
实施例5Example 5 | 1414 | 1100011000 |
实施例6Example 6 | 1515 | 1400014000 |
实施例7Example 7 | 1616 | 1500015000 |
实施例8Example 8 | 1515 | 1000010000 |
对比例1Comparative example 1 | 1010 | 20002000 |
对比例2Comparative example 2 | 55 | 30003000 |
由表一可知,实施例1-7的量子点光电器件的外量子效率及寿命明显高于对比例1的量子点光电器件的外量子效率及寿命,实施例8的有机光电器件的外量子效率及寿命明显高于对比例2的有机光电器件的外量子效率及寿命。As can be seen from Table 1, 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.
以上对本申请实施例所提供的氧化钨纳米材料及其制备方法、光电器件进行了详细介绍,本文中应用了具体个例对本申请的原理及实施方式进行了阐述,以上实施例的说明只是用于帮助理解本申请的方法及其核心思想;同时,对于本领域的技术人员,依据本申请的思想,在具体实施方式及应用范围上均会有改变之处,综上所述,本说明书内容不应理解为对本申请的限制。The tungsten oxide nanomaterials and their preparation methods and optoelectronic devices provided by the embodiments of the present application have been described in detail above. In this paper, specific examples are used to illustrate the principles and implementation methods of the present application. The descriptions of the above embodiments are only for To help understand the method and its core idea of this application; at the same time, for those skilled in the art, according to the idea of this application, there will be changes in the specific implementation and application scope. In summary, the content of this specification does not It should be understood as a limitation on the application.
Claims (20)
- 一种氧化钨纳米材料的制备方法,其中,包括如下步骤:A method for preparing tungsten oxide nanomaterials, comprising the steps of:提供钨酸;Provide tungstic acid;将所述钨酸与卤代化合物混合,其中,所述卤代化合物选自卤代酸和卤代醇中的一种或多种,加热反应,得到氧化钨纳米材料,所述氧化钨纳米材料包括氧化钨纳米颗粒及连接在所述氧化钨纳米颗粒表面的配体,所述配体包括卤代酸配体和卤代醇配体中的一种或多种。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.
- 如权利要求1所述的制备方法,其中,所述加热反应的温度范围为40-80℃,所述加热反应时间为48-72h。The preparation method according to claim 1, wherein the temperature range of the heating reaction is 40-80°C, and the heating reaction time is 48-72h.
- 如权利要求1所述的制备方法,其中,所述钨酸与所述卤代化合物的质量比的范围为(1.0:1)-(9.1:1)。The preparation method according to claim 1, wherein the range of the mass ratio of the tungstic acid to the halogenated compound is (1.0:1)-(9.1:1).
- 如权利要求3所述的制备方法,其中,所述钨酸的制备方法为:将钨酸盐与酸混合,反应,得到钨酸。The preparation method as claimed in claim 3, wherein, the preparation method of the tungstic acid is: mixing tungstate with acid and reacting to obtain tungstic acid.
- 如权利要求4所述的制备方法,其中,所述钨酸盐选自钨酸钠、钨酸钛、钨酸镍及钨酸镁中的一种或多种。The preparation method according to claim 4, wherein the tungstate is selected from one or more of sodium tungstate, titanium tungstate, nickel tungstate and magnesium tungstate.
- 如权利要求4所述的制备方法,其中,所述钨酸盐包括钨酸钛、钨酸镍及钨酸镁中的一种或多种,所述氧化钨纳米颗粒中掺杂有掺杂金属元素,所述掺杂金属元素选自Ti、Ni及Mg中的一种或多种。The preparation method according to claim 4, wherein the tungstate comprises one or more of titanium tungstate, nickel tungstate and magnesium tungstate, and the tungsten oxide nanoparticles are doped with doping metal element, the doping metal element is selected from one or more of Ti, Ni and Mg.
- 如权利要求6所述的制备方法,其中,所述掺杂金属元素的摩尔量为所述氧化钨的摩尔量的1-20%。The preparation method according to claim 6, wherein the molar amount of the doping metal element is 1-20% of the molar amount of the tungsten oxide.
- 如权利要求1所述的制备方法,其中,所述钨酸与所述卤代化合物混合后,还包括加入弱碱的步骤,其中,所述弱碱选自K 2CO 3、KHCO 3、Na 2CO 3及NaHCO 3中的一种或多种。 The preparation method according to claim 1, wherein, after the tungstic acid is mixed with the halogenated compound, it also includes the step of adding a weak base, wherein the weak base is selected from K 2 CO 3 , KHCO 3 , Na One or more of 2 CO 3 and NaHCO 3 .
- 如权利要求8所述的制备方法,其中,所述钨酸与所述弱碱的摩尔比的范围为(1:1.1)-(1:1.5)。The preparation method according to claim 8, wherein the molar ratio of the tungstic acid to the weak base is in the range of (1:1.1)-(1:1.5).
- 如权利要求1所述的制备方法,其中,所述卤代酸为卤代乙酸,所述卤代醇为卤代乙醇。The preparation method according to claim 1, wherein the halogenated acid is halogenated acetic acid, and the halogenated alcohol is halogenated alcohol.
- 如权利要求10所述的制备方法,其中,所述卤代乙酸选自一氯化乙酸、二氯化乙酸及三氯代乙酸中的一种或多种,所述卤代乙醇选自一氯化乙醇、 二氯化乙醇及三氯代乙醇中的一种或多种。The preparation method according to claim 10, wherein, the halogenated acetic acid is selected from one or more of monochlorinated acetic acid, dichlorinated acetic acid and trichloroacetic acid, and the halogenated alcohol is selected from monochloroacetic acid One or more of trichloroethanol, dichloroethanol and trichloroethanol.
- 一种氧化钨纳米材料,其中,所述氧化钨纳米材料包括氧化钨纳米颗粒及连接在所述氧化钨纳米颗粒表面的配体,所述配体包括卤代酸配体和卤代醇配体中的一种或多种。A tungsten oxide nanomaterial, wherein the tungsten oxide nanomaterial includes tungsten oxide nanoparticles and ligands connected to the surface of the tungsten oxide nanoparticles, and the ligands include haloacid ligands and halohydrin ligands one or more of.
- 如权利要求12所述的氧化钨纳米材料,其中,所述氧化钨纳米材料中,所述配体的含量范围为10-50wt%。The tungsten oxide nanomaterial according to claim 12, wherein, in the tungsten oxide nanomaterial, the content of the ligand is in the range of 10-50wt%.
- 如权利要求12所述的氧化钨纳米材料,其中,所述氧化钨纳米颗粒中掺杂有掺杂金属元素,所述掺杂金属元素选自Ti、Ni及Mg中的一种或多种。The tungsten oxide nanomaterial according to claim 12, wherein 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.
- 如权利要求14所述的氧化钨纳米材料,其中,所述掺杂金属元素的摩尔量为所述氧化钨的摩尔量的1-20%。The tungsten oxide nanomaterial according to claim 14, wherein the molar amount of the doping metal element is 1-20% of the molar amount of the tungsten oxide.
- 如权利要求12所述的氧化钨纳米材料,其中,所述氧化钨纳米颗粒的平均粒径为8-15nm。The tungsten oxide nanomaterial according to claim 12, wherein the average particle diameter of the tungsten oxide nanoparticles is 8-15nm.
- 如权利要求12所述的氧化钨纳米材料,其中,所述卤代酸配体中的卤代酸为卤代乙酸,所述卤代醇配体中的卤代醇为卤代乙醇。The tungsten oxide nanomaterial according to claim 12, wherein the haloacid in the haloacid ligand is haloacetic acid, and the halohydrin in the halohydrin ligand is haloethanol.
- 如权利要求17所述的氧化钨纳米材料,所述卤代乙酸选自一氯化乙酸、二氯化乙酸及三氯代乙酸中的一种或多种,所述卤代乙醇选自一氯化乙醇、二氯化乙醇及三氯代乙醇中的一种或多种。The tungsten oxide nanomaterial according to claim 17, wherein the halogenated acetic acid is selected from one or more of monochlorinated acetic acid, dichlorinated acetic acid and trichloroacetic acid, and the halogenated alcohol is selected from monochloroacetic acid One or more of trichloroethanol, dichloroethanol and trichloroethanol.
- 一种光电器件,包括层叠的阳极、空穴功能层、发光层及阴极,其中,所述空穴功能层中包括权利要求12-18任意一项所述的氧化钨纳米材料。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 tungsten oxide nanomaterial according to any one of claims 12-18.
- 如权利要求19所述的氧化钨纳米材料,其中,所述阳极选自掺杂金属氧化物电极或复合电极,所述掺杂金属氧化物电极选自铟掺杂氧化锡、氟掺杂氧化锡、锑掺杂氧化锡、铝掺杂氧化锌、镓掺杂氧化锌、铟掺杂氧化锌、镁掺杂氧化锌及铝掺杂氧化镁中的一种或多种,所述复合电极选自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或ZnS/Al/ZnS; The tungsten oxide nanomaterial according to claim 19, wherein the anode is selected from a doped metal oxide electrode or a composite electrode, and the doped metal oxide electrode is selected from indium-doped tin oxide, fluorine-doped tin oxide , one or more of antimony-doped tin oxide, aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, magnesium-doped zinc oxide and aluminum-doped magnesium oxide, and 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;所述发光层为有机发光层或量子点发光层,所述有机发光层的材料选自4,4'-双(N-咔唑)-1,1'-联苯:三[2-(对甲苯基)吡啶-C2,N)合铱(III)、4,4',4”-三(咔唑-9-基)三苯胺:三[2-(对甲苯基)吡啶-C2,N)合铱(III)、二芳香基蒽衍生物、二苯 乙烯芳香族衍生物、芘衍生物、芴衍生物、TBPe荧光材料、TTPA荧光材料、TBRb荧光材料、及DBP荧光材料中的一种或多种,所述量子点发光层的材料选自单一结构量子点及核壳结构量子点中的一种或多种,所述单一结构量子点选自II-VI族化合物、III-V族化合物和I-III-VI族化合物中的一种或多种,所述II-VI族化合物选自CdSe、CdS、CdTe、ZnSe、ZnS、CdTe、ZnTe、CdZnS、CdZnSe、CdZnTe、ZnSeS、ZnSeTe、ZnTeS、CdSeS、CdSeTe、CdTeS、CdZnSeTe及CdZnSTe中的一种或多种,所述III-V族化合物选自InP、InAs、GaP、GaAs、GaSb、AlN、AlP、InAsP、InNP、InNSb、GaAlNP及InAlNP中的一种或多种,所述I-III-VI族化合物选自CuInS 2、CuInSe 2及AgInS 2中的一种或多种,所述核壳结构的量子点选自CdSe/ZnS、CdSe/ZnSe/ZnS、ZnCdSe/ZnSe/ZnS、ZnSe/ZnS、ZnSeTe/ZnS、CdSe/CdZnSeS/ZnS、InP/ZnSe/ZnS及InP/ZnSeS/ZnS中的一种或多种; The light-emitting layer is an organic light-emitting layer or a quantum dot light-emitting layer, and 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) One or more of 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, and the single-structure quantum dots are selected from II-VI group compounds and III-V group compounds And one or more of I-III-VI group compounds, the II-VI group compound is selected from CdSe, CdS, CdTe, ZnSe, ZnS, CdTe, ZnTe, CdZnS, CdZnSe, CdZnTe, ZnSeS, ZnSeTe, ZnTeS , CdSeS, CdSeTe, CdTeS, CdZnSeTe and CdZnSTe one or more, the III-V compound is selected from InP, InAs, GaP, GaAs, GaSb, AlN, AlP, InAsP, InNP, InNSb, GaAlNP and InAlNP One or more of them, the I-III-VI group compound is selected from one or more of CuInS 2 , CuInSe 2 and AgInS 2 , and the quantum dots of the core-shell structure are selected from CdSe/ZnS, CdSe One or more of /ZnSe/ZnS, ZnCdSe/ZnSe/ZnS, ZnSe/ZnS, ZnSeTe/ZnS, CdSe/CdZnSeS/ZnS, InP/ZnSe/ZnS and InP/ZnSeS/ZnS;所述阴极选自Ag电极、Al电极、Au电极、Pt电极、Ag/IZO电极、IZO电极或合金电极的一种或多种。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.
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