WO2024021335A1 - Matériau composite et son procédé de préparation, et diode électroluminescente - Google Patents

Matériau composite et son procédé de préparation, et diode électroluminescente Download PDF

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WO2024021335A1
WO2024021335A1 PCT/CN2022/127734 CN2022127734W WO2024021335A1 WO 2024021335 A1 WO2024021335 A1 WO 2024021335A1 CN 2022127734 W CN2022127734 W CN 2022127734W WO 2024021335 A1 WO2024021335 A1 WO 2024021335A1
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ligand
composite material
group
light
inorganic semiconductor
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PCT/CN2022/127734
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Chinese (zh)
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郭煜林
吴龙佳
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Tcl科技集团股份有限公司
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10—OLED displays
    • H10K59/12—Active-matrix OLED [AMOLED] displays

Definitions

  • the present application relates to the field of display technology, and in particular to a composite material, a preparation method of the composite material, and a light-emitting diode.
  • OLED organic light-emitting diodes
  • QLED quantum dot light-emitting diodes
  • Traditional OLED and QLED device structures generally include anode, hole injection layer, hole transport layer, light emitting layer, electron transport layer, electron injection layer and cathode. Under the action of the electric field, the holes generated by the anode and the electrons generated by the cathode of the light-emitting device move, are injected into the hole transport layer and electron transport layer respectively, and finally migrate to the light-emitting layer. When the two meet in the light-emitting layer, a Energy excitons, which excite light-emitting molecules and ultimately produce visible light.
  • ZnO is a direct band gap n-type semiconductor material with a wide bandgap of 3.37eV and a low work function of 3.7eV. It also has the advantages of good stability, high transparency, safety and non-toxicity, making ZnO a suitable electronic material. Transmission layer material.
  • ZnO currently prepared by solution method or sol-gel method has many surface defects, which are large and non-uniform in size. It is easy to form electron capture centers and exciton recombination centers. As a result, the transmission efficiency of the ZnO electron transport layer is not high enough, which in turn leads to device failure. The luminous efficiency is low.
  • this application provides a composite material, a preparation method thereof, and a light-emitting diode.
  • Embodiments of the present application provide a composite material, including: a ligand-modified inorganic semiconductor material having a biurea group.
  • the composite material is composed of the inorganic semiconductor material and the ligand having a biurea group.
  • the ligand with a biuret group is selected from one of biuret ligands, ethylene diurea ligands, dithiobiuret ligands and 2,5-dithiodiurea ligands. or more.
  • the inorganic semiconductor material is a metal oxide nanoparticle, and the material of the metal oxide nanoparticle is selected from one or more of ZnO, TiO 2 , SnO 2 , Ta 2 O 3 , ZrO 2 , and NiO. kind.
  • the metal oxide particles are also doped with a doping element, and the doping element includes one or more of Li, Al, Mg, Be, Sn and In.
  • the molar ratio of the inorganic semiconductor material to the ligand having a bis-urea group is 1: (0.05-2).
  • the average particle size of the metal oxide nanoparticles is 5 to 20 nm.
  • this application also provides a method for preparing composite materials, including:
  • the first solvent in the solution is removed to obtain the composite material.
  • the molar ratio of the inorganic semiconductor material to the ligand having a bis-urea group is 1: (0.1-2.5).
  • the ligand with a biuret group is selected from one of biuret ligands, ethylene diurea ligands, dithiobiuret ligands and 2,5-dithiodiurea ligands. or more.
  • the inorganic semiconductor material is a metal oxide nanoparticle, and the material of the metal oxide nanoparticle is selected from one or more of ZnO, TiO 2 , SnO 2 , Ta 2 O 3 , ZrO 2 , and NiO. kind.
  • the metal oxide particles are also doped with a doping element, and the doping element includes one or more of Li, Al, Mg, Be, Sn and In.
  • the molar concentration of the inorganic semiconductor material in the solution is 0.1-1 mol/L.
  • the first solvent is selected from one of methanol, ethanol, propanol, butanol, pentanol, hexanol, ethylene glycol, triethylene glycol, glycerin, butylene glycol and hexylene glycol.
  • methanol ethanol
  • propanol propanol
  • butanol pentanol
  • hexanol ethylene glycol
  • triethylene glycol glycerin
  • butylene glycol and hexylene glycol hexylene glycol
  • the reaction condition is heating, the heating temperature is 40-80°C, and the heating time is 10 min-2h.
  • reaction conditions are ultrasonic at 20-40°C for 10 minutes-4 hours.
  • this application also provides a light-emitting diode, which includes: an anode, a light-emitting layer, an electron transport layer and a cathode stacked in sequence.
  • the material of the electron transport layer includes the above composite material.
  • the anode is selected from a doped metal oxide electrode, a composite electrode, a graphene electrode, and a carbon nanotube electrode, wherein the material of the doped metal oxide electrode is selected from the group consisting of indium-doped tin oxide, fluorine-doped One or more of mixed tin oxide, 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, the composite The 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; and/or
  • the light-emitting layer is an organic light-emitting layer or a quantum dot light-emitting layer, wherein the material of the organic light-emitting layer is selected from the group consisting of 4,4'-bis(N-carbazole)-1,1'-biphenyl:tris[2- (p-Tolyl)pyridine-C2,N)iridium(III), 4,4',4′′-tris(carbazol-9-yl)triphenylamine:tris[2-(p-tolyl)pyridine-C2, N) One or more of iridium, diarylanthracene derivatives, stilbene aromatic derivatives, pyrene derivatives, fluorene derivatives, TBPe fluorescent materials, TTPX fluorescent materials, TBRb fluorescent materials and DBP fluorescent materials , the material of the quantum dot light-emitting layer is selected from one or more of single structure quantum dots and core-shell structure quantum dots.
  • the material of the shell of the structural quantum dot is selected from the group consisting of CdSe, CdS, CdTe, ZnSe, ZnS, CdTe, ZnTe, CdZnS, CdZnSe, CdZnTe, ZnSeS, ZnSeTe, ZnTeS, GaAs, GaP, GaSb, HgS, HgSe, HgTe, CdSeS, CdSeTe , one or more of CdTeS, CdZnSeTe, CdZnSTe, InAs, InP, InSb, InAs, AlAs, AlP, AlN, InAsP, InNP, InNSb, GaAlNP, InAlNP, CuInS, CuInSe and AgInS 2 ; and/or
  • the material of the cathode is selected from one or more of Ag, Al, Au, Pt, Ca and Ba.
  • Figure 1 is a flow chart of a composite material preparation method provided by an embodiment of the present application.
  • Figure 2 is a schematic structural diagram of a light-emitting diode provided by an embodiment of the present application.
  • Figure 3 is a schematic structural diagram of another light-emitting diode provided by an embodiment of the present application.
  • Figure 4 is an AFM image of a composite material film prepared from the composite material of Example 1 of the present application.
  • Figure 5 is an AFM image of a film prepared from ZnO particles in Comparative Example 1 of the present application.
  • Expressions such as "one or more” in this application refer to one or more of the listed items, and “multiple” refers to any combination of two or more of these items, including a single item (species). ) or any combination of plural items (kinds), for example, “at least one (kind) of a, b, or c" or “at least one (kind) 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, and c can be single or multiple respectively.
  • Embodiments of the present application provide a composite material, including a ligand-modified inorganic semiconductor material having a biurea group. Specifically, the ligand having a bis-urea group is connected to the surface of the inorganic semiconductor material.
  • the composite material is composed of the inorganic semiconductor material and the ligand having a bis-urea group.
  • the inorganic semiconductor material may be selected from, but is not limited to, metal oxide particles.
  • the material of the metal oxide particles may be selected from, but is not limited to, one or more of ZnO, TiO 2 , SnO 2 , Ta 2 O 3 , ZrO 2 and NiO.
  • the metal oxide particles may also be doped with Li, Al, Mg, Be, Sn, In, etc.
  • the metal oxide particles are doped metal oxide particles, for example , the material of the doped metal oxide particles can be selected from but not limited to one or more of TiLiO, ZnAlO, ZnMgO, ZnBeO, ZnSnO, ZnLiO and InSnO.
  • the metal oxide particles are selected from ZnO or ZnMgO.
  • the average particle size of the metal oxide nanoparticles is 5-20 nm.
  • Metal oxide nanoparticles with the above average particle size have better electron transmission characteristics, stability and film-forming properties.
  • the ligand having a biuret group may be selected from, but is not limited to, one of biuret ligands, ethylene diurea ligands, dithiobiuret ligands and 2,5-dithiodiurea ligands. or more. It should be noted that the above-mentioned ligand having a biurea group can be combined with the surface of the inorganic semiconductor material through its own carbonyl structure, for example, through van der Waals forces, coordination bonds and/or chemical bonds.
  • the molar ratio of the inorganic semiconductor material to the ligand having a bis-urea group is 1: (0.05-2), such as 1: (0.1-1.8), or 1 (0.18 ⁇ 1.5), or 1: (0.3 ⁇ 1.6), or 1: (0.4 ⁇ 1.2), or 1: (0.5 ⁇ 1.2), or 1: (0.8 ⁇ 1).
  • the surface of the inorganic semiconductor material can be fully passivated and the composite material can have good film-forming properties.
  • the composite material is an electron transport material used to prepare the electron transport layer.
  • the composite material may also include a layer of polymethylmethacrylate (PMMA), polymer 2,2′,7,7′-tetrakis[N,N-bis(4-methoxybenzene) Materials such as Spiro-OMeTAD, etc. are known to be added to the electron transport layer to improve the performance of the electron transport layer.
  • PMMA polymethylmethacrylate
  • Spiro-OMeTAD Spiro-OMeTAD, etc.
  • the composite material described in the present application contains the inorganic semiconductor material modified by the ligand with a bis-urea group.
  • the ligand with the bis-urea group may be connected to the inorganic semiconductor material through van der Waals forces, coordination bonds and/or chemical bonds.
  • the surface of the inorganic semiconductor material is modified, thereby passivating the surface defects of the inorganic semiconductor material.
  • the ligand with a biurea group may also form a strong bond with the metal atom-oxygen atom inorganic framework in the inorganic semiconductor material through one or two carbonyl groups in the unique symmetrical carbonyl structure of the ligand with the biurea group. Coordination, thereby effectively passivating metal ion dangling bonds and oxygen defects on the surface of inorganic semiconductor materials, thereby avoiding the problem of large and uneven crystal sizes caused by rapid crystallization of inorganic semiconductor materials during annealing and film formation.
  • the ligand having a biurea group can also be coordinated to the surface of the inorganic semiconductor material through the amine group in its structure, thereby further passivating surface defects of the inorganic semiconductor material.
  • the unique symmetrical carbonyl structure in the ligand with biurea group forms a strong coordination with the metal atom-oxygen atom inorganic framework in the inorganic semiconductor material, and the composite material can also be used to prepare the electron transport of light-emitting diodes. layer, it can effectively alleviate the oxidation tendency of the cathode in contact with the electron transport layer.
  • the inorganic semiconductor material connected with the ligand having a bis-urea group has good surface morphology, high surface coverage and low roughness.
  • the ligand with a biurea group can induce a highly uniform crystal orientation, producing a synergistic effect of metal atom-oxygen atom anchoring and crystallization regulation on the inorganic semiconductor material. , which is conducive to the preparation of flat, dense, and well-crystallized composite films.
  • embodiments of the present application also provide a method for preparing the composite material, which includes the following steps:
  • Step S1 Dissolve the inorganic semiconductor material and the ligand having a bis-urea group in the first solvent and react to obtain a solution;
  • Step S2 Remove the first solvent in the solution to obtain the composite material.
  • the inorganic semiconductor material is as described above.
  • the inorganic semiconductor material is prepared by a solution method or a sol-gel method.
  • the ligand having a biuret group may be selected from, but is not limited to, one of biuret ligands, ethylene diurea ligands, dithiobiuret ligands and 2,5-dithiodiurea ligands. or more.
  • the molar ratio of the inorganic semiconductor material to the ligand having a bis-urea group is 1: (0.1-2.5), such as 1: (0.2-2.5), or 1: (0.3-2.2), or 1: (0.4) ⁇ 2), or 1: (0.5 ⁇ 1.8), or 1: (0.8 ⁇ 1.5), or 1: (1 ⁇ 2), or 1: (1.2 ⁇ 2.1).
  • a composite material with a suitable proportion can be prepared, and a composite material with good film-forming properties, electron transport properties and other properties can be prepared.
  • the amount of the first solvent is added in an amount such that the molar concentration of the inorganic semiconductor material is 0.1 ⁇ 1 mol/L.
  • the ligand having a bis-urea group can react quickly with the inorganic semiconductor material, so that the ligand having a bis-urea group can be combined with the surface of the inorganic semiconductor material through its own carbonyl structure.
  • the first solvent may be selected from, but is not limited to, one of methanol, ethanol, propanol, butanol, pentanol, hexanol, ethylene glycol, triethylene glycol, glycerin, butylene glycol and hexylene glycol. Kind or variety.
  • the reaction conditions are heating or ultrasound, which can effectively promote the reaction between the inorganic semiconductor material and the compound having a bis-urea group.
  • the heating temperature is 40-80°C and the heating time is 10 min-2h.
  • the ultrasound is performed at 20 to 40° C. for 10 min to 4 hours, for example, at room temperature for 10 min to 4 hours.
  • step S2
  • the method for removing the first solvent in the solution is one or more of heating drying, cooling drying and reduced pressure drying.
  • Embodiments of the present application also provide a composite material film.
  • the material of the composite material film includes the above-mentioned composite material, or the composite material film is prepared from the above-mentioned composite material through a film forming process.
  • the composite material film can be produced by the following method: dissolving the composite material in a second solvent to obtain a composite material solution, disposing the composite material solution on a substrate, and removing the second solvent through post-processing. Two solvents were used to obtain the composite film.
  • the method of disposing the composite material solution on the substrate may be a solution method or an evaporation method.
  • the solution method may be a spin coating method, a printing method, an inkjet printing method, a blade coating method, a printing method, a dip pulling method, a soaking method, a spray coating method, a roller coating method, a casting method, a slit coating method, and Strip coating method, etc.
  • the post-processing may be one or more of heating drying, cooling drying and reduced pressure drying.
  • the second solvent may be selected from, but is not limited to, one of methanol, ethanol, propanol, butanol, pentanol, hexanol, ethylene glycol, triethylene glycol, glycerol, butylene glycol and hexylene glycol. Kind or variety.
  • the composite material film includes the composite material, and has the characteristics of flatness, density, and good crystallization, and also has excellent optical stability and humidity stability, so that the light-emitting diode including the composite material film has higher Maximum brightness, higher maximum external quantum efficiency, lower turn-on voltage and longer life.
  • an embodiment of the present application also provides a light-emitting diode 100 , including an anode 10 , a light-emitting layer 20 , an electron transport layer 30 and a cathode 40 stacked in sequence.
  • the electron transport layer 30 is made of the above-mentioned composite material, or the electron transport layer 30 is the above-mentioned composite material film.
  • the light-emitting diode 100 further includes a hole transport layer 50 located between the anode 10 and the light-emitting layer 20 .
  • the light-emitting diode 100 includes an anode 10, a hole transport layer 50, a light-emitting layer 20, an electron transport layer 30 and a cathode 40 stacked in sequence.
  • the anode 10 is an anode known in the art for use in light-emitting diodes, and may be selected from, but not limited to, doped metal oxide electrodes, composite electrodes, graphene electrodes, and carbon nanotube electrodes.
  • the material of the doped metal oxide electrode may be selected from, but is not limited to, indium doped tin oxide (ITO), fluorine doped tin oxide (FTO), antimony doped tin oxide (ATO), aluminum doped zinc oxide (AZO) ), one or more of gallium-doped zinc oxide (GZO), indium-doped zinc oxide (IZO), magnesium-doped zinc oxide (MZO), and aluminum-doped magnesium oxide (AMO).
  • the composite electrode is a composite electrode with metal sandwiched between doped or non-doped transparent metal oxides, such as AZO/Ag/AZO, AZO/Al/AZO, ITO/Ag/ITO, ITO/Al/ITO, ZnO/Ag/ZnO, ZnO/Al/ZnO, TiO 2 /Ag/TiO 2 , TiO 2 /Al/TiO 2 , ZnS/Ag/ZnS, ZnS/Al/ZnS, etc.
  • "/" represents a stacked structure.
  • AZO/Ag/AZO represents a composite electrode with a stacked structure formed by sequentially stacking an AZO layer, an Ag layer, and an AZO layer.
  • the light-emitting layer 20 may be an organic light-emitting layer or a quantum dot light-emitting layer.
  • the light-emitting diode 100 may be an organic light-emitting diode; when the light-emitting layer 20 is a quantum dot light-emitting layer, the light-emitting diode 100 may be a quantum dot light-emitting diode.
  • the material of the organic light-emitting layer is a material known in the art for the organic light-emitting layer of a light-emitting diode.
  • it 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)), TCTX:Ir(mmpy)(4,4',4"-tris(carb Azol-9-yl)triphenylamine: tris[2-(p-tolyl)pyridine-C2,N)iridium), diarylanthracene derivatives, stilbene aromatic derivatives, pyrene derivatives, fluorene derivatives , one or more of TBPe fluorescent material that emits blue light, TTPX fluorescent material that emits green light, TBRb fluorescent material that emits orange light, and DBP fluorescent material that emits 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 a light-emitting diode.
  • it can be selected from but not limited to one of single structure quantum dots and core-shell structure quantum dots, or Various.
  • the materials of the single structure quantum dots, the core materials of the core-shell structure quantum dots, and the shell materials of the core-shell structure quantum dots can be selected from, but are not limited to, II-VI compounds, III-V compounds and I-III- One or more compounds of Group VI.
  • the material of the single structure quantum dot, the material of the core of the core-shell structure quantum dot, and the material of the shell of the core-shell structure quantum dot can be selected from but not limited to CdSe, CdS, CdTe, ZnSe, ZnS, CdTe, ZnTe , CdZnS, CdZnSe, CdZnTe, ZnSeS, ZnSeTe, ZnTeS, GaAs, GaP, GaSb, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdTeS, CdZnSeTe, CdZnSTe, InAs, InP, InSb, InAs, AlAs, AlP, AlN, InAsP , one or more of InNP, InNSb, GaAlNP, InAlNP, CuInS, CuInSe and AgInS 2 .
  • the quantum dots of the core-shell structure may be selected from, but are not limited to, CdSe/CdSeS/CdS, InP/ZnSeS/ZnS, CdZnSe/ZnSe/ZnS, CdSeS/ZnSeS/ZnS, CdSe/ZnS, CdSe/ZnSe/ZnS , ZnSe/ZnS, ZnSeTe/ZnS, CdSe/CdZnSeS/ZnS and one or more of InP/ZnSe/ZnS.
  • the material of the cathode 40 is a cathode material known in the art for use in light-emitting diodes, and may be selected from, but not limited to, one or more of Ag, Al, Au, Pt, Ca, and Ba.
  • the material of the hole transport layer 50 can also be a material known in the art for hole transport layers, for example, it can be selected from but not limited to poly[bis(4-phenyl)(2,4,6-tris)].
  • Methylphenyl)amine] PTAA
  • 2,2',7,7'-tetrakis[N,N-bis(4-methoxyphenyl)amino]-9,9'-spirobifluorene (spiro -omeTAD)
  • TAPC 4,4'-cyclohexylbis[N,N-bis(4-methylphenyl)aniline]
  • NPB 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-dioctylflu
  • the light-emitting diode 100 can also add some functional layers known in the art for light-emitting diodes that help improve the performance of the light-emitting diode, such as an electron blocking layer, a hole blocking layer, an electron injection layer, and a hole injection layer. , interface modification layer, etc.
  • each layer of the light-emitting diode 100 can be adjusted according to the lighting requirements of the light-emitting diode 100 .
  • the light-emitting diode 100 can be a positive light-emitting diode or an inverted light-emitting diode.
  • the electron transport layer 30 of the light-emitting diode 100 contains the composite material described in this application, so that it has higher luminous efficiency and longer life.
  • the present application also relates to a display device, which includes the light-emitting diode 100 .
  • Zinc chloride is added to DMF (N,N-dimethylformamide) to form a zinc salt solution with a total concentration of 0.5M; an ethanol solution of NaOH with a concentration of 0.6M is added dropwise to the zinc salt solution at room temperature. , continue stirring for 1.5h to obtain a clear and transparent solution, add acetone to the clear and transparent solution, precipitate ZnO particles, collect after centrifugation, and obtain ZnO particles;
  • the composite material of this embodiment includes ZnO particles modified with biuret ligands.
  • the molar ratio of ZnO particles to biuret ligand is 1:0.4.
  • This embodiment is basically the same as Example 1. The difference is that in this embodiment, zinc nitrate hexahydrate is used to replace the zinc chloride in Example 1, an ethanol solution of KOH is used to replace the ethanol solution of NaOH in Example 1, and ethylene dihydrogen is used.
  • the urea ligand replaces the biuret ligand in Example 1.
  • the composite material of this embodiment includes ZnO particles modified with ethylenediurea ligands.
  • the molar ratio of ZnO particles to ethylene diurea ligand is 1:0.4.
  • This embodiment is basically the same as Example 1. The difference is that this embodiment uses zinc acetate dihydrate to replace the zinc chloride in Example 1, and uses an ethanol solution of tetramethylammonium hydroxide to replace the NaOH in ethanol in Example 1. solution, using dithiobiuret ligand to replace the biuret ligand in Example 1.
  • the composite material of this embodiment includes ZnO particles modified with dithiobiuret ligands.
  • the molar ratio of ZnO particles to dithiobiuret ligands is 1:0.3.
  • This embodiment is basically the same as Example 1. The difference is that in this embodiment, ethylene diurea ligand and 2,5-dithiodiurea ligand are added to the above-mentioned ZnO ethanol solution. Among them, ZnO particles, ethylene diurea The molar ratio of ligand and 2,5-dithiodiurea ligand is 1:0.5:0.5.
  • the composite material in this embodiment includes ZnO particles modified with ethylenediurea ligand and 2,5-dithiodiurea ligand.
  • the molar ratio of ZnO particles, ethylene diurea ligand, and 2,5-disulfide ligand is 1:0.4:0.4.
  • This embodiment is basically the same as Example 1, except that the molar ratio of ZnO particles to biuret ligands during the preparation process of the composite material in this embodiment is 1:0.3.
  • the molar ratio of ZnO particles to biuret ligand is 1:0.18.
  • This embodiment is basically the same as Example 1, except that the molar ratio of ZnO particles to biuret ligands during the preparation process of the composite material in this embodiment is 1:1.
  • the molar ratio of ZnO particles to biuret ligand is 1:0.8.
  • This embodiment is basically the same as Example 1, except that the molar ratio of ZnO particles to biuret ligands during the preparation of the composite material in this embodiment is 1:2.2.
  • the molar ratio of ZnO particles to biuret ligand is 1:1.5.
  • This embodiment is basically the same as Example 1, except that the molar ratio of ZnO particles to biuret ligands during the preparation process of the composite material in this embodiment is 1:0.05.
  • the molar ratio of ZnO particles to biuret ligand is 1:0.01.
  • This embodiment is basically the same as Example 1, except that the molar ratio of ZnO particles to biuret ligands during the preparation process of the composite material in this embodiment is 1:3.
  • the molar ratio of ZnO particles to biuret ligand is 1:2.
  • Example 2 This example is basically the same as Example 1. The difference is that in this example, an ethanol solution of NaOH with a concentration of 0.6M is added dropwise to the zinc salt solution at room temperature and 0.025 mol of magnesium nitrate is added at the same time.
  • the particles prepared are: ZnMgO particles.
  • the composite material of this embodiment includes ZnMgO particles modified with biuret ligands.
  • the molar ratio of ZnMgO particles to biuret ligand is 1:0.4.
  • Embodiment 1 This embodiment is basically the same as Embodiment 1, except that this embodiment uses tin chloride to replace zinc chloride in Embodiment 1.
  • the composite material of this embodiment includes biuret ligand-modified SnO particles .
  • the molar ratio of SnO 2 particles to the biuret ligand is 1:0.4.
  • Zinc chloride is added to DMF (N,N-dimethylformamide) to form a zinc salt solution with a total concentration of 0.5M; an ethanol solution of NaOH with a concentration of 0.6M is added dropwise to the zinc salt solution at room temperature. , continue stirring for 1.5 h to obtain a clear and transparent solution; add acetone to the clear and transparent solution to precipitate ZnO particles, collect them after centrifugation, and obtain ZnO particles.
  • DMF N,N-dimethylformamide
  • This comparative example is basically the same as Comparative Example 1, except that this comparative example uses 1-methylurea ligand (monourea-based ligand) to replace the biuret ligand in Example 1.
  • 1-methylurea ligand diourea-based ligand
  • the composite material of this comparative example includes ZnO particles modified with 1-methylurea ligand.
  • the molar ratio of ZnO particles to 1-methylurea ligand is 1:0.4.
  • This comparative example is basically the same as Example 11, except that this comparative example uses 1-methylurea ligand (monourea-based ligand) to replace the biuret ligand in Example 11.
  • 1-methylurea ligand diourea-based ligand
  • the composite material of this comparative example includes 1-methylurea ligand- modified SnO particles.
  • the molar ratio of SnO 2 particles to the 1-methylurea ligand is 1:0.4.
  • Example 1 and Comparative Examples 1 to 2 were respectively dissolved in ethanol to obtain a solution with a concentration of 30 mg/mL.
  • the solution was spin-coated on a glass substrate and annealed at 100°C for 20 min to obtain a thickness of 40 nm. composite film.
  • AFM test was performed to obtain the AFM image of the composite film prepared from the composite material of Example 1 (see Figure 4), the AFM image of the film prepared from the ZnO particles of Comparative Example 1 (see Figure 5), and the AFM image of the film prepared from the ZnO particles of Comparative Example 1 (see Figure 5), and The roughness of the composite material film prepared from the composite material, the composite material film prepared from the composite material of Comparative Example 2, and the film prepared from the ZnO particles of Comparative Example 1 (see Table 1).
  • ITO anode 10 with a thickness of 55nm
  • Example 1 The composite material in Example 1 was dissolved in ethanol to obtain a composite material solution with a concentration of 30 mg/mL.
  • the composite material solution was spin-coated on the light-emitting layer 20 and annealed at 100°C for 20 minutes to obtain a composite material with a thickness of 40 nm.
  • Material film i.e. electron transport layer 30;
  • Al is evaporated on the electron transport layer 30 to obtain a cathode 40 with a thickness of 100 nm;
  • Device Embodiments 2 to 11 are basically the same as Device Embodiment 1, except that Device Embodiments 2 to 11 use the composite materials of Embodiments 2 to 11 respectively to replace the composite materials in Device Embodiment 1.
  • Device Comparative Examples 1 to 3 are basically the same as Device Embodiment 1. The difference is that Device Comparative Examples 1 to 3 use the materials of Comparative Examples 1 to 3 respectively to replace the composite material in Device Embodiment 1.
  • the light-emitting diodes of Device Examples 1 to 11 and Device Comparative Examples 1 to 3 were tested for turn-on voltage, maximum luminous efficiency, maximum brightness and lifetime T95@1000nit. The test results are shown in Table 2.
  • the test method of the turn-on voltage is: using the efficiency test system built by Keithley 6485 to obtain the voltage value when the brightness reaches 1nit, which is the turn-on voltage;
  • the maximum luminous efficiency and maximum brightness are measured using luminance meters PR650 and Keithley respectively to test the brightness and current.
  • the current density is obtained according to the luminous area.
  • the maximum brightness is obtained by the luminance meter test.
  • the ratio of the maximum brightness to the current density is the measurement of the maximum luminous efficiency;
  • the life test refers to measuring the time it takes for the brightness of the device to decay to a certain proportion of the maximum brightness under constant current or voltage driving. The time when the brightness decays to 95% of the maximum brightness is defined as T95. This life is the measured life.
  • the device life test is usually performed at high brightness by accelerating device aging, and the life at low brightness is obtained by fitting the attenuation fitting formula. For example, the life at 1000 nits is recorded as T95@1000 nits, and the calculation formula is: :
  • T95 L is the life under low brightness, generally taking the life under 1000nits
  • T95 H is the life under high brightness, which is the measured life
  • L H is the maximum brightness that the device accelerates to
  • L L is generally 1000nits
  • A is The acceleration factor is 1.7.
  • the driving current used in the above test of this application is 2mA.
  • the light-emitting diodes of Examples 1-7 and 10-11 Compared with the light-emitting diodes of Comparative Examples 1-3, the light-emitting diodes of Examples 1-7 and 10-11 have lower turn-on voltage, higher luminous efficiency, greater maximum brightness and longer life;
  • the light-emitting diodes of Embodiments 8-9 Compared with the light-emitting diodes of Embodiments 1 and 5-7, the light-emitting diodes of Embodiments 8-9 have higher turn-on voltage, lower luminous efficiency, smaller maximum brightness, and shorter life. The reason may be due to the implementation of The composite material of Example 8 has a lower content of biuret ligand, while the composite material of Example 9 has a higher content of biuret ligand.

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  • Physics & Mathematics (AREA)
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Abstract

La présente demande divulgue un matériau composite et un procédé de préparation, et une diode électroluminescente. Le matériau composite comprend un matériau semi-conducteur inorganique modifié par un ligand diureido. Selon le matériau composite, une structure carbonyle symétrique unique dans le ligand diuréido et la structure inorganique d'atome d'oxygène-atome métallique dans le matériau semi-conducteur inorganique forment un effet de coordination ferme, de telle sorte que les défauts de la surface du matériau semi-conducteur inorganique sont efficacement passivés, ce qui facilite la préparation d'un film de matériau composite de transport d'électrons ayant de bonnes performances.
PCT/CN2022/127734 2022-07-25 2022-10-26 Matériau composite et son procédé de préparation, et diode électroluminescente WO2024021335A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014093328A (ja) * 2012-10-31 2014-05-19 Fujifilm Corp 半導体膜、半導体膜の製造方法、太陽電池、発光ダイオード、薄膜トランジスタおよび電子デバイス
CN104403120A (zh) * 2014-11-14 2015-03-11 无锡中洁能源技术有限公司 一种高强度锂离子电池用隔膜的制备方法
CN105845914A (zh) * 2016-05-26 2016-08-10 江苏深苏电子科技有限公司 一种锂离子电池负极复合材料的制备方法
CN110741042A (zh) * 2017-06-15 2020-01-31 阿科玛法国公司 粘附性提高的基于氟化聚合物的墨
CN111384261A (zh) * 2018-12-28 2020-07-07 Tcl集团股份有限公司 一种薄膜及其制备方法与量子点发光二极管

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014093328A (ja) * 2012-10-31 2014-05-19 Fujifilm Corp 半導体膜、半導体膜の製造方法、太陽電池、発光ダイオード、薄膜トランジスタおよび電子デバイス
CN104403120A (zh) * 2014-11-14 2015-03-11 无锡中洁能源技术有限公司 一种高强度锂离子电池用隔膜的制备方法
CN105845914A (zh) * 2016-05-26 2016-08-10 江苏深苏电子科技有限公司 一种锂离子电池负极复合材料的制备方法
CN110741042A (zh) * 2017-06-15 2020-01-31 阿科玛法国公司 粘附性提高的基于氟化聚合物的墨
CN111384261A (zh) * 2018-12-28 2020-07-07 Tcl集团股份有限公司 一种薄膜及其制备方法与量子点发光二极管

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