WO2022121802A1 - Nanoparticule composite, diode électroluminescente à points quantiques et procédé de préparation - Google Patents

Nanoparticule composite, diode électroluminescente à points quantiques et procédé de préparation Download PDF

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WO2022121802A1
WO2022121802A1 PCT/CN2021/135444 CN2021135444W WO2022121802A1 WO 2022121802 A1 WO2022121802 A1 WO 2022121802A1 CN 2021135444 W CN2021135444 W CN 2021135444W WO 2022121802 A1 WO2022121802 A1 WO 2022121802A1
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quantum dot
dot light
layer
transport layer
emitting diode
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李龙基
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Tcl科技集团股份有限公司
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass

Definitions

  • the present disclosure relates to the field of quantum dots, and in particular, to composite nanoparticles, quantum dot light-emitting diodes and preparation methods.
  • quantum dots have the advantages of high light color purity, high luminescence quantum efficiency, tunable luminescence color, and high quantum yield, and can be prepared by printing process
  • quantum dot-based light emitting diodes QLEDs
  • QLEDs quantum dot-based light emitting diodes
  • Its device performance indicators are also developing rapidly.
  • N-type oxide nanoparticles are widely used as electron transport layer materials for electroluminescent devices because of their advantages of high transmittance, high electron mobility, low cost, environmental compatibility and simple preparation process. The efficiency of the device is greatly improved, but the problem of the short service life of the device still cannot be solved.
  • the purpose of the present disclosure is to provide a composite nanoparticle, a quantum dot light-emitting diode and a preparation method thereof, aiming at solving the problem of surface defects of oxide nanoparticles.
  • a composite nanoparticle comprising oxide nanoparticles containing hydroxyl groups on the surface and a passivator containing phosphorus-oxygen double bonds, the hydroxyl groups on the surface of the oxide nanoparticles and the phosphorus-oxygen double bonds in the passivator form hydrogen bonds.
  • the passivating agent is triphenylphosphine oxide.
  • the composite nanoparticles wherein the passivating agent is a triphenylphosphine oxide derivative, and the triphenylphosphine oxide derivative is One of them, wherein R 1 , R 2 and R 3 are delocalized and delocalized ⁇ -bonded groups; the delocalized and delocalized ⁇ -bonded groups are directly connected to the triphenylphosphine oxide, or the A delocalized pi-bond group is attached to the triphenylphosphine oxide through a pi-bond containing group.
  • the passivating agent is a triphenylphosphine oxide derivative
  • the triphenylphosphine oxide derivative is One of them, wherein R 1 , R 2 and R 3 are delocalized and delocalized ⁇ -bonded groups; the delocalized and delocalized ⁇ -bonded groups are directly connected to the triphenylphosphine oxide, or the A delocalized pi-bond group is attached to the triphenylphosphine oxide through a pi-bond containing group.
  • the composite nanoparticle wherein, the delocalized delocalized ⁇ bond group is one of a benzene ring or a butylene group; and/or, the group containing a ⁇ bond is a vinyl group or One of the acetylene groups.
  • the oxide nanoparticles are one or more of ZnO, TiO 2 , SnO 2 , Ta 2 O 3 , ZnMgO, ZnAlO and SnInO.
  • the composite nanoparticles wherein the composite nanoparticles are ZnO containing hydroxyl groups on the surface and triphenylphosphine oxide forming hydrogen bonds with the hydroxyl groups.
  • a quantum dot light-emitting diode comprising an electron transport layer, and the material of the electron transport layer is the composite nanoparticles described in this disclosure.
  • the quantum dot light-emitting diode further comprises a cathode, an anode and a quantum dot light-emitting layer arranged between the cathode and the anode, and the electron transport layer is arranged between the cathode and the quantum dot light-emitting layer .
  • the quantum dot light-emitting diode further comprises a hole function layer disposed between the anode and the quantum dot light-emitting layer, wherein the hole function layer is an electron blocking layer, a hole injection layer and a hole one or more of the transport layers.
  • the quantum dot light-emitting diode wherein the quantum dot light-emitting layer material is one or more of red light quantum dots, green light quantum dots and blue light quantum dots, the red light quantum dots, green light quantum dots and blue light quantum dots Independently selected from CdS, CdSe, CdTe, InP, AgS, PbS, HgS, ZnCdS, CuInS, ZnCdSe, ZnSeS, ZnCdTe, PbSeS, ZnCdS/ZnSe, CuInS/ZnS, ZnCdSe/ZnS, CuInSeS, ZnCdTe/ZnS, PbSeS/ZnS one or more of.
  • the anode is ITO, FTO or ZTO.
  • the cathode is one or more of Au, Ag, Al, Cu, and Mo.
  • a preparation method of a quantum dot light-emitting diode comprising the steps of:
  • An electron transport layer is prepared by depositing a composite nanoparticle solution on the substrate, the composite nanoparticle solution including an organic alcohol, and composite nanoparticles as described in the present disclosure dispersed in the organic alcohol.
  • the preparation method of the quantum dot light-emitting diode, wherein, the step of providing the substrate comprises:
  • the method further includes: preparing a cathode on the surface of the electron transport layer.
  • the method for preparing a quantum dot light-emitting diode comprises: providing a cathode substrate to form the substrate;
  • the method further includes:
  • An anode is prepared on the surface of the hole injection layer.
  • the mass fraction of the composite nanoparticle solution is 0.1-10%.
  • the organic alcohol is one of ethanol, propanol or butanol.
  • the thickness of the electron transport layer is 10-60 nm.
  • the phosphorus-oxygen double bond in the passivation agent can easily interact with the hydroxyl groups on the surface of the oxide nanoparticles to form hydrogen bonds, thereby playing a passivation effect on the oxide nanoparticles , reduce its surface defects.
  • FIG. 1 is a schematic structural diagram of a preferred embodiment of a positive structure quantum dot light emitting diode disclosed.
  • FIG. 2 is a schematic structural diagram of a preferred embodiment of an inversion structure quantum dot light emitting diode disclosed.
  • FIG. 3 is a flow chart of a preferred embodiment of a method for fabricating a quantum dot light-emitting diode with a positive structure disclosed.
  • FIG. 4 is a flow chart of a preferred embodiment of a method for fabricating a quantum dot light-emitting diode with an inversion structure disclosed.
  • the present disclosure provides a composite nanoparticle, a quantum dot light-emitting diode and a preparation method.
  • a composite nanoparticle a quantum dot light-emitting diode and a preparation method.
  • the present disclosure will be further described below in detail. It should be understood that the embodiments described herein are only used to explain the present disclosure, but not to limit the present disclosure.
  • embodiments of the present disclosure provide a nanocomposite particle, which includes oxide nanoparticles containing hydroxyl groups on the surface and a passivator containing phosphorus-oxygen double bonds.
  • the hydroxyl groups form hydrogen bonds with the phosphorus-oxygen double bonds in the passivator.
  • the oxygen atom in the phosphorus-oxygen double bond of the passivating agent can interact with the hydroxyl group on the surface of the oxide nanoparticle to form a hydrogen bond, so as to passivate the surface of the oxide nanoparticle and reduce its Surface defects.
  • the passivating agent is triphenylphosphine oxide
  • its chemical structural formula is The oxygen atoms in the phosphorus-oxygen double bond of the triphenylphosphine oxide interact with the hydroxyl groups on the surface of the oxide nanoparticles to form hydrogen bonds, so as to passivate the oxide nanoparticles, and the triphenylphosphine oxide
  • the superstructure or the formation of periodic closely-packed interconnected structures can be achieved through ⁇ - ⁇ conjugated self-assembly, thereby improving the passivation stability of the surface of the oxide nanoparticles, and the oxide nanoparticles can be stably passivated surface, thereby reducing its surface defects more effectively.
  • the passivating agent is a triphenylphosphine oxide derivative
  • the triphenylphosphine oxide derivative is One of them, wherein R 1 , R 2 and R 3 are delocalized and delocalized ⁇ -bonded groups; the delocalized and delocalized ⁇ -bonded groups are directly connected to the triphenylphosphine oxide, or the A delocalized pi-bond group is attached to the triphenylphosphine oxide through a pi-bond containing group.
  • the oxygen atom in the phosphorus-oxygen double bond of the triphenylphosphine oxide derivative can interact with the hydroxyl group on the surface of the oxide nanoparticles to form hydrogen bonds, so as to passivate the oxide nanoparticles , and triphenylphosphine oxide derivatives can achieve superstructures or form periodic closely-packed interconnected structures through ⁇ – ⁇ conjugated self-assembly, thereby improving the passivation stability of the oxide nanoparticle surface. , which can stably passivate the surface of oxide nanoparticles and reduce their surface defects more effectively.
  • the delocalized ⁇ -bonded delocalized ⁇ -bonded groups are directly connected to triphenyl
  • phosphine oxide can avoid increasing the steric hindrance effect, so as to avoid weakening the interaction between the phosphorus-oxygen double bond and the hydroxyl group.
  • the ⁇ bond forms conjugation, thereby achieving a wider range of conjugation, expanding the conjugation area of triphenylphosphine oxide derivatives, facilitating the formation of periodic closely-packed interconnected structures, thereby improving its passivation N-type oxidation stability of nanoparticles.
  • the R 1 , R 2 and R 3 are delocalized ⁇ bond delocalized ⁇ bond groups, and the delocalized ⁇ bond delocalized ⁇ bond group is connected to the The triphenylphosphine oxide link.
  • a delocalized pi-bonded pi-bonded group is attached to the triphenylphosphine oxide through a vinyl or ethynyl group.
  • the delocalized ⁇ -bond delocalized ⁇ -bond group in this embodiment can also form conjugation with the ⁇ -bond on triphenylphosphine oxide, thereby realizing a wider range of conjugation and expanding triphenylphosphine oxide derivatives
  • the conjugation area is convenient to form periodic close-packed interconnected structures, thereby improving the stability of their passivated N-type oxide nanoparticles.
  • the delocalized ⁇ -bond delocalized ⁇ -bond group is one of a butylene group or a benzene ring, but is not limited thereto.
  • a molecule composed of multiple atoms if there are parallel p orbitals, they coherently overlap together to form a whole, and p electrons move between multiple atoms to form a ⁇ -type chemical bond.
  • the bond is called delocalized ⁇ bond, or conjugated delocalized ⁇ bond delocalized ⁇ bond, referred to as delocalized ⁇ bond delocalized ⁇ bond.
  • Delocalized ⁇ bond is a ⁇ bond formed by 3 or more atoms parallel to each other with p orbitals overlapping each other from the side.
  • the molecular structure of benzene ring is that all six carbon atoms are sp2 heterozygous.
  • the p orbitals are combined into a regular hexagon in the same plane, and the remaining p orbitals that are not hybridized on each carbon atom are parallel to the plane formed by the benzene molecule, so all p orbitals can be Overlapping each other; the delocalized ⁇ bonds of benzene
  • the delocalized ⁇ bonds are evenly distributed on six carbon atoms, so the bond length and bond energy of each carbon-carbon bond in the benzene molecule are equal.
  • 1,3-butadiene its 4 carbon atoms are adjacent to 3 atoms, so sp hybridization is adopted, and these hybrid orbitals overlap each other to form a molecular ⁇ skeleton, so all atoms are in the same plane;
  • Each carbon atom also has a p orbital that is not involved in hybridization, which is perpendicular to the molecular plane.
  • There is one electron in each p orbital so there is a p-p delocalized ⁇ bond delocalized with "4 orbitals and 4 electrons" in the butadiene molecule. pi key.
  • the ⁇ bond-containing group is one of a vinyl group or an acetylene group.
  • the orbital (p orbital) of two atoms approaches from the direction perpendicular to the internuclear connecting line of the bonding atoms, the electron clouds overlap to form a bond, and the covalent bond formed in this way is called a ⁇ bond.
  • the oxide nanoparticles are N-type oxide nanoparticles.
  • the N-type oxide nanoparticles are one or more of ZnO, TiO 2 , SnO 2 , Ta 2 O 3 , ZnMgO, ZnAlO and SnInO, but are not limited thereto.
  • the composite nanoparticles are ZnO with hydroxyl groups on the surface and triphenylphosphine oxide hydrogen-bonded with the hydroxyl groups.
  • the oxygen atoms in the triphenylphosphine oxide interact with the hydroxyl groups on the surface of the N-type oxide nanoparticles to form hydrogen bonds, and the triphenylphosphine oxide molecules are self-assembled through ⁇ – ⁇ conjugated to achieve ultra-high structure, thereby improving the passivation stability, which can stably passivate the surface of N-type oxide nanoparticles, reduce surface defects, and eliminate the hydroxyl groups suspended on the surface, so as to continuously and effectively exert the electron transport performance of composite nanoparticles.
  • a quantum dot light-emitting diode which includes an electron transport layer, and the material of the electron transport layer is composite nanoparticles, and the composite nanoparticles include oxide nanoparticles containing hydroxyl groups on the surface and phosphorus oxide nanoparticles A passivating agent for double bonds, the hydroxyl groups on the surface of the oxide nanoparticles form hydrogen bonds with the phosphorus-oxygen double bonds in the passivating agent.
  • the surface of the oxide nanoparticles in the composite nanoparticles can be passivated.
  • the hanging hydroxyl groups can be prevented from being oxidized under the influence of long-term electrification conditions and the surrounding environment to form highly oxidizing OH radicals, so that the active OH radicals can be prevented from oxidizing organic substances, thereby reducing the shedding of ligands on the surface of quantum dots, and at the same time effectively exerting the electron transport properties of oxide nanoparticles. Therefore, using the composite nanoparticles as the electron transport layer material of the quantum dot light emitting diode can effectively improve the luminous efficiency and service life of the quantum dot light emitting diode.
  • a quantum dot light-emitting diode which includes an electron transport layer, and the material of the electron transport layer is composite nanoparticles, and the composite nanoparticles include oxide nanoparticles containing hydroxyl groups on the surface and triphenylene
  • the hydroxyl groups on the surface of the oxide nanoparticles form hydrogen bonds with the phosphorus-oxygen double bonds in the triphenylphosphine oxide.
  • the oxygen atoms in the phosphorus-oxygen double bond of the triphenylphosphine oxide interact with the hydroxyl groups on the surface of the oxide nanoparticles to form hydrogen bonds, so as to passivate the oxide nanoparticles, and the The triphenylphosphine oxide can realize superstructure or form a periodic closely packed interconnected structure through ⁇ - ⁇ conjugated self-assembly, thereby improving the passivation stability of the surface of the oxide nanoparticles, which can stabilize Passivate the surface of oxide nanoparticles, thereby reducing their surface defects more effectively.
  • the suspended hydroxyl groups can be prevented from being oxidized to generate highly oxidative OH radicals under the influence of long-term electrification conditions and the surrounding environment, so that active OH radicals can be avoided. Oxidize organic matter, thereby reducing the shedding of ligands on the surface of quantum dots, and at the same time effectively exerting the electron transport properties of oxide nanoparticles. Therefore, using the composite nanoparticles as the electron transport layer material of the quantum dot light emitting diode can effectively improve the luminous efficiency and service life of the quantum dot light emitting diode.
  • a quantum dot light-emitting diode which includes an electron transport layer, and the material of the electron transport layer is composite nanoparticles, and the composite nanoparticles include oxide nanoparticles containing hydroxyl groups on the surface and triphenylene A phosphine oxide derivative, the hydroxyl group on the surface of the oxide nanoparticle forms a hydrogen bond with the phosphorus-oxygen double bond in the triphenylphosphine oxide derivative, the passivating agent is a triphenylphosphine oxide derivative, the Triphenylphosphine oxide derivatives are One of, wherein, R 1 , R 2 and R 3 are delocalized ⁇ bond delocalized ⁇ bond groups; the delocalized ⁇ bond delocalized ⁇ bond group is directly connected to the triphenylphosphine oxide, Alternatively, the delocalized pi-bond group is linked to the triphenylphosphine oxide through a pi-bond-containing group.
  • the oxygen atom in the phosphorus-oxygen double bond of the triphenylphosphine oxide derivative can interact with the hydroxyl group on the surface of the oxide nanoparticles to form hydrogen bonds, so as to passivate the oxide nanoparticles , and triphenylphosphine oxide derivatives can realize superstructures or form periodic closely-packed interconnected structures through ⁇ – ⁇ conjugated self-assembly, thereby improving the passivation stability of the oxide nanoparticle surfaces. , which can stably passivate the surface of oxide nanoparticles and reduce their surface defects more effectively.
  • the R 1 , R 2 and R 3 are delocalized ⁇ bond groups directly connected to the triphenylphosphine oxide, on the one hand, it can avoid increasing the steric hindrance effect, thereby avoiding weakening the phosphorus-oxygen double bond.
  • the interaction with the hydroxyl group on the other hand, the delocalized ⁇ -bonded group can also form conjugation with the ⁇ -bond on triphenylphosphine oxide, thereby realizing a wider range of conjugation and expanding the derivatization of triphenylphosphine oxide.
  • the conjugated area of the compound facilitates the formation of periodic close-packed interconnected structures, thereby improving the stability of their passivated N-type oxide nanoparticles.
  • the surface of the oxide nanoparticles After the surface of the oxide nanoparticles is stably passivated, it can more effectively prevent the hanging hydroxyl groups from being oxidized to generate highly oxidative OH radicals under the influence of long-term power-on conditions and the surrounding environment, so as to avoid active
  • the OH radicals oxidize organic matter, thereby reducing the shedding of ligands on the surface of quantum dots, and at the same time effectively exerting the electron transport properties of oxide nanoparticles. Therefore, using the composite nanoparticles as the material of the electron transport layer of the quantum dot light emitting diode can effectively improve the luminous efficiency and service life of the quantum dot light emitting diode.
  • the R 1 , R 2 and R 3 are delocalized pi-bonded groups, and the delocalized pi-bonded groups are linked to the triphenylphosphine oxide through a pi-bond-containing group,
  • a delocalized pi-bonded group is attached to the triphenylphosphine oxide through a vinyl group.
  • the delocalized ⁇ -bond group in this embodiment can also form conjugation with the ⁇ -bond on triphenylphosphine oxide, thereby realizing a wider range of conjugation and expanding the conjugation area of triphenylphosphine oxide derivatives , facilitating the formation of periodic closely-packed interconnected structures, thereby enhancing the stability of their passivated N-type oxide nanoparticles.
  • a quantum dot light-emitting diode which includes an electron transport layer, and the material of the electron transport layer is ZnO containing hydroxyl groups on the surface and triphenylphosphine oxide forming hydrogen bonds with the hydroxyl groups.
  • the oxygen atoms in the triphenylphosphine oxide interact with the hydroxyl groups on the surface of the N-type oxide nanoparticles to form hydrogen bonds, and the triphenylphosphine oxide molecules are self-assembled through ⁇ – ⁇ conjugated to achieve ultra-high structure, thereby improving the passivation stability, which can stably passivate the surface of N-type oxide nanoparticles, reduce surface defects, and eliminate the hydroxyl groups suspended on the surface, so as to continuously and effectively exert the electron transport performance of the electron transport layer material.
  • a quantum dot light-emitting diode which includes a cathode, an anode, and a quantum dot light-emitting layer disposed between the cathode and the anode, and an electron transport layer is disposed between the cathode and the quantum dot light-emitting layer , a hole functional layer is arranged between the anode and the quantum dot light-emitting layer, wherein the electron transport layer materials are N-type oxide nanoparticles containing hydroxyl groups on the surface and triphenyl groups that form hydrogen bonds with the hydroxyl groups Phosphine oxide or triphenylphosphine oxide derivatives, the hole functional layer is one or more of an electron blocking layer, a hole injection layer and a hole transport layer, but is not limited thereto.
  • a quantum dot light-emitting diode with a positive structure is provided, as shown in FIG. 1 , which includes an anode disposed on the surface of a substrate, a hole injection layer disposed on the surface of the anode, and a hole injection layer disposed on the surface of the anode.
  • a hole transport layer on the surface a quantum dot light-emitting layer arranged on the surface of the hole transport layer, an electron transport layer arranged on the surface of the quantum dot light-emitting layer, and a cathode arranged on the surface of the electron transport layer, wherein the electron transport layer
  • the materials are N-type oxide nanoparticles containing hydroxyl groups on the surface and triphenylphosphine oxide or triphenylphosphine oxide derivatives that form hydrogen bonds with the hydroxyl groups.
  • a quantum dot light-emitting diode with an inversion structure is also provided, as shown in FIG. 2 , which includes a cathode disposed on the surface of the substrate, an electron transport layer disposed on the surface of the cathode, and an electron transport layer disposed on the surface of the electron transport layer.
  • the materials of each functional layer are common materials in the art, such as:
  • the substrate may be a rigid substrate (glass) or a flexible substrate.
  • the anode may be ITO, FTO, or ZTO.
  • the hole injection layer material may be water-soluble PEDOT:PSS, or may be other materials with good hole injection properties, such as NiO, MoO 3 , WO 3 or V 2 O 5 .
  • the hole injection layer material is PEDOT:PSS, and its thickness is 10-100 nm.
  • the hole transport layer material may be commonly used poly(9,9-dioctylfluorene-CO-N-(4-butylphenyl)diphenylamine) (TFB), poly(N ,N'bis(4-butylphenyl)-N,N'-bis(phenyl)benzidine)(Poly-TPD), poly(9,9-dioctylfluorene-co-bis-N,N -Phenyl-1,4-phenylenediamine) (PFB), 4,4',4"-tris(carbazol-9-yl)triphenylamine (TCTA), 4,4'-bis(9-carbazole) ) biphenyl (CBP), N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine (TPD), One or more of N,N'-diphenyl-N,N'-dipheny
  • the hole transport layer has a thickness of 1-100 nm.
  • the quantum dot light-emitting layer material may be one or more of common red light quantum dots, green light quantum dots and blue light quantum dots.
  • the cathode may be Au, Ag, Al, Cu, Mo, or alloys thereof.
  • the cathode has a thickness of 60-120 nm.
  • a method for preparing a positive structure quantum dot light-emitting diode is also provided, as shown in FIG. 3 , which includes the steps:
  • the preparation method of each layer may be a chemical method or a physical method, wherein the chemical method includes but is not limited to chemical vapor deposition method, continuous ion layer adsorption and reaction method, anodization method, electrolytic deposition method, co-precipitation method
  • chemical methods include but are not limited to solution methods (such as spin coating, printing, blade coating, dip-pulling, immersion, spraying, roll coating, casting, slot coating method or strip coating method, etc.), evaporation method (such as thermal evaporation method, electron beam evaporation method, magnetron sputtering method or multi-arc ion coating method, etc.), deposition method (such as physical vapor deposition method) , atomic layer deposition, pulsed laser deposition, etc.) one or more.
  • solution methods such as spin coating, printing, blade coating, dip-pulling, immersion, spraying, roll coating, casting, slot coating method or strip coating method, etc.
  • evaporation method such as thermal evaporation method, electron beam
  • the preparation of the composite material solution includes the steps of: adding triphenylphosphine oxide or a triphenylphosphine oxide derivative to the organic alcohol solution of N-type oxide nanoparticles containing hydroxyl groups on the surface, and sonicating Dispersion treatment is performed to obtain the composite material solution.
  • the organic alcohol is one of ethanol, propanol or butanol, but not limited thereto; the mass fraction of the composite material solution is 0.1-10%.
  • the electron transport layer has a thickness of 10-60 nm.
  • a preparation method of an inversion structure quantum dot light-emitting diode is also provided, as shown in FIG. 4 , which includes the steps:
  • an anode is prepared on the surface of the hole injection layer to prepare the quantum dot light-emitting diode.
  • An embodiment of the present disclosure provides a method for fabricating a positive-type quantum dot light-emitting diode, including the following steps:
  • the green quantum dot luminescent material was spin-coated on the surface of the hole transport layer with a thickness of 20 nm. residual solvent;
  • triphenylphosphorus oxide was added to 10 ml of an ethanol solution of ZnO nanoparticles with a concentration of 30 mg/mL, and then deposited on the quantum dot layer as an electron transport layer with a thickness of 30 nm. Place on a heating stage at 80°C for 10 minutes to remove residual solvent.
  • the wafers with each functional layer deposited are placed in an evaporation chamber and a layer of aluminum is thermally evaporated as a cathode through a mask plate, with a thickness of 100 nm, the device preparation is completed, and the quantum dot light-emitting diode is obtained.
  • the efficiency and service life of the quantum dot light-emitting diode prepared in Example 1 were tested. Compared with ZnO nanoparticles as the electron transport layer, the external quantum efficiency did not change much, from 16.8% to 16.9%, and the device life was T95@1000nits From 1100 hours to 2300 hours, the improvement is obvious.
  • An embodiment of the present disclosure provides a method for fabricating an inversion structure quantum dot light-emitting diode, which includes the following steps:
  • the patterned ITO substrate was placed in acetone, washing solution, deionized water and isopropanol in sequence for ultrasonic cleaning, and each step of the above ultrasonics lasted about 15 minutes. After the ultrasonic is completed, the ITO is placed in a clean oven for drying for use; after the ITO substrate is dried, the surface of the ITO is treated with ultraviolet ozone for 5 minutes to further remove the organic matter attached to the surface of the ITO.
  • triphenylphosphorus oxide was added to 10 mL of an ethanol solution of ZnO nanoparticles with a concentration of 30 mg/mL, mixed uniformly, and then spin-coated on ITO as an electron transport layer with a thickness of 25 nm. Heat on a heating stage at 80°C for 10 minutes to remove residual solvent.
  • the red quantum dot luminescent material was spin-coated on the surface of the electron transport layer with a thickness of 20 nm. After this step of deposition is completed, the wafer is placed on a heating table at 80°C for 10 minutes to remove residual solvent;
  • a layer of hole transport layer material NPB is evaporated, and the thickness of this layer is 10 nm.
  • the wafers with each functional layer deposited are placed in an evaporation chamber, and a layer of silver is thermally evaporated through a mask as an anode, with a thickness of 80 nm, the device preparation is completed, and the quantum dot light-emitting diode is obtained.
  • the efficiency and service life of the quantum dot light-emitting diode prepared in Example 2 were tested. Compared with ZnO nanoparticles as the electron transport layer, the external quantum efficiency did not change much, from 18.1% to 19.2%, and the device life was T95@1000nits There are 4400 hours increased to 6500 hours, the improvement is obvious.
  • An embodiment of the present disclosure provides a method for fabricating a positive-type quantum dot light-emitting diode, including the following steps:
  • the green quantum dot luminescent material was spin-coated on the surface of the hole transport layer with a thickness of 20 nm. residual solvent;
  • R 1 is a butylene group, which is then deposited on the quantum dot layer as an electron transport layer with a thickness of 30 nm. After the deposition is completed, the film is placed on a heating table at 80 ° C and heated for 10 minutes to remove residues solvent.
  • the wafers with each functional layer deposited are placed in an evaporation chamber and a layer of aluminum is thermally evaporated as a cathode through a mask plate, with a thickness of 100 nm, the device preparation is completed, and the quantum dot light-emitting diode is obtained.
  • the efficiency and service life of the quantum dot light-emitting diode prepared in Example 3 were tested. Compared with ZnO nanoparticles as the electron transport layer, the external quantum efficiency did not change much, from 16.8% to 17.5%, and the device life was T95@1000nits From 1200 hours to 3500 hours, the improvement is obvious.
  • An embodiment of the present disclosure provides a method for fabricating a positive-type quantum dot light-emitting diode, including the following steps:
  • the green quantum dot luminescent material was spin-coated on the surface of the hole transport layer with a thickness of 20 nm. residual solvent;
  • triphenylphosphine oxide derivative was added to 10 mL of 30 mg/mL ethanol solution of ZnO nanoparticles,
  • R 2 is a benzene ring, and the benzene ring is connected to the triphenylphosphine oxide through a vinyl group, and then it is deposited on the quantum dot layer as an electron transport layer with a thickness of 30 nm. After the deposition is completed, the The slides were placed on a heating stage at 80°C for 10 minutes to remove residual solvent.
  • the wafers with each functional layer deposited are placed in an evaporation chamber and a layer of aluminum is thermally evaporated as a cathode through a mask plate, with a thickness of 100 nm, the device preparation is completed, and the quantum dot light-emitting diode is obtained.
  • the efficiency and service life of the quantum dot light-emitting diode prepared in Example 4 were tested. Compared with ZnO nanoparticles as the electron transport layer, the external quantum efficiency did not change much, from 16.8% to 17.3%, and the device life was T95@1000nits From 1200 hours to 3300 hours, the improvement is obvious.
  • the quantum dot light-emitting diode includes an electron transport layer, and the material of the electron transport layer is oxide nanoparticles containing hydroxyl groups on the surface and triphenylphosphine oxide or triphenylphosphine oxide that forms hydrogen bonds with the hydroxyl groups. Phenylphosphine oxide derivatives.
  • the oxygen atoms in the phosphorus-oxygen double bond of the triphenylphosphine oxide and its derivatives can easily interact with the hydroxyl groups on the surface of the oxide nanoparticles to form hydrogen bonds, so as to passivate the oxide nanoparticles, and the three Phenylphosphine oxide or its derivatives can achieve superstructures or form periodic closely-packed interconnected structures through ⁇ – ⁇ conjugated self-assembly, thereby improving passivation stability and stabilizing passivation oxide nanoparticles surface, reduce surface defects, and eliminate the hydroxyl groups hanging on the surface of the oxide nanoparticles, so as to prevent the hanging hydroxyl groups from being oxidized to generate highly oxidizing OH radicals, so as to reduce the shedding of ligands on the surface of quantum dots, and at the same time effectively play the role of
  • the electron transport performance of the electron transport material can greatly improve the luminous efficiency and service life of the quantum dot light-emitting diode.

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  • Crystallography & Structural Chemistry (AREA)
  • Optics & Photonics (AREA)
  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

La présente divulgation concerne une nanoparticule composite, une diode électroluminescente à points quantiques et un procédé de préparation. La nanoparticule composite comprend une nanoparticule d'oxyde contenant des groupes hydroxyle en surface et un agent de passivation à double liaison phosphore-oxygène, et le groupe hydroxyle en surface de la nanoparticule d'oxyde forme une liaison hydrogène avec la double liaison phosphore-oxygène dans l'agent de passivation.
PCT/CN2021/135444 2020-12-08 2021-12-03 Nanoparticule composite, diode électroluminescente à points quantiques et procédé de préparation WO2022121802A1 (fr)

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CN202011423461.1 2020-12-08

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1951156A (zh) * 2004-04-20 2007-04-18 九州电力株式会社 有机场致发光元件及其制造方法和含磷有机化合物及其制备方法
US20080220244A1 (en) * 2004-01-21 2008-09-11 Chien M Wai Supercritical Fluids in the Formation and Modification of Nanostructures and Nanocomposites
US20120292594A1 (en) * 2011-05-16 2012-11-22 Zhou Zhaoqun Device including quantum dots and method for making same
US20150001528A1 (en) * 2011-12-08 2015-01-01 Qd Vision, Inc. Solution-processed sol-gel films, devices including same, and methods

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080220244A1 (en) * 2004-01-21 2008-09-11 Chien M Wai Supercritical Fluids in the Formation and Modification of Nanostructures and Nanocomposites
CN1951156A (zh) * 2004-04-20 2007-04-18 九州电力株式会社 有机场致发光元件及其制造方法和含磷有机化合物及其制备方法
US20120292594A1 (en) * 2011-05-16 2012-11-22 Zhou Zhaoqun Device including quantum dots and method for making same
US20150001528A1 (en) * 2011-12-08 2015-01-01 Qd Vision, Inc. Solution-processed sol-gel films, devices including same, and methods

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