WO2023197658A1 - Light-emitting device, preparation method for light-emitting device, and display apparatus - Google Patents

Light-emitting device, preparation method for light-emitting device, and display apparatus Download PDF

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Publication number
WO2023197658A1
WO2023197658A1 PCT/CN2022/140025 CN2022140025W WO2023197658A1 WO 2023197658 A1 WO2023197658 A1 WO 2023197658A1 CN 2022140025 W CN2022140025 W CN 2022140025W WO 2023197658 A1 WO2023197658 A1 WO 2023197658A1
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compound
light
emitting device
transport layer
layer
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PCT/CN2022/140025
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French (fr)
Chinese (zh)
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罗强
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Tcl科技集团股份有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • 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
    • H10K50/165—Electron transporting layers comprising dopants
    • 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]
    • H10K50/18—Carrier blocking layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass

Definitions

  • the present application relates to the field of optoelectronic technology, and specifically to a light-emitting device, a method for preparing the light-emitting device, and a display device.
  • Light-emitting devices include but are not limited to organic light-emitting diodes (OLED) and quantum dot light-emitting diodes (QLED).
  • the light-emitting devices have a "sandwich" structure, which includes an anode, a cathode and a light-emitting layer. Wherein, the anode and the cathode are arranged oppositely, and the luminescent layer is arranged between the anode and the cathode.
  • the light-emitting principle of a light-emitting device is: electrons are injected from the cathode of the device to the light-emitting area, holes are injected from the anode of the device to the light-emitting area, electrons and holes recombine in the light-emitting area to form excitons, and the recombined excitons transition through radiation. Release photons, thereby emitting light.
  • QLED has the problem of unbalanced carrier injection. That is, the existing QLED generally has the problem that electron injection is greater than hole injection during operation, causing the phenomenon of electron accumulation in the light-emitting layer, thus increasing the non-linearity. Energy is lost due to the probability of luminous recombination (such as Auger recombination), resulting in performance degradation problems during QLED operation, such as reduced luminous efficiency, shortened service life, etc.
  • the present application provides a light-emitting device, a method for preparing the light-emitting device, and a display device to improve the luminous efficiency and working life of the light-emitting device.
  • this application provides a light-emitting device, which includes:
  • the cathode is arranged opposite to the anode
  • An electron transport layer is provided between the cathode and the light-emitting layer
  • the material of the electron transport layer includes a first compound and a second compound, the first compound is a nanometal oxide, and the second compound is a nucleating agent.
  • the first compound is selected from ZnO, TiO 2 , SnO 2 , BaO, Ta 2 O 3 , ZrO 2 , TiLiO, ZnGaO, ZnAlO, ZnMgO, ZnSnO, ZnLiO, InSnO, AlZnO, ZnOCl or ZnOF. At least one.
  • the average particle size of the first compound is 2 nm to 15 nm.
  • the nucleating agent is selected from one or more of organic nucleating agents and inorganic nucleating agents;
  • the organic nucleating agent is selected from one or more of carboxylic acid metal salt compounds, sorbitol compounds, polymer nucleating agents and ⁇ crystal nucleating agents;
  • the inorganic nucleating agent is selected from one or more types of carbon black, calcium oxide, mica, talc and kaolin.
  • the carboxylic acid metal salt compound is selected from the group consisting of sodium succinate, sodium glutarate, sodium caproate, sodium 4-methylvalerate, adipic acid, aluminum adipate, and aluminum tert-butyl benzoate. , one or more of aluminum benzoate, potassium benzoate, lithium benzoate, sodium cinnamate and sodium beta-naphthoate;
  • the sorbitol compound is selected from one or more of dibenzylidene sorbitol, di(p-monomethylbenzylidene) sorbitol, and di(p-chlorosubstituted benzylidene) sorbitol;
  • the polymer nucleating agent is selected from one or more of polyvinylcyclohexane, polyethylenepentane and ethylene/acrylate copolymer;
  • the ⁇ -crystalline nucleating agent is selected from ⁇ -type polypropylene.
  • the molar ratio of the first compound:the second compound is 1: (0.1 ⁇ 0.2).
  • the material of the light-emitting layer is quantum dots, and the quantum dots are selected from the group consisting of single-component quantum dots, core-shell structure quantum dots, inorganic perovskite quantum dots, and organic-inorganic hybrid perovskite quantum dots. one or more;
  • the materials of the single-component quantum dots, the core materials of the core-shell structure quantum dots, and the core-shell structure quantum dots are independently selected from at least one of II-VI compounds, III-V compounds, IV-VI compounds or I-III-VI compounds, wherein the II-VI compounds are selected from CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, At least one of HgZnS, HgZnSe, H
  • the materials of the anode and the cathode are independently selected from one or more of metals, carbon materials and metal oxides, wherein the metal is selected from Al, Ag, Cu, Mo, Au, Ba, Ca and one or more of Mg; the carbon material is selected from one or more of graphite, carbon nanotubes, graphene and carbon fiber; the metal oxide is selected from indium tin oxide, fluorine-doped tin oxide , one or more of tin antimony oxide, aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, and magnesium-doped zinc oxide.
  • the light-emitting device further includes a hole function layer, the hole function layer is disposed between the anode and the light-emitting layer;
  • the hole function layer includes one or more of a hole injection layer and a hole transport layer.
  • the hole function layer includes a hole transport layer and a hole injection layer arranged in a stack, the hole function layer The transport layer is close to the light-emitting layer, and the hole injection layer is close to the anode;
  • the material of the hole transport layer is selected from NiO, WO 3 , MoO 3 , CuO, poly(9,9-dioctylfluorene-CO-N-(4-butylphenyl)diphenylamine), 3-hexyl Substituted polythiophene, poly(9-vinylcarbazole), poly[bis(4-phenyl)(4-butylphenyl)amine], poly(N,N'-bis(4-butylphenyl)- N,N'-diphenyl-1,4-phenylenediamine-CO-9,9-dioctylfluorene), 4,4',4′′-tris(carbazol-9-yl)triphenylamine, 4 ,4'-bis(9-carbazole)biphenyl, N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4'
  • the material of the hole injection layer is selected from poly(3,4-ethylenedioxythiophene): poly(styrenesulfonic acid), copper phthalocyanine, 2,3,5,6-tetrafluoro-7,7',8,8'-tetracyanodimethylp-benzoquinone, 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazabenzophenanthrene, One or more of transition metal oxides and transition metal chalcogenide compounds, wherein the transition metal oxide is selected from one or more of NiO x , MoO x , WO x and CrO x , and the transition metal oxide
  • the metal chalcogenide compound is selected from one or more of MoS x , MoS x , WS x , WSe x and CuS.
  • this application provides a method for preparing a light-emitting device, which method includes the following steps:
  • a laminated structure Apply a mixed solution containing a first compound and a second compound on one side of the laminated structure, and dry it to obtain an electron transport layer;
  • the first compound is a nanometal oxide
  • the second compound is a nucleating agent
  • the stacked structure is a substrate including an anode and a light-emitting layer, and the electron transport layer is formed on the side of the light-emitting layer away from the anode;
  • the stacked structure is a substrate including a cathode, and the electron transport layer is formed on one side of the cathode.
  • the first compound is selected from ZnO, TiO 2 , SnO 2 , BaO, Ta 2 O 3 , ZrO 2 , TiLiO, ZnGaO, ZnAlO, ZnMgO, ZnSnO, ZnLiO, InSnO, AlZnO, ZnOCl or ZnOF. At least one.
  • the average particle size of the first compound is 2 nm to 15 nm.
  • the nucleating agent is selected from one or more of organic nucleating agents and inorganic nucleating agents;
  • the organic nucleating agent is selected from one or more of carboxylic acid metal salt compounds, sorbitol compounds, polymer nucleating agents and beta crystal nucleating agents;
  • the carboxylic acid metal salt compound Selected from sodium succinate, sodium glutarate, sodium caproate, sodium 4-methylvalerate, adipic acid, aluminum adipate, tert-butyl aluminum benzoate, aluminum benzoate, potassium benzoate, lithium benzoate , sodium cinnamate and sodium ⁇ -naphthoate, one or more;
  • the sorbitol compound is selected from dibenzyl sorbitol, di(p-monomethylbenzyl) sorbitol and di(p-chloro substituted benzyl sorbitol) ) one or more of sorbitol;
  • the polymer nucleating agent is selected from one or more of polyvinylcyclohexane, polyethylene pentane and ethylene/acrylate copolymer; the
  • the inorganic nucleating agent is selected from one or more types of carbon black, calcium oxide, mica, talc and kaolin.
  • the molar ratio of the first compound:the second compound is 1: (0.1 ⁇ 0.2).
  • the second compound is a solid, and in the mixed liquid, the mass ratio of the first compound to the second compound is 1: (0.02-0.05).
  • the second compound is a liquid
  • the preparation method of the mixed solution includes the steps of: providing a solution containing the first compound, and mixing the second compound with the solution containing the first compound to prepare the mixed liquid;
  • the concentration of the first compound is 30 mg/mL to 60 mg/mL;
  • the volume ratio of the solution containing the first compound: the second compound is 1: (0.01 ⁇ 0.0125).
  • applying a mixed liquid containing the first compound and the second compound on one side of the laminated structure includes the steps of: providing a mixed liquid containing the first compound and the second compound, and placing the mixed liquid. Process the AC electric field for a preset time.
  • the intensity of the AC electric field is 100v/m to 500v/m
  • the frequency of the AC electric field is 50Hz to 100Hz
  • the effective voltage value of the AC electric field is 100V to 200V.
  • the preset time is 1 min to 5 min.
  • the present application provides a display device.
  • the display device includes a light-emitting device, and the light-emitting device includes:
  • the cathode is arranged opposite to the anode
  • An electron transport layer is provided between the cathode and the light-emitting layer
  • the material of the electron transport layer includes a first compound and a second compound, the first compound is a nanometal oxide, and the second compound is a nucleating agent.
  • the first compound is selected from ZnO, TiO 2 , SnO 2 , BaO, Ta 2 O 3 , ZrO 2 , TiLiO, ZnGaO, ZnAlO, ZnMgO, ZnSnO, ZnLiO, InSnO, AlZnO, ZnOCl or ZnOF. at least one;
  • the nucleating agent is selected from one or more organic nucleating agents and inorganic nucleating agents; the organic nucleating agent is selected from carboxylic acid metal salt compounds, sorbitol compounds, polymer nucleating agents, and One or more beta crystal nucleating agents, the carboxylic acid metal salt compound is selected from the group consisting of sodium succinate, sodium glutarate, sodium hexanoate, sodium 4-methylvalerate, adipic acid, and adipic acid.
  • the sorbitol compound is selected from dibenzylidene One or more of sorbitol, di(p-monomethylbenzyl) sorbitol and di(p-chlorosubstituted benzylidene) sorbitol
  • the polymer nucleating agent is selected from polyvinylcyclohexane, poly One or more of ethylene pentane and ethylene/acrylate copolymer
  • the ⁇ crystalline nucleating agent is selected from ⁇ -type polypropylene
  • the inorganic nucleating agent is selected from carbon black, calcium oxide, mica, talc One or more of powder and kaolin;
  • the molar ratio of the first compound:the second compound is 1: (0.1 ⁇ 0.2).
  • adding a tangible nucleating agent to the electron transport layer can promote the non-spontaneous nucleation of nano-metal oxides to increase the number of nuclei, achieve the purpose of refining the grains of nano-metal oxides, and increase electron transmission.
  • the number of grain boundaries of the layer, and the particle size of the nanometal oxide will not change significantly, thereby increasing the grain size of the electron transport layer, causing the grain boundary barrier to increase, effectively increasing the resistance of the electron transport layer , thereby increasing the difficulty of electron migration and reducing the electron mobility of the light-emitting device, so that under the same energization conditions, the electron injection level of the light-emitting device in the embodiment of the present application is lower than that of the existing light-emitting device, thereby improving It solves the problem of existing light-emitting devices that electron injection is greater than hole injection, improves the electron-hole transmission matching degree, effectively promotes the carrier injection balance of the light-emitting device, and is conducive to improving the luminous efficiency and working life of the light-emitting device.
  • the electron transport layer is prepared by mixing the nanometer metal oxide and the nucleating agent in a solution, which increases the number of heterogeneous cores and promotes the non-spontaneous nucleation of the nanometer metal oxide.
  • the number of grain boundaries of the electron transport layer is increased, thereby increasing the grain size of the electron transport layer, causing the grain boundary barrier to increase, thereby effectively increasing the resistance of the electron transport layer. It improves the difficulty of electron migration, reduces the level of electron injection, promotes the balance of electron-hole transport, and thereby improves the luminous efficiency and working life of the light-emitting device.
  • Applying the light-emitting device of the present application to a display device is beneficial to improving the display effect of the display device and extending the service life of the display device.
  • FIG. 1 is a schematic structural diagram of a first light-emitting device provided in an embodiment of the present application.
  • FIG. 2 is a schematic structural diagram of a second light-emitting device provided in an embodiment of the present application.
  • Figure 3 is a schematic diagram of the grain size of the electron transport layer provided in the embodiment of the present application under different processing methods.
  • FIG. 4 is a schematic structural diagram of a third light-emitting device provided in an embodiment of the present application.
  • Embodiments of the present application provide a quantum dot light-emitting diode device, a preparation method thereof, and a display panel. Each is explained in detail below. It should be noted that the order of description of the following embodiments does not limit the preferred order of the embodiments.
  • the term "and/or” is used to describe the association relationship of associated objects, indicating that there can be three relationships.
  • a and/or B can represent three situations: the first situation is that A alone exists ; The second case is when A and B exist at the same time; the third case is when B exists alone, where A and B can be singular or plural respectively.
  • the term "at least one” refers to one or more, and "a plurality” refers to two or more than two.
  • the term “at least one” or similar expressions thereof refers to any combination of these species, including any combination of a single species or a plurality of species.
  • "at least one (number) of a, b or c" or “at least one (number) of a, b and c” can be expressed as: a, b, c, a-b (i.e. a and b ), a-c, b-c or a-b-c, where a, b and c can be a single species (number) or multiple species (number) respectively.
  • the embodiment of the present application provides a light-emitting device.
  • the light-emitting device 1 includes an anode 11, a cathode 12, a luminescent layer 13 and an electron transport layer 14.
  • the anode 11 and the cathode 12 are arranged opposite to each other, and the luminescent layer 13 is arranged between the anode 11 and the cathode 12 , the electron transport layer 14 is disposed between the cathode 12 and the light-emitting layer 13 .
  • the material of the electron transport layer 14 includes a first compound and a second compound, the first compound is a nanometal oxide, and the second compound is a nucleating agent.
  • nucleating agent also known as nucleating agent, refers to a type of compound that can change the partial crystallization behavior of nanometer metal oxides.
  • the principle of action is to provide the crystal nuclei required for the nucleation of nanometer metal oxides, so that Nano-metal oxides change from homogeneous nucleation to heterogeneous nucleation to increase the number of nuclei, thereby accelerating the crystallization speed and refining the grain structure, and the particle size of nano-metal oxides does not change significantly.
  • Adding a nucleating agent to the electron transport layer can promote the non-spontaneous nucleation of nanometal oxides to refine the grains of nanometal oxides, increase the number of grain boundaries of the electron transport layer, thereby improving the grain size of the electron transport layer. Therefore, the grain boundary barrier increases, effectively increasing the resistance of the electron transport layer, thereby increasing the difficulty of electron migration and reducing the electron mobility of the light-emitting device.
  • the electron injection level of the light-emitting device in the embodiment of the present application is lower than that of the existing light-emitting device, thereby improving the problem that the electron injection is greater than the hole injection in the existing light-emitting device, and improving It improves the electron-hole transmission matching degree, effectively promotes the carrier injection balance of the light-emitting device, and is beneficial to improving the luminous efficiency and working life of the light-emitting device.
  • grain boundary refers to the interface between grains belonging to the same solid phase but with different orientations.
  • grain size is a measure of the average size of grains in a nanometal oxide; the more grain boundaries, the larger the grain size.
  • the first compound may be an undoped nanometer metal oxide or a doped nanometer metal oxide.
  • the first compound is selected from ZnO, TiO 2 , SnO 2 , BaO, Ta 2 O 3 , ZrO 2 , TiLiO, ZnGaO, ZnAlO, ZnMgO, ZnSnO, ZnLiO, InSnO, AlZnO, ZnOCl or At least one of ZnOF.
  • the average particle diameter of the first compound may be, for example, 2 nm to 15 nm.
  • the second compound is selected from an organic nucleating agent and/or an inorganic nucleating agent.
  • the organic nucleating agent is selected from at least one of carboxylic acid metal salt compounds, sorbitol compounds, polymer nucleating agents or beta crystal nucleating agents.
  • the carboxylic acid metal salt compound is selected from sodium succinate, sodium glutarate, sodium caproate, sodium 4-methylvalerate, adipic acid, aluminum adipate, tert-butyl aluminum benzoate, At least one of aluminum benzoate, potassium benzoate, lithium benzoate, sodium cinnamate or sodium beta-naphthoate, and the sorbitol compound is selected from dibenzyl sorbitol, di(p-monomethylbenzyl) sorbitol or At least one of di(p-chloro-substituted benzylidene) sorbitol, the polymer nucleating agent is selected from at least one of polyvinylcyclohexane, polyethylenepentane or ethylene/acrylate copolymer, the ⁇ The crystal nucleating agent is selected from ⁇ -type polypropylene; the inorganic nucleating agent is selected from at least one of carbon black, calcium oxide, mica, talc or
  • the second compound is selected from dibenzylidene sorbitol, which has the advantages of being cheap, easy to obtain, and causing little environmental harm.
  • dibenzylidene sorbitol is a colorless material
  • dibenzylidene sorbitol is Alcohol will not affect the transparency of the electron transport layer and thus will not have a negative impact on the luminous efficiency of the light-emitting device.
  • the molar ratio of the first compound to the second compound in the electron transport layer is 1: (0.1 ⁇ 0.2), which is conducive to further promoting nanometal oxidation While non-spontaneous nucleation of matter is achieved, the matching degree between the electron injection level and the hole injection level of the light-emitting device is maximized.
  • the materials of the anode 11, the cathode 12 and the light-emitting layer 13 can be common materials in the art, such as:
  • the materials of the anode 11 and the cathode 12 are independently selected from at least one of metals, carbon materials or metal oxides, and the metal is selected from at least one of Al, Ag, Cu, Mo, Au, Ba, Ca or Mg;
  • the carbon material is selected from at least one of graphite, carbon nanotubes, graphene or carbon fiber;
  • the metal oxide can be doped or non-doped metal oxide, for example, selected from indium tin oxide (ITO), fluorine-doped tin oxide (FTO), antimony tin oxide (ATO), aluminum-doped zinc oxide (AZO), gallium-doped zinc oxide (GZO), indium-doped zinc oxide (IZO) or magnesium-doped zinc oxide (MZO) at least one of them.
  • the anode 11 or the cathode 12 can also be selected from a composite electrode with metal sandwiched between doped or non-doped transparent metal oxides.
  • the composite electrode includes but is not limited to AZO/Ag/AZO, AZO/Al/AZO, and ITO/Ag.
  • the thickness of the anode 11 may be, for example, 40 nm to 160 nm, and the thickness of the cathode 12 may be, for example, 20 nm to 120 nm.
  • the material of the light-emitting layer 13 is quantum dots, and the thickness of the light-emitting layer 13 may be, for example, 20 nm to 100 nm.
  • Quantum dots include, but are not limited to, at least one of red quantum dots, green quantum dots, or blue quantum dots, and quantum dots include, but are not limited to, single-component quantum dots, core-shell structure quantum dots, and inorganic perovskite quantum dots. dots or at least one of organic-inorganic hybrid perovskite quantum dots.
  • the particle size of the quantum dots may be, for example, 5 nm to 10 nm.
  • the materials of the single-component quantum dots, the core materials of the core-shell structure quantum dots, and the shell materials of the core-shell structure quantum dots are mutually exclusive.
  • the II-VI compound is selected from CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZ nSe,
  • CdZnSe only means that it is composed of three elements: Cd, Zn and Se. If it means the content of each element, it corresponds to Cd x Zn 1-x Se, 0 ⁇ x ⁇ 1.
  • inorganic perovskite quantum dots the general structural formula of inorganic perovskite quantum dots is AMX 3 , where A is Cs + ion, M is a divalent metal cation, and M includes but is not limited to Pb 2+ , Sn 2+ , Cu 2+ , Ni 2+ , Cd 2+ , Cr 2+ , Mn 2+ , Co 2+ , Fe 2+ , Ge 2+ , Yb 2+ or Eu 2+ , X is a halogen anion, including but not limited to Cl - , Br - or I - .
  • organic-inorganic hybrid perovskite quantum dots the general structural formula of organic-inorganic hybrid perovskite quantum dots is BMX 3 , where B is an organic amine cation, including but not limited to CH 3 (CH 2 ) n - 2NH 3+ (n ⁇ 2) or NH 3 (CH 2 ) n NH 3 2+ (n ⁇ 2), M is a divalent metal cation, M includes but is not limited to Pb 2+ , Sn 2+ , Cu 2+ , Ni 2+ , Cd 2+ , Cr 2+ , Mn 2+ , Co 2+ , Fe 2+ , Ge 2+ , Yb 2+ or Eu 2+ , X is a halogen anion, including but not limited to Cl - , Br - or I - .
  • the material of the light-emitting layer when the material of the light-emitting layer includes quantum dots, the material of the light-emitting layer also includes ligands connected to the surface of the quantum dots.
  • the ligands include but are not limited to amine ligands, carboxylic acid ligands, and thiols.
  • At least one of the thiol ligands is selected from ethyl mercaptan, propyl mercaptan, mercaptoethanol, benzene mercaptan, octyl mercaptan, octadecyl mercaptan, dodecyl mercaptan
  • the light-emitting device 1 also includes a hole function layer 15 , and the hole function layer 15 is disposed on the anode 11 and the light-emitting layer 13 between.
  • the hole function layer 15 includes a hole injection layer and/or a hole transport layer.
  • the hole function layer includes a hole transport layer and a hole injection layer arranged in a stack, the hole transport layer is close to the light-emitting layer, and the hole injection layer close to the anode.
  • the thickness of the hole function layer 15 may be, for example, 20 nm to 200 nm.
  • the material of the hole transport layer includes but is not limited to poly(9,9-dioctylfluorene-CO-N-(4-butylphenyl)diphenylamine) (TFB for short, CAS number: 220797-16-0 ), 3-hexyl substituted polythiophene (CAS number: 104934-50-1), poly(9-vinylcarbazole) (abbreviated as PVK, CAS number: 25067-59-8), poly[bis(4-phenyl) )(4-butylphenyl)amine] (referred to as Poly-TPD, CAS number is 472960-35-3), poly(N,N'-di(4-butylphenyl)-N,N'- Diphenyl-1,4-phenylenediamine-CO-9,9-dioctylfluorene) (referred to as PFB, CAS number is 223569-28-6), 4,4',4"-tris(carbazole)
  • the materials of the hole injection layer include but are not limited to poly(3,4-ethylenedioxythiophene): poly(styrenesulfonic acid) (CAS number: 155090-83-8), copper phthalocyanine (referred to as CuPc, CAS number is 147-14-8), 2,3,5,6-tetrafluoro-7,7',8,8'-tetracyanodimethyl-p-benzoquinone (referred to as F4-TCNQ, CAS number is 29261 -33-4), 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazabenzophenanthrene (referred to as HATCN,
  • transition metal oxides or transition metal chalcogenide compounds wherein the transition metal oxide can be at least one of NiO x , MoO x , WO x or CrO x
  • the metal chalcogenide compound may be at least one of MoS x , MoS x , WS x , WSe x or CuS.
  • the thickness of the hole transport layer may be, for example, 20 nm to 100 nm.
  • the light-emitting device may also include other layer structures.
  • the light-emitting device may also include an electron injection layer.
  • the electron injection layer is disposed between the electron transport layer and the cathode.
  • the material of the electron injection layer includes but is not limited to alkali metal halide.
  • the alkali metal halide includes but is not limited to LiF.
  • the alkali metal organic complex includes but is not limited to lithium 8-hydroxyquinolate.
  • the organic phosphine compound Including but not limited to at least one of organic phosphorus oxides, organic thiophosphine compounds or organic selenophosphine compounds.
  • the embodiments of the present application also provide a method for preparing a light-emitting device.
  • the preparation method includes the following steps:
  • the stacked structure is a substrate including an anode and a light-emitting layer, and the electron transport layer is formed on the side of the light-emitting layer away from the anode; when the light-emitting device has an inverted structure, the stacked structure is A substrate containing a cathode with an electron transport layer formed on one side of the cathode.
  • the selected types of nanometal oxides and nucleating agents are as described above and will not be repeated here; the application methods of the mixed solution include but are not limited to spin coating, coating, inkjet printing, blade coating, and dipping. At least one of pulling, soaking, spraying, rolling or casting.
  • nanometal oxides and nucleating agents By mixing nanometal oxides and nucleating agents in a solution to increase the number of heterogeneous cores, promote the non-spontaneous nucleation of nanometal oxides to achieve grain refinement, and increase the grain boundaries of the electron transport layer number, thereby increasing the grain size of the electron transport layer, causing the grain boundary barrier to increase, thereby effectively increasing the resistance of the electron transport layer, increasing the difficulty of electron migration, reducing the electron injection level, and promoting electron-vacancy
  • the hole transport is balanced, thereby improving the luminous efficiency and working life of the light-emitting device.
  • drying treatment includes all processes that can enable the wet film to obtain higher energy and transform into a dry film, including but not limited to heat treatment and standing to dry naturally.
  • heat treatment can be constant temperature It can also be a non-isothermal heat treatment (for example, the temperature changes in a gradient manner).
  • drying treatment refers to a constant temperature heat treatment at 100°C to 200°C for 15 minutes to 30 minutes.
  • the second compound is solid, and in the mixed solution, the mass ratio of the first compound: the second compound is 1: (0.02 ⁇ 0.05).
  • the solvent of the mixed liquid is selected from at least one of ethanol, ethylene glycol methyl ether or glacial acetic acid.
  • the second compound is a liquid
  • the preparation method of the mixed solution includes the steps of: providing a solution containing the first compound, mixing the second compound and the solution containing the first compound to prepare a mixed solution; wherein, in the solution containing the first compound , the concentration of the first compound is 30 mg/mL to 60 mg/mL, and the volume ratio of the solution containing the first compound: the second compound is 1: (0.01 ⁇ 0.0125).
  • the solvent in the solution containing the first compound is selected from at least one of ethanol, ethylene glycol methyl ether or glacial acetic acid.
  • applying a mixed liquid containing the first compound and the second compound on one side of the stacked structure includes the step of: providing a liquid containing the first compound and the second compound.
  • the mixed liquid is placed in an AC electric field for a preset time.
  • A is the grain size of the electron transport layer without nucleating agent
  • B is the grain size of the electron transport layer with nucleating agent added
  • C is the nucleating agent added and treated with AC electric field.
  • the grain size of the final electron transport layer where cracks represent grain boundaries. The more cracks, the more grain boundaries, and correspondingly the larger the grain size.
  • C has the largest grain size
  • A has the smallest grain size.
  • the intensity of the AC electric field is 100v/m to 500v/m
  • the frequency of the AC electric field is 50Hz to 100Hz
  • the effective voltage value of the AC electric field is 100V to 200V
  • the preset time is 1min to 5min.
  • the preparation method when the light-emitting device has an upright structure, the preparation method further includes the step of preparing and forming a cathode on the side of the electron transport layer away from the light-emitting layer.
  • the stacked structure may be, for example, a substrate including an anode, a hole functional layer and a light-emitting layer.
  • the anode is arranged opposite to the light-emitting layer, and the hole functional layer is arranged between the anode and the light-emitting layer.
  • the electron transport layer is formed on the side of the light-emitting layer away from the hole functional layer.
  • the preparation method includes the following steps:
  • step S4 is replaced with "Providing a first A mixed solution of the compound and the second compound, the mixed solution is placed in an AC electric field for a preset time to obtain a reaction solution, and then the reaction solution is applied to the side of the light-emitting layer away from the hole functional layer, and the drying process is performed to obtain electron transmission. layer".
  • the preparation method further includes the following steps:
  • An anode is prepared on the side of the light-emitting layer away from the electron transport layer.
  • preparing and forming an anode on the side of the light-emitting layer away from the electron transport layer includes the following steps:
  • An anode is prepared on the side of the hole functional layer away from the light-emitting layer.
  • the preparation method includes the following steps:
  • step S4 is replaced with "Provide a first light-emitting device containing an inverted structure".
  • a mixed solution of a compound and a second compound the mixed solution is placed in an alternating current electric field for a preset time to obtain a reaction solution, and then the reaction solution is applied to the side of the cathode away from the substrate, and dried to obtain an electron transport layer.”
  • the preparation methods of other film layers in the light-emitting device include but are not limited to solution methods and deposition methods.
  • the solution methods include but are not limited to spin coating, coating, inkjet printing, Scratching, dipping, pulling, soaking, spraying, rolling or casting; deposition methods include chemical methods and physical methods.
  • Chemical methods include but are not limited to chemical vapor deposition, continuous ion layer adsorption and reaction method, anodizing method, electrolysis Deposition method or co-precipitation method, physical method including but not limited to thermal evaporation coating method, electron beam evaporation coating method, magnetron sputtering method, multi-arc ion coating method, physical vapor deposition method, atomic layer deposition method or pulse laser deposition Law.
  • a drying process needs to be added to convert the wet film into a dry film.
  • the method for preparing a light-emitting device may also include other steps, for example: after each layer of the light-emitting device is prepared, the light-emitting device needs to be packaged.
  • Embodiments of the present application also provide a display device, which includes a light-emitting device according to any one of the light-emitting devices described in the embodiments of the present application or a light-emitting device produced by any of the manufacturing methods of the light-emitting device.
  • the display device can be any electronic product with a display function, including but not limited to smart phones, tablet computers, laptops, digital cameras, digital camcorders, smart wearable devices, smart electronic weighing scales, vehicle monitors, and televisions.
  • an e-book reader where the smart wearable device can be, for example, a smart bracelet, a smart watch, a virtual reality (Virtual Reality, VR) helmet, etc.
  • the light-emitting device is a quantum dot light-emitting diode with an upright structure. As shown in Figure 4, in the direction from bottom to top, the light-emitting device 1 includes linings arranged in sequence. Bottom 10, anode 11, hole injection layer 151, hole transport layer 152, light emitting layer 13, electron transport layer 14 and cathode 12.
  • each layer in the light-emitting device 1 is as follows:
  • the material of the substrate 10 is glass, and the thickness of the substrate 10 is 1mm;
  • the material of the anode 11 is ITO, and the thickness of the anode 11 is 25nm;
  • the material of the cathode 12 is Ag, and the thickness of the cathode 12 is 35 nm;
  • the material of the luminescent layer 13 is ZnCdS/ZnS quantum dots (octanethiol ligands are connected to the surface), and the thickness of the luminescent layer 13 is 60nm;
  • the material of the electron transport layer 14 is composed of a first compound and a second compound.
  • the first compound is nano-ZnO (particle size is 12 nm); the second compound is dibenzyl sorbitol.
  • the molar ratio of the first compound to the second compound is 1:0.15, the thickness of the electron transport layer 14 is 60nm;
  • the material of the hole injection layer 151 is PEDOT:PSS, and the thickness is 50nm;
  • the hole transport layer 152 is made of TFB and has a thickness of 50 nm.
  • S1.1 Provide a substrate, sputter ITO on one side of the substrate to obtain the ITO layer, use a cotton swab to dip a small amount of soapy water to wipe the surface of the ITO layer to remove visible impurities on the surface, and then use the substrate including ITO in turn.
  • step S1.2 In an atmospheric environment of normal temperature and pressure, spin-coat the PEDOT:PSS aqueous solution on the side of the anode away from the substrate in step S1.1, and then place it for constant temperature heat treatment at 150°C for 20 minutes to obtain a hole injection layer;
  • step S1.3 In a nitrogen environment at normal temperature and pressure, spin-coat the TFB-chlorobenzene solution on the side of the hole injection layer away from the anode in step S1.2, and then place it at 150°C for constant temperature heat treatment for 20 minutes to obtain hole transport. layer;
  • step S1.4 In a nitrogen environment at normal temperature and pressure, spin-coat a ZnCdS/ZnS quantum dot-n-octane solution with a concentration of 20 mg/mL on the side of the hole transport layer away from the hole injection layer in step S1.3. Then place it for constant temperature heat treatment at 100°C for 10 minutes to obtain the luminescent layer;
  • nano-ZnO (particle size: 12 nm)-ethanol solution with a concentration of 45 mg/mL, and dissolve 1 mL of dibenzylidene sorbitol in 99 mL of nano-ZnO (particle size: 12 nm)-ethanol solution to prepare a mixture.
  • liquid in a nitrogen environment at normal temperature and pressure, spin-coat the mixed liquid on the side of the light-emitting layer away from the hole transport layer in step S1.4, and then place it for constant temperature heat treatment at 150°C for 20 minutes to obtain the electron transport layer;
  • step S1.6 In a vacuum environment with an air pressure of 4 ⁇ 10 -6 mbar, evaporate Ag on the side of the electron transport layer away from the light-emitting layer in step S1.5 to obtain a cathode, which is then encapsulated with UV curing glue to obtain a light-emitting device. .
  • This embodiment provides a light-emitting device and a preparation method thereof. Compared with the light-emitting device of Embodiment 1, the only difference between the light-emitting device of this embodiment is that: the molar ratio of the first compound: the second compound is 1: 0.1.
  • step S1.5 is replaced with "Providing nano-ZnO with a concentration of 60 mg/mL (particle size: 12nm)-ethanol solution, dissolve 1mL of dibenzylidene sorbitol in 99mL of nano-ZnO (particle size 12nm)-ethanol solution to prepare a mixed solution, in a nitrogen environment at normal temperature and pressure, in step S1.4
  • the side of the light-emitting layer away from the hole transport layer is spin-coated with the mixed solution, and then placed in a constant temperature heat treatment at 150°C for 20 minutes to obtain the electron transport layer.
  • This embodiment provides a light-emitting device and a preparation method thereof. Compared with the light-emitting device of Embodiment 1, the only difference between the light-emitting device of this embodiment is that: the molar ratio of the first compound: the second compound is 1: 0.2.
  • step S1.5 is replaced with "Providing nano-ZnO with a concentration of 30 mg/mL (particle size: 12nm)-ethanol solution, dissolve 1mL of dibenzylidene sorbitol in 99mL of nano-ZnO (particle size 12nm)-ethanol solution to prepare a mixed solution, in a nitrogen environment at normal temperature and pressure, in step S1.4
  • the side of the light-emitting layer away from the hole transport layer is spin-coated with the mixed solution, and then placed in a constant temperature heat treatment at 150°C for 20 minutes to obtain the electron transport layer.
  • This embodiment provides a light-emitting device and a preparation method thereof. Compared with the light-emitting device of Embodiment 1, the only difference between the light-emitting device of this embodiment is that: the molar ratio of the first compound: the second compound is 1: 0.3.
  • step S1.5 is replaced with "Providing nano-ZnO with a concentration of 15 mg/mL (particle size: 12nm)-ethanol solution, dissolve 1mL of dibenzylidene sorbitol in 99mL of nano-ZnO (particle size 12nm)-ethanol solution to prepare a mixed solution, in a nitrogen environment at normal temperature and pressure, in step S1.4
  • the side of the light-emitting layer away from the hole transport layer is spin-coated with the mixed solution, and then placed in a constant temperature heat treatment at 150°C for 20 minutes to obtain the electron transport layer.
  • This embodiment provides a light-emitting device and a preparation method thereof. Compared with the light-emitting device of Embodiment 1, the only difference between the light-emitting device of this embodiment is that: the molar ratio of the first compound: the second compound is 1: 0.05.
  • step S1.5 is replaced with "Provide nano-ZnO with a concentration of 120 mg/mL (particle size is 12nm)-ethanol solution, dissolve 1mL of dibenzylidene sorbitol in 99mL of nano-ZnO (particle size 12nm)-ethanol solution to prepare a mixed solution, in a nitrogen environment at normal temperature and pressure, in step S1.4
  • the side of the light-emitting layer away from the hole transport layer is spin-coated with the mixed solution, and then placed in a constant temperature heat treatment at 150°C for 20 minutes to obtain the electron transport layer.
  • This embodiment provides a method for preparing a light-emitting device and the light-emitting device prepared therefrom.
  • the only difference between the method for preparing the light-emitting device in this embodiment is that: Step S1.5 is replaced with "Provide a nano-ZnO (particle size of 12 nm)-ethanol solution with a concentration of 45 mg/mL, and dissolve 1 mL of dibenzyl sorbitol in 99 mL of nano-ZnO (particle size of 12 nm)-ethanol solution.
  • Step S1 Prepare a mixed liquid, and place the mixed liquid in a rectangular alternating current electric field with a frequency of 50Hz and a voltage of negative 200V to positive 200V to react for 1 min to obtain a reaction liquid; then, in a nitrogen environment at normal temperature and pressure, perform step S1. 4. Spin-coat the reaction solution on the side of the light-emitting layer away from the hole transport layer, and then place it for constant temperature heat treatment at 150°C for 20 minutes to obtain the electron transport layer.”
  • This embodiment provides a method for preparing a light-emitting device and the light-emitting device prepared therefrom. Compared with the method for preparing the light-emitting device in Embodiment 6, the only difference between the method for preparing the light-emitting device in this embodiment is that: The reaction time of the mixed solution placed under an alternating electric field is replaced from "1min" to "2min".
  • This embodiment provides a method for preparing a light-emitting device and the light-emitting device prepared therefrom. Compared with the method for preparing the light-emitting device in Embodiment 6, the only difference between the method for preparing the light-emitting device in this embodiment is that: The reaction time when the mixed solution is placed under an AC electric field is replaced from "1min" to "3min".
  • This embodiment provides a method for preparing a light-emitting device and the light-emitting device prepared therefrom. Compared with the method for preparing the light-emitting device in Embodiment 6, the only difference between the method for preparing the light-emitting device in this embodiment is that: The reaction time of the mixed solution placed under an AC electric field is replaced from "1min" to "4min".
  • This embodiment provides a method for preparing a light-emitting device and the light-emitting device prepared therefrom. Compared with the method for preparing the light-emitting device in Embodiment 6, the only difference between the method for preparing the light-emitting device in this embodiment is that: The reaction time of the mixed solution under AC electric field is replaced from "1min" to "5min".
  • This embodiment provides a method for preparing a light-emitting device and the light-emitting device prepared therefrom. Compared with the method for preparing the light-emitting device in Embodiment 6, the only difference between the method for preparing the light-emitting device in this embodiment is that: The reaction time of the mixed solution placed under an AC electric field is replaced from "1min" to "6min".
  • This embodiment provides a method for preparing a light-emitting device and the light-emitting device prepared therefrom. Compared with the method for preparing the light-emitting device in Embodiment 6, the only difference between the method for preparing the light-emitting device in this embodiment is that: The reaction time of the mixed solution placed under an AC electric field is replaced from "1min" to "7min".
  • This embodiment provides a method for preparing a light-emitting device and the light-emitting device prepared therefrom. Compared with the method for preparing the light-emitting device in Embodiment 6, the only difference between the method for preparing the light-emitting device in this embodiment is that: The reaction time of the mixed solution placed under an AC electric field is replaced from "1min" to "8min".
  • This embodiment provides a method for preparing a light-emitting device and the light-emitting device prepared therefrom.
  • Step S1.5 is replaced with "Provide a nano-ZnO (particle size: 12 nm)-ethanol solution with a concentration of 45 mg/mL, and dissolve 315 mg of sodium succinate in 100 mL of nano-ZnO (particle size: 12 nm)-ethanol solution to prepare
  • the mixed solution is then spin-coated on the side of the light-emitting layer away from the hole transport layer in step S1.4 under a nitrogen environment at normal temperature and pressure, and then placed in a constant temperature heat treatment of 150°C for 20 minutes to obtain an electron transport layer.
  • Step S1.5 is replaced with "Provide a nano-ZnO (particle size: 12 nm)-ethanol solution with a concentration of 45 mg/mL, and dissolve 315 mg of sodium succinate in 100 mL of nano-ZnO (particle size: 12 nm)-ethanol solution to prepare
  • This embodiment provides a method for preparing a light-emitting device and the light-emitting device prepared therefrom.
  • Step S1.5 is replaced with "Provide a nano-ZnO (particle size: 12 nm)-ethanol solution with a concentration of 45 mg/mL, and dissolve 315 mg of sodium succinate in 100 mL of nano-ZnO (particle size: 12 nm)-ethanol solution to prepare Mixed liquid, the mixed liquid is placed in a rectangular AC electric field with a frequency of 50Hz and a voltage of negative 200V to positive 200V to react for 5 minutes to obtain a reaction liquid; then, in a nitrogen environment at normal temperature and pressure, in step S1.4 The side of the light-emitting layer away from the hole transport layer is spin-coated with the reaction solution, and then placed in a constant temperature heat treatment at 150°C for 20 minutes to
  • This embodiment provides a method for preparing a light-emitting device and the light-emitting device prepared therefrom.
  • Step S1.5 is replaced with "Provide a nano-ZnO (particle diameter of 12 nm)-ethanol solution with a concentration of 45 mg/mL, and dissolve 1 mL of ⁇ -type polypropylene in 99 mL of nano-ZnO (particle diameter of 12 nm)-ethanol solution to prepare Obtain a mixed solution, and then spin-coat the mixed solution on the side of the light-emitting layer away from the hole transport layer in step S1.4 under a nitrogen environment at normal temperature and pressure, and then place it for constant temperature heat treatment at 150°C for 20 minutes to obtain electron transmission. layer".
  • This embodiment provides a method for preparing a light-emitting device and the light-emitting device prepared therefrom.
  • the only difference between the method for preparing the light-emitting device in this embodiment is that: Step S1.5 is replaced with "Provide a nano-ZnO (particle diameter of 12 nm)-ethanol solution with a concentration of 45 mg/mL, and dissolve 1 mL of ⁇ -type polypropylene in 99 mL of nano-ZnO (particle diameter of 12 nm)-ethanol solution to prepare
  • a mixed liquid is obtained, and the mixed liquid is placed in a rectangular AC electric field with a frequency of 50Hz and a voltage of negative 200V to positive 200V for 5 minutes to obtain a reaction liquid; then, in a nitrogen environment at normal temperature and pressure, in step S1.4
  • the side of the light-emitting layer away from the hole transport layer is spin-coated with the reaction solution, and then placed in a constant temperature heat treatment
  • This embodiment provides a method for preparing a light-emitting device and the light-emitting device prepared therefrom.
  • the only difference between the method for preparing the light-emitting device in this embodiment is that: Step S1.5 is replaced with "Provide a nano-ZnO (particle size: 12 nm)-ethanol solution with a concentration of 45 mg/mL, and dissolve 1575 mg of mica in 100 mL of nano-ZnO (particle size: 12 nm)-ethanol solution to prepare a mixed solution , and then spin-coat the mixed liquid on the side of the light-emitting layer away from the hole transport layer in step S1.4 under a nitrogen environment at normal temperature and pressure, and then place it for constant temperature heat treatment at 150°C for 20 minutes to obtain the electron transport layer.”
  • Step S1.5 is replaced with "Provide a nano-ZnO (particle size: 12 nm)-ethanol solution with a concentration of 45 mg/mL, and dissolve 1575 mg of mica in 100 mL of nano-ZnO (particle size: 12 nm)-ethanol solution to prepare a mixed solution
  • the mixed liquid was placed in a rectangular AC electric field with a frequency of 50Hz and a voltage of negative 200V to positive 200V to react for 5 minutes to obtain a reaction liquid; then, in a nitrogen environment at normal temperature and pressure, the luminescent layer in step S1.4 was Spin-coat the reaction solution on the side away from the hole transport layer, and then place it for constant temperature heat treatment at 150°C for 20 minutes to obtain the electron transport
  • This embodiment provides a light-emitting device and a preparation method thereof.
  • the only difference between the light-emitting device of this comparative example is that the material of the electron transport layer is nano-ZnO with a particle size of 12 nm. .
  • step S1.5 is replaced with "In a nitrogen environment at normal temperature and pressure, the light-emitting layer in step S1.4 is far away from hole transport."
  • One side of the layer is spin-coated with a nano-ZnO (particle size: 12 nm)-ethanol solution with a concentration of 45 mg/mL, and then placed in a constant temperature heat treatment at 150°C for 20 minutes to obtain an electron transport layer.”
  • the performance of the light-emitting devices from Examples 1 to 19 and Comparative Examples was tested using FPD optical property measurement equipment (an efficiency test system built by LabView controlling QE-PRO spectrometer, Keithley 2400 and Keithley 6485) to detect and obtain various Parameters such as voltage, current, brightness, and luminescence spectrum of the light-emitting device are then calculated to obtain key parameters such as External Quantum Efficiency (EQE) and power efficiency, and life testing equipment is used to test the service life of each of the above-mentioned light-emitting devices.
  • the external quantum efficiency test method is the integrating sphere test method; the life test uses the constant current method.
  • a silicon photosystem is used to test the brightness changes of each light-emitting device, and the brightness is recorded to be attenuated from 100%. to 95% (T95, h), and calculate the time required for each light-emitting device to decay from 100% to 95% brightness at a brightness of 1000 nit (LT95@1000nit, h).
  • Example 10 the CE@max of the light-emitting device in Example 10 is the CE of the comparative example.
  • Examples 1 to 5 It can be seen from the performance testing data of Examples 1 to 5 that the comprehensive performance of the light-emitting devices in Examples 1 to 3 is better than that of the light-emitting devices in Examples 4 and 5. Therefore, nanometallic materials in the electron transport layer are preferred.
  • the molar ratio of oxide: nucleating agent is 1: (0.1 ⁇ 0.2). If the content of nucleating agent is too high or too low, it will have limited effect on improving the overall performance of the light-emitting device.
  • the content of nucleating agent is too low (such as implementing Example 5), the promotion effect on the non-spontaneous nucleation of nanometal oxides is limited, so the improvement in the resistance of the electron transport layer is limited; if the content of the nucleating agent is too high (for example, Example 4), the effect on the resistance of the light-emitting device will be limited.
  • the degree of improvement in the matching between the electron injection level and the hole injection level is limited.
  • Example 6 to Example 13 The comprehensive performance of the light-emitting device in Example 1 is better than that of the light-emitting device of Example 1, and the comprehensive performance of the light-emitting device of Example 10 is the best, which fully demonstrates that: compared with the electron transport layer prepared from the mixed liquid without AC electric field treatment, The electron transport layer produced by the mixed liquid treated with AC electric field has a larger grain size, which is more conducive to improving the overall performance of the light-emitting device, especially conducive to improving the luminous efficiency and working life of the light-emitting device at low brightness (1000nit); From Example 6 to Example 13, it can be seen that under specific AC electric field conditions, the AC electric field treatment time is preferably 1 min to 5 min, and 5 min is more effective.
  • a longer or shorter AC electric field treatment time will have an impact on the overall performance of the light-emitting device.
  • the improvement effect is limited. If the AC electric field treatment time is short (for example, Example 6), the increase in the grain size will be limited, and thus the resistance improvement of the electron transport layer will be limited.
  • the AC electric field treatment time will be long (for example, Example 11). To Example 13), a certain degree of dislocation may occur due to excessively large crystal grains, resulting in an increase in crystal defects.
  • dibenzylsorbitol is preferred as the nucleating agent because: dibenzylsorbitol has the advantages of being cheap, easy to obtain, and less harmful to the environment, and because it is a colorless material, it does not Affects the transparency of the electron transport layer, thereby not negatively affecting the luminous efficiency of the light-emitting device.

Abstract

Disclosed in the present application are a light-emitting device, a preparation method for a light-emitting device, and a display apparatus. The light-emitting device comprises an anode; a cathode, which is arranged opposite to the anode; a light-emitting layer, which is arranged between the anode and the cathode; and an electron transport layer, which is arranged between the cathode and the light-emitting layer, wherein the electron transport layer is made of a nano metal oxide and a nucleating agent. Thus, the improvement of the light emission efficiency and service life of the light-emitting device is facilitated.

Description

发光器件、发光器件的制备方法及显示装置Light-emitting device, preparation method of light-emitting device and display device
本申请要求于2022年04月14日在中国专利局提交的、申请号为202210395518.4、申请名称为“发光器件、发光器件的制备方法以及显示装置”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 priority to the Chinese patent application filed with the China Patent Office on April 14, 2022, with the application number 202210395518.4 and the application name "Light-emitting device, preparation method of light-emitting device and display device", and its entire content is approved by This reference is incorporated into this application.
技术领域Technical field
本申请涉及光电技术领域，具体涉及一种发光器件、发光器件的制备方法以及显示装置。The present application relates to the field of optoelectronic technology, and specifically to a light-emitting device, a method for preparing the light-emitting device, and a display device.
背景技术Background technique
发光器件包括但不限于有机发光二极管(Organic Light-Emitting Diode,OLED)和量子点发光二极管(Quantum Dot Light Emitting Diodes,QLED)，发光器件为“三明治”结构，即包括阳极、阴极以及发光层，其中，阳极与阴极相对设置，发光层设置于阳极与阴极之间。发光器件的发光原理是：电子从器件的阴极注入至发光区，空穴从器件的阳极注入至发光区，电子和空穴在发光区复合形成激子，复合后的激子通过辐射跃迁的形式释放光子，从而发光。Light-emitting devices include but are not limited to organic light-emitting diodes (OLED) and quantum dot light-emitting diodes (QLED). The light-emitting devices have a "sandwich" structure, which includes an anode, a cathode and a light-emitting layer. Wherein, the anode and the cathode are arranged oppositely, and the luminescent layer is arranged between the anode and the cathode. The light-emitting principle of a light-emitting device is: electrons are injected from the cathode of the device to the light-emitting area, holes are injected from the anode of the device to the light-emitting area, electrons and holes recombine in the light-emitting area to form excitons, and the recombined excitons transition through radiation. Release photons, thereby emitting light.
技术问题technical problem
以QLED为例，目前，QLED存在载流子注入不平衡的问题，即现有的QLED在运行时普遍存在电子注入大于空穴注入的问题，使得发光层出现电子积累的现象，从而增大非发光复合的几率(例如俄歇复合)而损失能量，导致QLED在运行过程中出现性能衰减的问题，例如：发光效率下降、使用寿命缩短等。Take QLED as an example. Currently, QLED has the problem of unbalanced carrier injection. That is, the existing QLED generally has the problem that electron injection is greater than hole injection during operation, causing the phenomenon of electron accumulation in the light-emitting layer, thus increasing the non-linearity. Energy is lost due to the probability of luminous recombination (such as Auger recombination), resulting in performance degradation problems during QLED operation, such as reduced luminous efficiency, shortened service life, etc.
因此，如何改善发光器件的载流子注入不平衡问题以提高发光器件的发光效率和工作寿命，对发光器件的应用与发展具有重要意义。Therefore, how to improve the carrier injection imbalance problem of light-emitting devices to improve the luminous efficiency and working life of light-emitting devices is of great significance to the application and development of light-emitting devices.
技术解决方案Technical solutions
鉴于此，本申请提供了一种发光器件、发光器件的制备方法以及显示装置，以改善发光器件的发光效率和工作寿命。In view of this, the present application provides a light-emitting device, a method for preparing the light-emitting device, and a display device to improve the luminous efficiency and working life of the light-emitting device.
第一方面，本申请提供了一种发光器件，所述发光器件包括：In a first aspect, this application provides a light-emitting device, which includes:
阳极；anode;
阴极，与所述阳极相对设置；The cathode is arranged opposite to the anode;
发光层，设置于所述阳极与所述阴极之间；以及a light-emitting layer disposed between the anode and the cathode; and
电子传输层，设置于所述阴极与所述发光层之间；An electron transport layer is provided between the cathode and the light-emitting layer;
其中，所述电子传输层的材料包括第一化合物和第二化合物，所述第一化合物为纳米金属氧化物，所述第二化合物为形核剂。Wherein, the material of the electron transport layer includes a first compound and a second compound, the first compound is a nanometal oxide, and the second compound is a nucleating agent.
可选地，所述第一化合物选自ZnO、TiO 2、SnO 2、BaO、Ta 2O 3、ZrO 2、TiLiO、ZnGaO、ZnAlO、ZnMgO、ZnSnO、ZnLiO、InSnO、AlZnO、ZnOCl或ZnOF中的至少一种。 Optionally, the first compound is selected from ZnO, TiO 2 , SnO 2 , BaO, Ta 2 O 3 , ZrO 2 , TiLiO, ZnGaO, ZnAlO, ZnMgO, ZnSnO, ZnLiO, InSnO, AlZnO, ZnOCl or ZnOF. At least one.
可选地，所述第一化合物的平均粒径为2nm至15nm。Optionally, the average particle size of the first compound is 2 nm to 15 nm.
可选地，所述形核剂选自有机形核剂以及无机形核剂中的一种或多种；Optionally, the nucleating agent is selected from one or more of organic nucleating agents and inorganic nucleating agents;
其中，所述有机形核剂选自羧酸金属盐类化合物、山梨醇类化合物、聚合物形核剂以及β晶型形核剂中的一种或多种；Wherein, the organic nucleating agent is selected from one or more of carboxylic acid metal salt compounds, sorbitol compounds, polymer nucleating agents and β crystal nucleating agents;
所述无机形核剂选自炭黑、氧化钙、云母、滑石粉以及高岭土中的一种或多种。The inorganic nucleating agent is selected from one or more types of carbon black, calcium oxide, mica, talc and kaolin.
可选地，所述羧酸金属盐类化合物选自琥珀酸钠、戊二酸钠、己酸钠、4-甲基戊酸钠、己二酸、己二酸铝、特丁基苯甲酸铝、苯甲酸铝、苯甲酸钾、苯甲酸锂、肉桂酸钠以及β-萘甲酸钠中的一种或多种；Alternatively, the carboxylic acid metal salt compound is selected from the group consisting of sodium succinate, sodium glutarate, sodium caproate, sodium 4-methylvalerate, adipic acid, aluminum adipate, and aluminum tert-butyl benzoate. , one or more of aluminum benzoate, potassium benzoate, lithium benzoate, sodium cinnamate and sodium beta-naphthoate;
所述山梨醇类化合物选自二苄叉山梨醇、二(对一甲基苄叉)山梨醇以及二(对氯取代苄叉)山梨醇中的一种或多种；The sorbitol compound is selected from one or more of dibenzylidene sorbitol, di(p-monomethylbenzylidene) sorbitol, and di(p-chlorosubstituted benzylidene) sorbitol;
所述聚合物形核剂选自聚乙烯基环己烷、聚乙烯戊烷以及乙烯/丙烯酸酯共聚物中的一种或多种；The polymer nucleating agent is selected from one or more of polyvinylcyclohexane, polyethylenepentane and ethylene/acrylate copolymer;
所述β晶型形核剂选自β型聚丙烯。The β-crystalline nucleating agent is selected from β-type polypropylene.
可选地，在所述电子传输层中，所述第一化合物：所述第二化合物的摩尔比为1：(0.1～0.2)。Optionally, in the electron transport layer, the molar ratio of the first compound:the second compound is 1: (0.1˜0.2).
可选地，所述发光层的材料为量子点，所述量子点选自单一组分量子点、核壳结构量子点、无机钙钛矿量子点以及有机-无机杂化钙钛矿量子点的一种或多种；Optionally, the material of the light-emitting layer is quantum dots, and the quantum dots are selected from the group consisting of single-component quantum dots, core-shell structure quantum dots, inorganic perovskite quantum dots, and organic-inorganic hybrid perovskite quantum dots. one or more;
当所述量子点选自单一组分量子点或核壳结构量子点时，所述单一组分量子点的材料、所述核壳结构量子点的核的材料以及所述核壳结构量子点的壳的材料彼此独立地选自II-VI族化合物、III-V族化合物、IV-VI族化合物或I-III-VI族化合物中的至少一种，其中，所述II-VI族化合物选自CdS、CdSe、CdTe、ZnS、ZnSe、ZnTe、ZnO、HgS、HgSe、HgTe、CdSeS、CdSeTe、CdSTe、ZnSeS、ZnSeTe、ZnSTe、HgSeS、HgSeTe、HgSTe、CdZnS、CdZnSe、CdZnTe、CdHgS、CdHgSe、CdHgTe、HgZnS、HgZnSe、HgZnTe、CdZnSeS、CdZnSeTe、CdZnSTe、CdHgSeS、CdHgSeTe、CdHgSTe、HgZnSeS、HgZnSeTe或HgZnSTe中的至少一种，所述III-V族化合物选自GaN、GaP、GaAs、GaSb、AlN、AlP、AlAs、AlSb、InN、InP、InAs、InSb、GaNP、GaNAs、GaNSb、GaPAs、GaPSb、AlNP、AlNAs、AlNSb、AlPAs、AlPSb、InNP、InNAs、InNSb、InPAs、InPSb、GaAlNP、GaAlNAs、GaAlNSb、GaAlPAs、GaAlPSb、GaInNP、GaInNAs、GaInNSb、GaInPAs、GaInPSb、InAlNP、InAlNAs、InAlNSb、InAlPAs或InAlPSb中的至少一种，所述IV-VI族化合物选自SnS、SnSe、SnTe、PbS、PbSe、PbTe、SnSeS、SnSeTe、SnSTe、PbSeS、PbSeTe、PbSTe、SnPbS、SnPbSe、SnPbTe、SnPbSSe、SnPbSeTe或SnPbSTe中的至少一种，所述I-III-VI族化合物选自CuInS、CuInSe或AgInS中的至少一种；When the quantum dots are selected from single-component quantum dots or core-shell structure quantum dots, the materials of the single-component quantum dots, the core materials of the core-shell structure quantum dots, and the core-shell structure quantum dots The materials of the shell are independently selected from at least one of II-VI compounds, III-V compounds, IV-VI compounds or I-III-VI compounds, wherein the II-VI compounds are selected from CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, At least one of HgZnS, HgZnSe, HgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe or HgZnSTe, and the III-V compound is selected from GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, At least one of GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs or InAlPSb, and the IV-VI compound is selected from SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, At least one of SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, SnPbSeTe or SnPbSTe, and the Group I-III-VI compound is selected from at least one of CuInS, CuInSe or AgInS;
所述阳极和所述阴极的材料彼此独立地选自金属、碳材料以及金属氧化物中的一种或多种，其中，所述金属选自Al、Ag、Cu、Mo、Au、Ba、Ca以及Mg中的一种或多种；所述碳材料选自石墨、碳纳米管、石墨烯以及碳纤维中的一种或多种；所述金属氧化物选自氧化铟锡、氟掺杂氧化锡、氧化锡锑、铝掺杂的氧化锌、镓掺杂的氧化锌、铟掺杂的氧化锌以及镁掺杂的氧化锌中的一种或多种。The materials of the anode and the cathode are independently selected from one or more of metals, carbon materials and metal oxides, wherein the metal is selected from Al, Ag, Cu, Mo, Au, Ba, Ca and one or more of Mg; the carbon material is selected from one or more of graphite, carbon nanotubes, graphene and carbon fiber; the metal oxide is selected from indium tin oxide, fluorine-doped tin oxide , one or more of tin antimony oxide, aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, and magnesium-doped zinc oxide.
可选地，所述发光器件还包括空穴功能层，所述空穴功能层设置于所述阳极与所述发光层之间；Optionally, the light-emitting device further includes a hole function layer, the hole function layer is disposed between the anode and the light-emitting layer;
所述空穴功能层包括空穴注入层以及空穴传输层中的一种或多种，当所述空穴功能层包括层叠设置的空穴传输层和空穴注入层时，所述空穴传输层靠近所述发光层，且所述空穴注入层靠近所述阳极；The hole function layer includes one or more of a hole injection layer and a hole transport layer. When the hole function layer includes a hole transport layer and a hole injection layer arranged in a stack, the hole function layer The transport layer is close to the light-emitting layer, and the hole injection layer is close to the anode;
所述空穴传输层的材料选自NiO、WO 3、MoO 3、CuO、聚(9,9-二辛基芴 -CO-N-(4-丁基苯基)二苯胺)、3-己基取代聚噻吩、聚(9-乙烯咔唑)、聚[双(4-苯基)(4-丁基苯基)胺]、聚(N,N'-二(4-丁基苯基)-N,N'-二苯基-1,4-苯二胺-CO-9,9-二辛基芴)、4,4',4”-三(咔唑-9-基)三苯胺、4,4'-二(9-咔唑)联苯、N,N'-二苯基-N,N'-二(3-甲基苯基)-1,1'-联苯-4,4'-二胺以及N,N'-二苯基-N,N'-(1-萘基)-1,1'-联苯-4,4'-二胺的一种或多种； The material of the hole transport layer is selected from NiO, WO 3 , MoO 3 , CuO, poly(9,9-dioctylfluorene-CO-N-(4-butylphenyl)diphenylamine), 3-hexyl Substituted polythiophene, poly(9-vinylcarbazole), poly[bis(4-phenyl)(4-butylphenyl)amine], poly(N,N'-bis(4-butylphenyl)- N,N'-diphenyl-1,4-phenylenediamine-CO-9,9-dioctylfluorene), 4,4',4″-tris(carbazol-9-yl)triphenylamine, 4 ,4'-bis(9-carbazole)biphenyl, N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4' - One or more diamines and N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine;
所述空穴注入层的材料选自聚(3,4-乙烯二氧基噻吩)：聚(苯乙烯磺酸)、酞菁铜、2,3,5,6-四氟-7,7',8,8'-四氰二甲基对苯醌、2,3,6,7,10,11-六氰基-1,4,5,8,9,12-六氮杂苯并菲、过渡金属氧化物以及过渡金属硫系化合物中的一种或多种，其中，所述过渡金属氧化物选自NiO x、MoO x、WO x以及CrO x中的一种或多种，所述过渡金属硫系化合物选自MoS x、MoSe x、WS x、WSe x以及CuS中的一种或多种。 The material of the hole injection layer is selected from poly(3,4-ethylenedioxythiophene): poly(styrenesulfonic acid), copper phthalocyanine, 2,3,5,6-tetrafluoro-7,7',8,8'-tetracyanodimethylp-benzoquinone, 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazabenzophenanthrene, One or more of transition metal oxides and transition metal chalcogenide compounds, wherein the transition metal oxide is selected from one or more of NiO x , MoO x , WO x and CrO x , and the transition metal oxide The metal chalcogenide compound is selected from one or more of MoS x , MoS x , WS x , WSe x and CuS.
第二方面，本申请提供了一种发光器件的制备方法，所述制备方法包括如下步骤：In a second aspect, this application provides a method for preparing a light-emitting device, which method includes the following steps:
提供叠层结构，在所述叠层结构的一侧施加包含第一化合物和第二化合物的混合液，干燥处理获得电子传输层；Provide a laminated structure, apply a mixed solution containing a first compound and a second compound on one side of the laminated structure, and dry it to obtain an electron transport layer;
其中，所述第一化合物为纳米金属氧化物，所述第二化合物为形核剂；Wherein, the first compound is a nanometal oxide, and the second compound is a nucleating agent;
当所述发光器件为正置型结构时，所述叠层结构为包含阳极和发光层的基板，所述电子传输层形成于所述发光层远离所述阳极的一侧；When the light-emitting device has an upright structure, the stacked structure is a substrate including an anode and a light-emitting layer, and the electron transport layer is formed on the side of the light-emitting layer away from the anode;
当所述发光器件为倒置型结构时，所述叠层结构为包含阴极的基板，所述电子传输层形成于所述阴极的一侧。When the light-emitting device has an inverted structure, the stacked structure is a substrate including a cathode, and the electron transport layer is formed on one side of the cathode.
可选地，所述第一化合物选自ZnO、TiO 2、SnO 2、BaO、Ta 2O 3、ZrO 2、TiLiO、ZnGaO、ZnAlO、ZnMgO、ZnSnO、ZnLiO、InSnO、AlZnO、ZnOCl或ZnOF中的至少一种。 Optionally, the first compound is selected from ZnO, TiO 2 , SnO 2 , BaO, Ta 2 O 3 , ZrO 2 , TiLiO, ZnGaO, ZnAlO, ZnMgO, ZnSnO, ZnLiO, InSnO, AlZnO, ZnOCl or ZnOF. At least one.
可选地，所述第一化合物的平均粒径为2nm至15nm。Optionally, the average particle size of the first compound is 2 nm to 15 nm.
可选地，所述形核剂选自有机形核剂以及无机形核剂中的一种或多种；Optionally, the nucleating agent is selected from one or more of organic nucleating agents and inorganic nucleating agents;
其中，所述有机形核剂选自羧酸金属盐类化合物、山梨醇类化合物、聚合物形核剂以及β晶型形核剂中的一种或多种；所述羧酸金属盐类化合物选自琥珀酸钠、戊二酸钠、己酸钠、4-甲基戊酸钠、己二酸、己二酸铝、特丁基苯甲酸铝、苯甲酸铝、苯甲酸钾、苯甲酸锂、肉桂酸钠以及β-萘甲酸钠中的一种或 多种；所述山梨醇类化合物选自二苄叉山梨醇、二(对一甲基苄叉)山梨醇以及二(对氯取代苄叉)山梨醇中的一种或多种；所述聚合物形核剂选自聚乙烯基环己烷、聚乙烯戊烷以及乙烯/丙烯酸酯共聚物中的一种或多种；所述β晶型形核剂选自β型聚丙烯；Wherein, the organic nucleating agent is selected from one or more of carboxylic acid metal salt compounds, sorbitol compounds, polymer nucleating agents and beta crystal nucleating agents; the carboxylic acid metal salt compound Selected from sodium succinate, sodium glutarate, sodium caproate, sodium 4-methylvalerate, adipic acid, aluminum adipate, tert-butyl aluminum benzoate, aluminum benzoate, potassium benzoate, lithium benzoate , sodium cinnamate and sodium β-naphthoate, one or more; the sorbitol compound is selected from dibenzyl sorbitol, di(p-monomethylbenzyl) sorbitol and di(p-chloro substituted benzyl sorbitol) ) one or more of sorbitol; the polymer nucleating agent is selected from one or more of polyvinylcyclohexane, polyethylene pentane and ethylene/acrylate copolymer; the β crystal Type nucleating agent is selected from β-type polypropylene;
所述无机形核剂选自炭黑、氧化钙、云母、滑石粉以及高岭土中的一种或多种。The inorganic nucleating agent is selected from one or more types of carbon black, calcium oxide, mica, talc and kaolin.
可选地，在所述电子传输层中，所述第一化合物：所述第二化合物的摩尔比为1：(0.1～0.2)。Optionally, in the electron transport layer, the molar ratio of the first compound:the second compound is 1: (0.1˜0.2).
可选地，所述第二化合物为固体，且在所述混合液中，所述第一化合物：所述第二化合物的质量比为1：(0.02～0.05)。Optionally, the second compound is a solid, and in the mixed liquid, the mass ratio of the first compound to the second compound is 1: (0.02-0.05).
可选地，所述第二化合物为液体，所述混合液的制备方法包括步骤：提供包含第一化合物的溶液，将所述第二化合物与所述包含第一化合物的溶液混合制得所述混合液；Optionally, the second compound is a liquid, and the preparation method of the mixed solution includes the steps of: providing a solution containing the first compound, and mixing the second compound with the solution containing the first compound to prepare the mixed liquid;
其中，在所述包含第一化合物的溶液中，所述第一化合物的浓度为30mg/mL至60mg/mL；Wherein, in the solution containing the first compound, the concentration of the first compound is 30 mg/mL to 60 mg/mL;
所述包含第一化合物的溶液：所述第二化合物的体积比为1：(0.01～0.0125)。The volume ratio of the solution containing the first compound: the second compound is 1: (0.01~0.0125).
可选地，所述在所述叠层结构的一侧施加包含第一化合物和第二化合物的混合液，包括步骤：提供包含第一化合物和第二化合物的混合液，将所述混合液置于交流电场处理预设时间。Optionally, applying a mixed liquid containing the first compound and the second compound on one side of the laminated structure includes the steps of: providing a mixed liquid containing the first compound and the second compound, and placing the mixed liquid. Process the AC electric field for a preset time.
可选地，所述交流电场的强度为100v/m至500v/m，所述交流电场的频率为50Hz至100Hz，所述交流电场的有效电压值为100V至200V。Optionally, the intensity of the AC electric field is 100v/m to 500v/m, the frequency of the AC electric field is 50Hz to 100Hz, and the effective voltage value of the AC electric field is 100V to 200V.
可选地，所述预设时间为1min至5min。Optionally, the preset time is 1 min to 5 min.
第三方面，本申请提供了一种显示装置，所述显示装置包括发光器件，所述发光器件包括：In a third aspect, the present application provides a display device. The display device includes a light-emitting device, and the light-emitting device includes:
阳极；anode;
阴极，与所述阳极相对设置；The cathode is arranged opposite to the anode;
发光层，设置于所述阳极与所述阴极之间；以及a light-emitting layer disposed between the anode and the cathode; and
电子传输层，设置于所述阴极与所述发光层之间；An electron transport layer is provided between the cathode and the light-emitting layer;
其中，所述电子传输层的材料包括第一化合物和第二化合物，所述第一化合物为纳米金属氧化物，所述第二化合物为形核剂。Wherein, the material of the electron transport layer includes a first compound and a second compound, the first compound is a nanometal oxide, and the second compound is a nucleating agent.
可选地，所述第一化合物选自ZnO、TiO 2、SnO 2、BaO、Ta 2O 3、ZrO 2、TiLiO、ZnGaO、ZnAlO、ZnMgO、ZnSnO、ZnLiO、InSnO、AlZnO、ZnOCl或ZnOF中的至少一种； Optionally, the first compound is selected from ZnO, TiO 2 , SnO 2 , BaO, Ta 2 O 3 , ZrO 2 , TiLiO, ZnGaO, ZnAlO, ZnMgO, ZnSnO, ZnLiO, InSnO, AlZnO, ZnOCl or ZnOF. at least one;
所述形核剂选自有机形核剂以及无机形核剂中的一种或多种；所述有机形核剂选自羧酸金属盐类化合物、山梨醇类化合物、聚合物形核剂以及β晶型形核剂中的一种或多种，所述羧酸金属盐类化合物选自琥珀酸钠、戊二酸钠、己酸钠、4-甲基戊酸钠、己二酸、己二酸铝、特丁基苯甲酸铝、苯甲酸铝、苯甲酸钾、苯甲酸锂、肉桂酸钠以及β-萘甲酸钠中的一种或多种，所述山梨醇类化合物选自二苄叉山梨醇、二(对一甲基苄叉)山梨醇以及二(对氯取代苄叉)山梨醇中的一种或多种，所述聚合物形核剂选自聚乙烯基环己烷、聚乙烯戊烷以及乙烯/丙烯酸酯共聚物中的一种或多种，所述β晶型形核剂选自β型聚丙烯；所述无机形核剂选自炭黑、氧化钙、云母、滑石粉以及高岭土中的一种或多种；The nucleating agent is selected from one or more organic nucleating agents and inorganic nucleating agents; the organic nucleating agent is selected from carboxylic acid metal salt compounds, sorbitol compounds, polymer nucleating agents, and One or more beta crystal nucleating agents, the carboxylic acid metal salt compound is selected from the group consisting of sodium succinate, sodium glutarate, sodium hexanoate, sodium 4-methylvalerate, adipic acid, and adipic acid. One or more of aluminum diphosphate, tert-butyl aluminum benzoate, aluminum benzoate, potassium benzoate, lithium benzoate, sodium cinnamate and sodium β-naphthoate, and the sorbitol compound is selected from dibenzylidene One or more of sorbitol, di(p-monomethylbenzyl) sorbitol and di(p-chlorosubstituted benzylidene) sorbitol, the polymer nucleating agent is selected from polyvinylcyclohexane, poly One or more of ethylene pentane and ethylene/acrylate copolymer, the β crystalline nucleating agent is selected from β-type polypropylene; the inorganic nucleating agent is selected from carbon black, calcium oxide, mica, talc One or more of powder and kaolin;
在所述电子传输层中，所述第一化合物：所述第二化合物的摩尔比为1：(0.1～0.2)。In the electron transport layer, the molar ratio of the first compound:the second compound is 1: (0.1˜0.2).
有益效果beneficial effects
在本申请的发光器件中，电子传输层中添加有形核剂，能够促进纳米金属氧化物非自发形核以增加核的数量，达到细化纳米金属氧化物的晶粒的目的，增加了电子传输层的晶界数，且纳米金属氧化物的粒径不会发生明显变化，从而提升了电子传输层的晶粒度，使得晶界势垒随之增大，有效地提高了电子传输层的电阻，进而加大了电子迁移难度，降低了发光器件的电子迁移率，使得在相同的通电条件下，本申请实施例中发光器件的电子注入水平低于现有发光器件的电子注入水平，从而改善了现有发光器件存在的电子注入大于空穴注入的问题，提高了电子-空穴传输匹配度，有效促进了发光器件的载流子注入平衡，有利于提高发光器件的发光效率和工作寿命。In the light-emitting device of the present application, adding a tangible nucleating agent to the electron transport layer can promote the non-spontaneous nucleation of nano-metal oxides to increase the number of nuclei, achieve the purpose of refining the grains of nano-metal oxides, and increase electron transmission. The number of grain boundaries of the layer, and the particle size of the nanometal oxide will not change significantly, thereby increasing the grain size of the electron transport layer, causing the grain boundary barrier to increase, effectively increasing the resistance of the electron transport layer , thereby increasing the difficulty of electron migration and reducing the electron mobility of the light-emitting device, so that under the same energization conditions, the electron injection level of the light-emitting device in the embodiment of the present application is lower than that of the existing light-emitting device, thereby improving It solves the problem of existing light-emitting devices that electron injection is greater than hole injection, improves the electron-hole transmission matching degree, effectively promotes the carrier injection balance of the light-emitting device, and is conducive to improving the luminous efficiency and working life of the light-emitting device.
在本申请的发光器件的制备方法中，通过将纳米金属氧化物和形核剂以溶液的方式混合以制备电子传输层，增加了异质核心的数量，促进纳米金属氧化 物非自发形核以达到细化晶粒的目的，增加了电子传输层的晶界数，从而提升了电子传输层的晶粒度，使得晶界势垒随之增大，从而有效增大了电子传输层的电阻，提高了电子迁移难度，降低了电子注入水平，促进电子-空穴传输平衡，进而提升了发光器件的发光效率以及工作寿命。In the preparation method of the light-emitting device of the present application, the electron transport layer is prepared by mixing the nanometer metal oxide and the nucleating agent in a solution, which increases the number of heterogeneous cores and promotes the non-spontaneous nucleation of the nanometer metal oxide. To achieve the purpose of refining the grains, the number of grain boundaries of the electron transport layer is increased, thereby increasing the grain size of the electron transport layer, causing the grain boundary barrier to increase, thereby effectively increasing the resistance of the electron transport layer. It improves the difficulty of electron migration, reduces the level of electron injection, promotes the balance of electron-hole transport, and thereby improves the luminous efficiency and working life of the light-emitting device.
将本申请的发光器件应用于显示装置中，有利于提高显示装置的显示效果和延长显示装置的使用寿命。Applying the light-emitting device of the present application to a display device is beneficial to improving the display effect of the display device and extending the service life of the display device.
附图说明Description of the drawings
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 needed 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 exerting creative efforts.
图1为本申请实施例中提供的第一种发光器件的结构示意图。FIG. 1 is a schematic structural diagram of a first light-emitting device provided in an embodiment of the present application.
图2为本申请实施例中提供的第二种发光器件的结构示意图。FIG. 2 is a schematic structural diagram of a second light-emitting device provided in an embodiment of the present application.
图3为本申请实施例中提供的电子传输层在不同处理方式下的晶粒度示意图。Figure 3 is a schematic diagram of the grain size of the electron transport layer provided in the embodiment of the present application under different processing methods.
图4为本申请实施例中提供的第三种发光器件的结构示意图。FIG. 4 is a schematic structural diagram of a third light-emitting device provided in an embodiment of the present application.
本申请的实施方式Implementation Mode 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 technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present application. Obviously, the described embodiments are only some of the embodiments of the present application, rather than all of the embodiments. Based on the embodiments in this application, all other embodiments obtained by those skilled in the art without creative efforts shall fall within the scope of protection of this application.
本申请实施例提供一种量子点发光二极管器件及其制备方法与显示面板。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。Embodiments of the present application provide a quantum dot light-emitting diode device, a preparation method thereof, and a display panel. Each is explained in detail below. It should be noted that the order of description of the following embodiments does not limit the preferred order of the embodiments.
另外，在本申请的描述中，术语“包括”是指“包括但不限于”。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。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)。In addition, in the description of this application, the term "including" means "including but not limited to." 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 simplicity and should not be understood as a hard limit to the scope of the present application; therefore, the described scope should be considered The description has specifically disclosed all possible subranges as well as the single numerical 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 A single number within the stated range, such as 1, 2, 3, 4, 5, and 6, applies regardless of the range. Whenever a numerical range is stated herein, it is intended to include any cited number (fractional or whole) within the indicated range.
在本申请中，术语“和/或”用于描述关联对象的关联关系，表示可以存在三种关系，例如，“A和/或B”可以表示三种情况：第一种情况是单独存在A；第二种情况是同时存在A和B；第三种情况是单独存在B的情况，其中，A和B分别可以是单数或者复数。In this application, the term "and/or" is used to describe the association relationship of associated objects, indicating that there can be three relationships. For example, "A and/or B" can represent three situations: the first situation is that A alone exists ; The second case is when A and B exist at the same time; the third case is when B exists alone, where A and B can be singular or plural respectively.
在本申请中，术语“至少一种”是指一种或多种，“多种”是指两种或两种以上。术语“至少一种(个)”或其类似表达，指的是这些种(个)中的任意组合，包括单种(个)或复数种(个)的任意组合。例如，“a、b或c中的至少一种(个)”或“a,b和c中的至少一种(个)”均可表示为：a、b、c、a-b(即a和b)、a-c、b-c或a-b-c，其中，a,b和c分别可以是单种(个)或多种(个)。In this application, the term "at least one" refers to one or more, and "a plurality" refers to two or more than two. The term "at least one" or similar expressions thereof refers to any combination of these species, including any combination of a single species or a plurality of species. For example, "at least one (number) of a, b or c" or "at least one (number) of a, b and c" can be expressed as: a, b, c, a-b (i.e. a and b ), a-c, b-c or a-b-c, where a, b and c can be a single species (number) or multiple species (number) respectively.
本申请实施例提供了一种发光器件，如图1所示，发光器件1包括阳极11、阴极12、发光层13以及电子传输层14，其中，阳极11与阴极12相对设置，发光层13设置于阳极11与阴极12之间，电子传输层14设置于阴极12与发光层13之间。The embodiment of the present application provides a light-emitting device. As shown in Figure 1, the light-emitting device 1 includes an anode 11, a cathode 12, a luminescent layer 13 and an electron transport layer 14. The anode 11 and the cathode 12 are arranged opposite to each other, and the luminescent layer 13 is arranged Between the anode 11 and the cathode 12 , the electron transport layer 14 is disposed between the cathode 12 and the light-emitting layer 13 .
其中，电子传输层14的材料包括第一化合物和第二化合物，第一化合物为纳米金属氧化物，第二化合物为形核剂。The material of the electron transport layer 14 includes a first compound and a second compound, the first compound is a nanometal oxide, and the second compound is a nucleating agent.
如本申请所用，“形核剂”又称成核剂，是指一类能够改变纳米金属氧化物部分结晶行为的化合物，作用原理为：提供纳米金属氧化物成核所需的晶核，使得纳米金属氧化物由均相成核转变为异相成核以增加核的数量，从而加速了结晶速度，使晶粒结构细化，且纳米金属氧化物的粒径不会发生明显变化。在电子传输层中添加形核剂，能够促进纳米金属氧化物非自发形核以细化纳米金属氧化物的晶粒，增加了电子传输层的晶界数，从而提升了电子传输层的晶粒度，使得晶界势垒随之增大，有效地提高了电子传输层的电阻，进而加大了电子迁移难度，降低了发光器件的电子迁移率。因此，在相同的通电条件下，本申请实施例中发光器件的电子注入水平低于现有发光器件的电子注入水平，从 而改善了现有发光器件存在的电子注入大于空穴注入的问题，提高了电子-空穴传输匹配度，有效促进了发光器件的载流子注入平衡，有利于提高发光器件的发光效率和工作寿命。As used in this application, "nucleating agent", also known as nucleating agent, refers to a type of compound that can change the partial crystallization behavior of nanometer metal oxides. The principle of action is to provide the crystal nuclei required for the nucleation of nanometer metal oxides, so that Nano-metal oxides change from homogeneous nucleation to heterogeneous nucleation to increase the number of nuclei, thereby accelerating the crystallization speed and refining the grain structure, and the particle size of nano-metal oxides does not change significantly. Adding a nucleating agent to the electron transport layer can promote the non-spontaneous nucleation of nanometal oxides to refine the grains of nanometal oxides, increase the number of grain boundaries of the electron transport layer, thereby improving the grain size of the electron transport layer. Therefore, the grain boundary barrier increases, effectively increasing the resistance of the electron transport layer, thereby increasing the difficulty of electron migration and reducing the electron mobility of the light-emitting device. Therefore, under the same energization conditions, the electron injection level of the light-emitting device in the embodiment of the present application is lower than that of the existing light-emitting device, thereby improving the problem that the electron injection is greater than the hole injection in the existing light-emitting device, and improving It improves the electron-hole transmission matching degree, effectively promotes the carrier injection balance of the light-emitting device, and is beneficial to improving the luminous efficiency and working life of the light-emitting device.
如本申请所用，“晶界”是指属于同一固相但位向不同的晶粒之间的界面。As used herein, "grain boundary" refers to the interface between grains belonging to the same solid phase but with different orientations.
如本申请所用，“晶粒度”是衡量纳米金属氧化物中晶粒的平均大小的尺度；晶界越多，晶粒度越大。As used herein, "grain size" is a measure of the average size of grains in a nanometal oxide; the more grain boundaries, the larger the grain size.
第一化合物可以是未掺杂的纳米金属氧化物，也可以是掺杂的纳米金属氧化物。在本申请的一些实施例中，第一化合物选自ZnO、TiO 2、SnO 2、BaO、Ta 2O 3、ZrO 2、TiLiO、ZnGaO、ZnAlO、ZnMgO、ZnSnO、ZnLiO、InSnO、AlZnO、ZnOCl或ZnOF中的至少一种。第一化合物的平均粒径例如可以是2nm至15nm。 The first compound may be an undoped nanometer metal oxide or a doped nanometer metal oxide. In some embodiments of the present application, the first compound is selected from ZnO, TiO 2 , SnO 2 , BaO, Ta 2 O 3 , ZrO 2 , TiLiO, ZnGaO, ZnAlO, ZnMgO, ZnSnO, ZnLiO, InSnO, AlZnO, ZnOCl or At least one of ZnOF. The average particle diameter of the first compound may be, for example, 2 nm to 15 nm.
第二化合物选自有机形核剂和/或无机形核剂，有机形核剂选自羧酸金属盐类化合物、山梨醇类化合物、聚合物形核剂或β晶型形核剂中的至少一种，其中，羧酸金属盐类化合物选自琥珀酸钠、戊二酸钠、己酸钠、4-甲基戊酸钠、己二酸、己二酸铝、特丁基苯甲酸铝、苯甲酸铝、苯甲酸钾、苯甲酸锂、肉桂酸钠或β-萘甲酸钠中的至少一种，山梨醇类化合物选自二苄叉山梨醇、二(对一甲基苄叉)山梨醇或二(对氯取代苄叉)山梨醇中的至少一种，聚合物形核剂选自聚乙烯基环己烷、聚乙烯戊烷或乙烯/丙烯酸酯共聚物中的至少一种，所述β晶型形核剂选自β型聚丙烯；无机形核剂选自炭黑、氧化钙、云母、滑石粉或高岭土中的至少一种。The second compound is selected from an organic nucleating agent and/or an inorganic nucleating agent. The organic nucleating agent is selected from at least one of carboxylic acid metal salt compounds, sorbitol compounds, polymer nucleating agents or beta crystal nucleating agents. One, wherein the carboxylic acid metal salt compound is selected from sodium succinate, sodium glutarate, sodium caproate, sodium 4-methylvalerate, adipic acid, aluminum adipate, tert-butyl aluminum benzoate, At least one of aluminum benzoate, potassium benzoate, lithium benzoate, sodium cinnamate or sodium beta-naphthoate, and the sorbitol compound is selected from dibenzyl sorbitol, di(p-monomethylbenzyl) sorbitol or At least one of di(p-chloro-substituted benzylidene) sorbitol, the polymer nucleating agent is selected from at least one of polyvinylcyclohexane, polyethylenepentane or ethylene/acrylate copolymer, the β The crystal nucleating agent is selected from β-type polypropylene; the inorganic nucleating agent is selected from at least one of carbon black, calcium oxide, mica, talc or kaolin.
在本申请的至少一个实施例中，第二化合物选自二苄叉山梨醇，具有廉价易得、环境危害小的优点，此外，由于二苄叉山梨醇为无色材料，所以二苄叉山梨醇不会影响电子传输层的透明度，从而不会对发光器件的发光效率造成负面影响。In at least one embodiment of the present application, the second compound is selected from dibenzylidene sorbitol, which has the advantages of being cheap, easy to obtain, and causing little environmental harm. In addition, since dibenzylidene sorbitol is a colorless material, dibenzylidene sorbitol is Alcohol will not affect the transparency of the electron transport layer and thus will not have a negative impact on the luminous efficiency of the light-emitting device.
为了进一步地提高发光器件的综合性能，在本申请的一些实施例中，电子传输层中第一化合物：第二化合物的摩尔比为1：(0.1～0.2)，有利于进一步地促进纳米金属氧化物的非自发形核的同时，最大化地提高发光器件的电子注入水平与空穴注入水平之间的匹配度。In order to further improve the overall performance of the light-emitting device, in some embodiments of the present application, the molar ratio of the first compound to the second compound in the electron transport layer is 1: (0.1~0.2), which is conducive to further promoting nanometal oxidation While non-spontaneous nucleation of matter is achieved, the matching degree between the electron injection level and the hole injection level of the light-emitting device is maximized.
在本申请实施例的发光器件中，阳极11、阴极12和发光层13的材料可 以是本领域常见的材料，例如：In the light-emitting device of the embodiment of the present application, the materials of the anode 11, the cathode 12 and the light-emitting layer 13 can be common materials in the art, such as:
阳极11和阴极12的材料彼此独立地选自金属、碳材料或金属氧化物中的至少一种，金属选自Al、Ag、Cu、Mo、Au、Ba、Ca或Mg中的至少一种；碳材料选自石墨、碳纳米管、石墨烯或碳纤维中的至少一种；金属氧化物可以是掺杂或非掺杂金属氧化物，例如选自氧化铟锡(ITO)、氟掺杂氧化锡(FTO)、氧化锡锑(ATO)、铝掺杂的氧化锌(AZO)、镓掺杂的氧化锌(GZO)、铟掺杂的氧化锌(IZO)或镁掺杂的氧化锌(MZO)中的至少一种。阳极11或阴极12也可以选自掺杂或非掺杂透明金属氧化物之间夹着金属的复合电极，复合电极包括但不限于是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、TiO 2/Ag/TiO 2或TiO 2/Al/TiO 2中的至少一种。阳极11的厚度例如可以是40nm至160nm，阴极12的厚度例如可以是20nm至120nm。 The materials of the anode 11 and the cathode 12 are independently selected from at least one of metals, carbon materials or metal oxides, and the metal is selected from at least one of Al, Ag, Cu, Mo, Au, Ba, Ca or Mg; The carbon material is selected from at least one of graphite, carbon nanotubes, graphene or carbon fiber; the metal oxide can be doped or non-doped metal oxide, for example, selected from indium tin oxide (ITO), fluorine-doped tin oxide (FTO), antimony tin oxide (ATO), aluminum-doped zinc oxide (AZO), gallium-doped zinc oxide (GZO), indium-doped zinc oxide (IZO) or magnesium-doped zinc oxide (MZO) at least one of them. The anode 11 or the cathode 12 can also be selected from a composite electrode with metal sandwiched between doped or non-doped transparent metal oxides. The composite electrode includes but is not limited to AZO/Ag/AZO, AZO/Al/AZO, and 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, TiO At least one of 2 /Ag/TiO 2 or TiO 2 /Al/TiO 2 . The thickness of the anode 11 may be, for example, 40 nm to 160 nm, and the thickness of the cathode 12 may be, for example, 20 nm to 120 nm.
发光层13的材料为量子点，发光层13的厚度例如可以是20nm至100nm。量子点包括但不限于是红色量子点、绿色量子点或蓝色量子点中的至少一种，并且量子点包括但不限于是单一组分量子点、核壳结构量子点、无机钙钛矿量子点或有机-无机杂化钙钛矿量子点的至少一种。量子点的粒径例如可以是5nm至10nm。The material of the light-emitting layer 13 is quantum dots, and the thickness of the light-emitting layer 13 may be, for example, 20 nm to 100 nm. Quantum dots include, but are not limited to, at least one of red quantum dots, green quantum dots, or blue quantum dots, and quantum dots include, but are not limited to, single-component quantum dots, core-shell structure quantum dots, and inorganic perovskite quantum dots. dots or at least one of organic-inorganic hybrid perovskite quantum dots. The particle size of the quantum dots may be, for example, 5 nm to 10 nm.
当量子点选自单一组分量子点或核壳结构量子点时，单一组分量子点的材料、所述核壳结构量子点的核的材料以及所述核壳结构量子点的壳的材料彼此独立地选自II-VI族化合物、III-V族化合物、IV-VI族化合物或I-III-VI族化合物中的至少一种，其中，所述II-VI族化合物选自CdS、CdSe、CdTe、ZnS、ZnSe、ZnTe、ZnO、HgS、HgSe、HgTe、CdSeS、CdSeTe、CdSTe、ZnSeS、ZnSeTe、ZnSTe、HgSeS、HgSeTe、HgSTe、CdZnS、CdZnSe、CdZnTe、CdHgS、CdHgSe、CdHgTe、HgZnS、HgZnSe、HgZnTe、CdZnSeS、CdZnSeTe、CdZnSTe、CdHgSeS、CdHgSeTe、CdHgSTe、HgZnSeS、HgZnSeTe或HgZnSTe中的至少一种，所述III-V族化合物选自GaN、GaP、GaAs、GaSb、AlN、AlP、AlAs、AlSb、InN、InP、InAs、InSb、GaNP、GaNAs、GaNSb、GaPAs、GaPSb、AlNP、AlNAs、AlNSb、AlPAs、AlPSb、InNP、InNAs、InNSb、InPAs、InPSb、GaAlNP、GaAlNAs、GaAlNSb、GaAlPAs、GaAlPSb、GaInNP、GaInNAs、GaInNSb、 GaInPAs、GaInPSb、InAlNP、InAlNAs、InAlNSb、InAlPAs或InAlPSb中的至少一种，所述IV-VI族化合物选自SnS、SnSe、SnTe、PbS、PbSe、PbTe、SnSeS、SnSeTe、SnSTe、PbSeS、PbSeTe、PbSTe、SnPbS、SnPbSe、SnPbTe、SnPbSSe、SnPbSeTe或SnPbSTe中的至少一种，所述I-III-VI族化合物选自CuInS、CuInSe或AgInS中的至少一种。需要说明的是，对于前述单一组分量子点的材料、或者核壳结构量子点的核的材料、或者核壳结构量子点的壳的材料，提供的化学式仅示明了元素组成，并未示明各个元素的含量，例如：CdZnSe仅表示由Cd、Zn和Se三种元素组成，若表示各个元素的含量，则对应为Cd xZn 1-xSe，0<x<1。 When the quantum dots are selected from single-component quantum dots or core-shell structure quantum dots, the materials of the single-component quantum dots, the core materials of the core-shell structure quantum dots, and the shell materials of the core-shell structure quantum dots are mutually exclusive. Independently selected from at least one group II-VI compound, III-V compound, IV-VI compound or I-III-VI compound, wherein the II-VI compound is selected from CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZ nSe, At least one of HgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe or HgZnSTe, the III-V compound is selected from GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, At least one of GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs or InAlPSb, the IV-VI compound is selected from SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, SnSeTe, SnSTe, At least one of PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, SnPbSeTe or SnPbSTe, and the Group I-III-VI compound is selected from at least one of CuInS, CuInSe or AgInS. It should be noted that for the aforementioned single-component quantum dot materials, or core-shell structure quantum dot core materials, or core-shell structure quantum dot shell materials, the chemical formulas provided only indicate the elemental composition and do not indicate The content of each element, for example: CdZnSe only means that it is composed of three elements: Cd, Zn and Se. If it means the content of each element, it corresponds to Cd x Zn 1-x Se, 0<x<1.
对于无机钙钛矿量子点，无机钙钛矿量子点的结构通式为AMX 3，其中A为Cs +离子，M为二价金属阳离子，M包括但不限于是Pb 2+、Sn 2+、Cu 2+、Ni 2+、Cd 2+、Cr 2+、Mn 2+、Co 2+、Fe 2+、Ge 2+、Yb 2+或Eu 2+，X为卤素阴离子，包括但不限于Cl -、Br -或I -。 For inorganic perovskite quantum dots, the general structural formula of inorganic perovskite quantum dots is AMX 3 , where A is Cs + ion, M is a divalent metal cation, and M includes but is not limited to Pb 2+ , Sn 2+ , Cu 2+ , Ni 2+ , Cd 2+ , Cr 2+ , Mn 2+ , Co 2+ , Fe 2+ , Ge 2+ , Yb 2+ or Eu 2+ , X is a halogen anion, including but not limited to Cl - , Br - or I - .
对于有机-无机杂化钙钛矿量子点，有机-无机杂化钙钛矿量子点的结构通式为BMX 3，其中B为有机胺阳离子，包括但不限于是CH 3(CH 2) n-2NH 3+(n≥2)或NH 3(CH 2) nNH 3 2+(n≥2)，M为二价金属阳离子，M包括但不限于是Pb 2+、Sn 2+、Cu 2+、Ni 2+、Cd 2+、Cr 2+、Mn 2+、Co 2+、Fe 2+、Ge 2+、Yb 2+或Eu 2+，X为卤素阴离子，包括但不限于Cl -、Br -或I -。 For organic-inorganic hybrid perovskite quantum dots, the general structural formula of organic-inorganic hybrid perovskite quantum dots is BMX 3 , where B is an organic amine cation, including but not limited to CH 3 (CH 2 ) n - 2NH 3+ (n≥2) or NH 3 (CH 2 ) n NH 3 2+ (n≥2), M is a divalent metal cation, M includes but is not limited to Pb 2+ , Sn 2+ , Cu 2+ , Ni 2+ , Cd 2+ , Cr 2+ , Mn 2+ , Co 2+ , Fe 2+ , Ge 2+ , Yb 2+ or Eu 2+ , X is a halogen anion, including but not limited to Cl - , Br - or I - .
可以理解的是，当发光层的材料包括量子点时，发光层的材料还包括连接于量子点表面的配体，配体包括但不限于是胺类配体、羧酸类配体、硫醇类配体、(氧)膦配体、磷脂、软磷脂或聚乙烯基吡啶中的至少一种，胺类配体例如选自油胺、正丁胺、正辛胺、八胺或1,2-乙二胺中的至少一种，羧酸类配体例如选自油酸、乙酸、丁酸、戊酸、己酸、花生酸、十酸、十一烯酸、十四酸或硬脂酸中的至少一种，硫醇类配体例如选自乙硫醇、丙硫醇、巯基乙醇、苯硫醇、辛硫醇、八烷基硫醇、十二烷基硫醇或十八烷基硫醇中的至少一种，(氧)膦配体选自三辛基膦或三辛基氧膦中的至少一种。It can be understood that when the material of the light-emitting layer includes quantum dots, the material of the light-emitting layer also includes ligands connected to the surface of the quantum dots. The ligands include but are not limited to amine ligands, carboxylic acid ligands, and thiols. At least one of ligands, (oxy)phosphine ligands, phospholipids, soft phospholipids or polyvinylpyridine, amine ligands, for example, selected from oleylamine, n-butylamine, n-octylamine, octaamine or 1,2 -At least one of ethylenediamine, the carboxylic acid ligand is selected from, for example, oleic acid, acetic acid, butyric acid, valeric acid, caproic acid, arachidic acid, decaic acid, undecenoic acid, myristate or stearic acid At least one of the thiol ligands is selected from ethyl mercaptan, propyl mercaptan, mercaptoethanol, benzene mercaptan, octyl mercaptan, octadecyl mercaptan, dodecyl mercaptan or octadecyl mercaptan. At least one of the thiols and the (oxy)phosphine ligand are selected from at least one of trioctylphosphine or trioctylphosphine oxide.
为了获得更佳的光电性能和使用寿命，在本申请的一些实施例中，如图2所示，发光器件1还包括空穴功能层15，空穴功能层15设置于阳极11与发光层13之间。空穴功能层15包括空穴注入层和/或空穴传输层，当空穴功能 层包括层叠设置的空穴传输层和空穴注入层时，空穴传输层靠近发光层，且空穴注入层靠近阳极。空穴功能层15的厚度例如可以是20nm至200nm。In order to obtain better photoelectric performance and service life, in some embodiments of the present application, as shown in FIG. 2 , the light-emitting device 1 also includes a hole function layer 15 , and the hole function layer 15 is disposed on the anode 11 and the light-emitting layer 13 between. The hole function layer 15 includes a hole injection layer and/or a hole transport layer. When the hole function layer includes a hole transport layer and a hole injection layer arranged in a stack, the hole transport layer is close to the light-emitting layer, and the hole injection layer close to the anode. The thickness of the hole function layer 15 may be, for example, 20 nm to 200 nm.
空穴传输层的材料包括但不限于是聚(9,9-二辛基芴-CO-N-(4-丁基苯基)二苯胺)(简称为TFB，CAS号为220797-16-0)、3-己基取代聚噻吩(CAS号为104934-50-1)、聚(9-乙烯咔唑)(简称为PVK，CAS号为25067-59-8)、聚[双(4-苯基)(4-丁基苯基)胺](简称为Poly-TPD，CAS号为472960-35-3)、聚(N,N'-二(4-丁基苯基)-N,N'-二苯基-1,4-苯二胺-CO-9,9-二辛基芴)(简称为PFB，CAS号为223569-28-6)、4,4',4”-三(咔唑-9-基)三苯胺(简称为TCTA，CAS号为139092-78-7)、4,4'-二(9-咔唑)联苯(简称为CBP，CAS号为58328-31-7)、N,N'-二苯基-N,N'-二(3-甲基苯基)-1,1'-联苯-4,4'-二胺(简称TPD，CAS号为65181-78-4)或N,N'-二苯基-N,N'-(1-萘基)-1,1'-联苯-4,4'-二胺(简称NPB，CAS号为123847-85-8)中的至少一种；此外，空穴传输层的材料还可以选自具有空穴传输能力的无机材料，包括但不限于是NiO、WO 3、MoO 3或CuO中的至少一种。空穴传输层的厚度例如可以是20nm至100nm。 The material of the hole transport layer includes but is not limited to poly(9,9-dioctylfluorene-CO-N-(4-butylphenyl)diphenylamine) (TFB for short, CAS number: 220797-16-0 ), 3-hexyl substituted polythiophene (CAS number: 104934-50-1), poly(9-vinylcarbazole) (abbreviated as PVK, CAS number: 25067-59-8), poly[bis(4-phenyl) )(4-butylphenyl)amine] (referred to as Poly-TPD, CAS number is 472960-35-3), poly(N,N'-di(4-butylphenyl)-N,N'- Diphenyl-1,4-phenylenediamine-CO-9,9-dioctylfluorene) (referred to as PFB, CAS number is 223569-28-6), 4,4',4"-tris(carbazole) -9-yl)triphenylamine (abbreviated as TCTA, CAS number: 139092-78-7), 4,4'-bis(9-carbazole)biphenyl (abbreviated as CBP, CAS number: 58328-31-7) , N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine (TPD for short, CAS number is 65181-78 -4) or N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine (NPB for short, CAS number is 123847-85 - at least one of 8); in addition, the material of the hole transport layer can also be selected from inorganic materials with hole transport capabilities, including but not limited to at least one of NiO, WO 3 , MoO 3 or CuO. The thickness of the hole transport layer may be, for example, 20 nm to 100 nm.
空穴注入层的材料包括但不限于是聚(3,4-乙烯二氧基噻吩)：聚(苯乙烯磺酸)(CAS号为155090-83-8)、酞菁铜(简称为CuPc,CAS号为147-14-8)、2,3,5,6-四氟-7,7',8,8'-四氰二甲基对苯醌(简称为F4-TCNQ,CAS号为29261-33-4)、2,3,6,7,10,11-六氰基-1,4,5,8,9,12-六氮杂苯并菲(简称为HATCN,The materials of the hole injection layer include but are not limited to poly(3,4-ethylenedioxythiophene): poly(styrenesulfonic acid) (CAS number: 155090-83-8), copper phthalocyanine (referred to as CuPc, CAS number is 147-14-8), 2,3,5,6-tetrafluoro-7,7',8,8'-tetracyanodimethyl-p-benzoquinone (referred to as F4-TCNQ, CAS number is 29261 -33-4), 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazabenzophenanthrene (referred to as HATCN,
CAS号为105598-27-4)、过渡金属氧化物或过渡金属硫系化合物中的一种或多种，其中，过渡金属氧化物可以是NiO x、MoO x、WO x或CrO x中的至少一种，金属硫系化合物可以是MoS x、MoSe x、WS x、WSe x或CuS中的至少一种。空穴传输层的厚度例如可以是20nm至100nm。 CAS number is 105598-27-4), one or more of transition metal oxides or transition metal chalcogenide compounds, wherein the transition metal oxide can be at least one of NiO x , MoO x , WO x or CrO x One, the metal chalcogenide compound may be at least one of MoS x , MoS x , WS x , WSe x or CuS. The thickness of the hole transport layer may be, for example, 20 nm to 100 nm.
需要说明的是，发光器件还可以包括其他层结构，例如发光器件还可以包括电子注入层，电子注入层设置于电子传输层与阴极之间，电子注入层的材料包括但不限于是碱金属卤化物、碱金属有机络合物或有机膦化合物中的至少一种，碱金属卤化物包括但不限于是LiF，碱金属有机络合物包括但不限于是8-羟基喹啉锂，有机膦化合物包括但不限于是有机氧化磷、有机硫代膦化合物或有机硒代膦化合物中的至少一种。It should be noted that the light-emitting device may also include other layer structures. For example, the light-emitting device may also include an electron injection layer. The electron injection layer is disposed between the electron transport layer and the cathode. The material of the electron injection layer includes but is not limited to alkali metal halide. At least one of an alkali metal organic complex or an organic phosphine compound. The alkali metal halide includes but is not limited to LiF. The alkali metal organic complex includes but is not limited to lithium 8-hydroxyquinolate. The organic phosphine compound Including but not limited to at least one of organic phosphorus oxides, organic thiophosphine compounds or organic selenophosphine compounds.
本申请实施例还提供了一种发光器件的制备方法，所述制备方法包括如下 步骤：The embodiments of the present application also provide a method for preparing a light-emitting device. The preparation method includes the following steps:
提供叠层结构，在所述叠层结构的一侧施加包含第一化合物和第二化合物的混合液，干燥处理获得电子传输层；其中，第一化合物为纳米金属氧化物，第二化合物为形核剂；当发光器件为正置型结构时，叠层结构为包含阳极和发光层的基板，电子传输层形成于发光层远离阳极的一侧；当发光器件为倒置型结构时，叠层结构为包含阴极的基板，电子传输层形成于阴极的一侧。Provide a laminated structure, apply a mixed liquid containing a first compound and a second compound on one side of the laminated structure, and dry it to obtain an electron transport layer; wherein the first compound is a nanometer metal oxide, and the second compound is a nano-metal oxide. Nucleating agent; when the light-emitting device has an upright structure, the stacked structure is a substrate including an anode and a light-emitting layer, and the electron transport layer is formed on the side of the light-emitting layer away from the anode; when the light-emitting device has an inverted structure, the stacked structure is A substrate containing a cathode with an electron transport layer formed on one side of the cathode.
需要说明的是，纳米金属氧化物和形核剂的选择种类参照前文描述，在此不再赘述；混合液的施加方式包括但不限于是旋涂、涂布、喷墨打印、刮涂、浸渍提拉、浸泡、喷涂、滚涂或浇铸中的至少一种。通过将纳米金属氧化物和形核剂以溶液的方式混合，以增加异质核心的数量，促进纳米金属氧化物非自发形核以达到细化晶粒的目的，增加了电子传输层的晶界数，从而提升了电子传输层的晶粒度，使得晶界势垒随之增大，从而有效增大了电子传输层的电阻，提高了电子迁移难度，降低了电子注入水平，促进电子-空穴传输平衡，进而提升了发光器件的发光效率以及工作寿命。It should be noted that the selected types of nanometal oxides and nucleating agents are as described above and will not be repeated here; the application methods of the mixed solution include but are not limited to spin coating, coating, inkjet printing, blade coating, and dipping. At least one of pulling, soaking, spraying, rolling or casting. By mixing nanometal oxides and nucleating agents in a solution to increase the number of heterogeneous cores, promote the non-spontaneous nucleation of nanometal oxides to achieve grain refinement, and increase the grain boundaries of the electron transport layer number, thereby increasing the grain size of the electron transport layer, causing the grain boundary barrier to increase, thereby effectively increasing the resistance of the electron transport layer, increasing the difficulty of electron migration, reducing the electron injection level, and promoting electron-vacancy The hole transport is balanced, thereby improving the luminous efficiency and working life of the light-emitting device.
此外，如本申请所用，“干燥处理”包括所有能使湿膜获得更高能量而转变为干膜的工序，包括但不限于是热处理和静置自然晾干，其中，“热处理”可以是恒温式热处理，也可以是非恒温式热处理(例如温度呈梯度式变化)，在本申请的至少一个实施例中，“干燥处理”是指在100℃至200℃下恒温热处理15min至30min。In addition, as used in this application, "drying treatment" includes all processes that can enable the wet film to obtain higher energy and transform into a dry film, including but not limited to heat treatment and standing to dry naturally. Among them, "heat treatment" can be constant temperature It can also be a non-isothermal heat treatment (for example, the temperature changes in a gradient manner). In at least one embodiment of the present application, "drying treatment" refers to a constant temperature heat treatment at 100°C to 200°C for 15 minutes to 30 minutes.
为了进一步地促进纳米金属氧化物的非自发形核以进一步地提高电子传输层的电阻，并且提升发光器件的电子注入水平与空穴注入水平之间的匹配度，在本申请的一些实施例中，第二化合物为固体，且在混合液中，第一化合物：第二化合物的质量比为1：(0.02～0.05)。需要说明的是，混合液的溶剂选自乙醇、乙二醇甲醚或冰醋酸中的至少一种。In order to further promote the non-spontaneous nucleation of nanometal oxides to further improve the resistance of the electron transport layer, and improve the matching between the electron injection level and the hole injection level of the light-emitting device, in some embodiments of the present application , the second compound is solid, and in the mixed solution, the mass ratio of the first compound: the second compound is 1: (0.02~0.05). It should be noted that the solvent of the mixed liquid is selected from at least one of ethanol, ethylene glycol methyl ether or glacial acetic acid.
为了进一步地促进纳米金属氧化物的非自发形核以进一步地提高电子传输层的电阻，并且提升发光器件的电子注入水平与空穴注入水平之间的匹配度，在本申请的另一些实施例中，第二化合物为液体，混合液的制备方法包括步骤：提供包含第一化合物的溶液，将第二化合物与包含第一化合物的溶液混合制得混合液；其中，在包含第一化合物的溶液中，第一化合物的浓度为 30mg/mL至60mg/mL，包含第一化合物的溶液：第二化合物的体积比为1：(0.01～0.0125)。需要说明的是，包含第一化合物的溶液中溶剂选自乙醇、乙二醇甲醚或冰醋酸中的至少一种。In order to further promote the non-spontaneous nucleation of nanometal oxides to further improve the resistance of the electron transport layer, and improve the matching between the electron injection level and the hole injection level of the light-emitting device, in other embodiments of the present application , the second compound is a liquid, and the preparation method of the mixed solution includes the steps of: providing a solution containing the first compound, mixing the second compound and the solution containing the first compound to prepare a mixed solution; wherein, in the solution containing the first compound , the concentration of the first compound is 30 mg/mL to 60 mg/mL, and the volume ratio of the solution containing the first compound: the second compound is 1: (0.01~0.0125). It should be noted that the solvent in the solution containing the first compound is selected from at least one of ethanol, ethylene glycol methyl ether or glacial acetic acid.
为了进一步地促进发光器件的电子-空穴传输平衡，所述在所述叠层结构的一侧施加包含第一化合物和第二化合物的混合液，包括步骤：提供包含第一化合物和第二化合物的混合液，将混合液置于交流电场处理预设时间。如图3所示，A为未加入形核剂的电子传输层的晶粒度情况，B为加入形核剂的电子传输层的晶粒度情况，C为加入形核剂并经交流电场处理后的电子传输层的晶粒度情况，其中，裂纹表示晶界，裂纹越多，则晶界越多，对应地晶粒度越大，C的晶粒度最大，且A的晶粒度最小，说明：采用交流电场处理混合液能够进一步地促进晶粒细化，从而进一步地提高电子传输层的电阻，进而提高发光器件的电子注入水平与空穴注入水平的匹配度。In order to further promote the electron-hole transport balance of the light-emitting device, applying a mixed liquid containing the first compound and the second compound on one side of the stacked structure includes the step of: providing a liquid containing the first compound and the second compound. The mixed liquid is placed in an AC electric field for a preset time. As shown in Figure 3, A is the grain size of the electron transport layer without nucleating agent, B is the grain size of the electron transport layer with nucleating agent added, and C is the nucleating agent added and treated with AC electric field. The grain size of the final electron transport layer, where cracks represent grain boundaries. The more cracks, the more grain boundaries, and correspondingly the larger the grain size. C has the largest grain size, and A has the smallest grain size. , explanation: Using an AC electric field to treat the mixed solution can further promote grain refinement, thereby further increasing the resistance of the electron transport layer, thereby improving the matching between the electron injection level and the hole injection level of the light-emitting device.
在本申请的一些实施例中，交流电场的强度为100v/m至500v/m，交流电场的频率为50Hz至100Hz，交流电场的有效电压值为100V至200V，预设时间为1min至5min。In some embodiments of the present application, the intensity of the AC electric field is 100v/m to 500v/m, the frequency of the AC electric field is 50Hz to 100Hz, the effective voltage value of the AC electric field is 100V to 200V, and the preset time is 1min to 5min.
本申请的一些实施例中，当发光器件为正置型结构时，所述制备方法还包括步骤：在电子传输层远离发光层的一侧制备形成阴极。In some embodiments of the present application, when the light-emitting device has an upright structure, the preparation method further includes the step of preparing and forming a cathode on the side of the electron transport layer away from the light-emitting layer.
可以理解的是，当发光器件为正置型结构时，叠层结构例如可以是包含阳极、空穴功能层和发光层的基板，阳极与发光层相对设置，空穴功能层设置于阳极与发光层之间，电子传输层形成于发光层远离空穴功能层的一侧。It can be understood that when the light-emitting device has a positive structure, the stacked structure may be, for example, a substrate including an anode, a hole functional layer and a light-emitting layer. The anode is arranged opposite to the light-emitting layer, and the hole functional layer is arranged between the anode and the light-emitting layer. The electron transport layer is formed on the side of the light-emitting layer away from the hole functional layer.
在本申请的一个实施例中，当发光器件为正置型结构时，所述制备方法包括如下步骤：In one embodiment of the present application, when the light-emitting device has an upright structure, the preparation method includes the following steps:
S1、提供衬底，在衬底的一侧制备形成阳极；S1. Provide a substrate and prepare an anode on one side of the substrate;
S2、在阳极远离衬底的一侧制备形成空穴功能层；S2. Prepare and form a hole functional layer on the side of the anode away from the substrate;
S3、在空穴功能层远离阳极的一侧制备形成发光层；S3. Prepare and form a light-emitting layer on the side of the hole functional layer away from the anode;
S4、在发光层远离空穴功能层的一侧施加包含第一化合物和第二化合物的混合液，干燥处理获得电子传输层；S4. Apply a mixed solution containing the first compound and the second compound on the side of the light-emitting layer away from the hole functional layer, and dry it to obtain an electron transport layer;
S5、在电子传输层远离发光层的一侧制备形成阴极。S5. Prepare and form a cathode on the side of the electron transport layer away from the light-emitting layer.
在本申请的另一个实施例中，当发光器件为正置型结构时，相较于前述具 有正置型结构的发光器件的制备方法，区别之处仅在于：将步骤S4替换为“提供包含第一化合物和第二化合物的混合液，将所述混合液置于交流电场处理预设时间，获得反应液，然后在发光层远离空穴功能层的一侧施加所述反应液，干燥处理获得电子传输层”。In another embodiment of the present application, when the light-emitting device has an upright structure, compared with the aforementioned method for preparing a light-emitting device with an upright structure, the only difference is that step S4 is replaced with "Providing a first A mixed solution of the compound and the second compound, the mixed solution is placed in an AC electric field for a preset time to obtain a reaction solution, and then the reaction solution is applied to the side of the light-emitting layer away from the hole functional layer, and the drying process is performed to obtain electron transmission. layer".
在本申请的另一些实施例中，当发光器件为倒置型结构时，所述制备方法还包括如下步骤：In other embodiments of the present application, when the light-emitting device has an inverted structure, the preparation method further includes the following steps:
在电子传输层远离阴极的一侧制备形成发光层；以及Prepare and form a light-emitting layer on the side of the electron transport layer away from the cathode; and
在发光层远离电子传输层的一侧制备形成阳极。An anode is prepared on the side of the light-emitting layer away from the electron transport layer.
进一步地，当发光器件为倒置型结构时，所述在发光层远离电子传输层的一侧制备形成阳极，包括如下步骤：Further, when the light-emitting device has an inverted structure, preparing and forming an anode on the side of the light-emitting layer away from the electron transport layer includes the following steps:
在发光层远离电子传输层的一侧制备形成空穴功能层；以及Prepare and form a hole functional layer on the side of the light-emitting layer away from the electron transport layer; and
在空穴功能层远离发光层的一侧制备形成阳极。An anode is prepared on the side of the hole functional layer away from the light-emitting layer.
在本申请的一个实施例中，当发光器件为倒置型结构时，所述制备方法包括如下步骤：In one embodiment of the present application, when the light-emitting device has an inverted structure, the preparation method includes the following steps:
S1’、提供衬底，在衬底的一侧制备形成阴极；S1', provide a substrate, prepare and form a cathode on one side of the substrate;
S2’、在阴极远离衬底的一侧施加包含第一化合物和第二化合物的混合液，干燥处理获得电子传输层；S2', apply a mixed solution containing the first compound and the second compound on the side of the cathode away from the substrate, and dry it to obtain an electron transport layer;
S3’、在电子传输层远离阴极的一侧制备形成发光层；S3', prepare and form a light-emitting layer on the side of the electron transport layer away from the cathode;
S4’、在发光层远离电子传输层的一侧制备形成空穴功能层；S4', prepare and form a hole functional layer on the side of the light-emitting layer away from the electron transport layer;
S5’、在空穴功能层远离发光层的一侧制备形成阳极。S5', prepare and form an anode on the side of the hole functional layer away from the light-emitting layer.
在本申请的另一个实施例中，当发光器件为倒置型结构时，相较于前述具有倒置型结构的发光器件的制备方法，区别之处仅在于：将步骤S4替换为“提供包含第一化合物和第二化合物的混合液，将所述混合液置于交流电场处理预设时间，获得反应液，然后在阴极远离衬底的一侧施加所述反应液，干燥处理获得电子传输层”。In another embodiment of the present application, when the light-emitting device has an inverted structure, compared with the aforementioned method for preparing a light-emitting device with an inverted structure, the only difference is that step S4 is replaced with "Provide a first light-emitting device containing an inverted structure". A mixed solution of a compound and a second compound, the mixed solution is placed in an alternating current electric field for a preset time to obtain a reaction solution, and then the reaction solution is applied to the side of the cathode away from the substrate, and dried to obtain an electron transport layer."
需要说明的是，除了电子传输层之外，发光器件中其他各个膜层的制备方法包括但不限于是溶液法和沉积法，溶液法包括但不限于是旋涂、涂布、喷墨打印、刮涂、浸渍提拉、浸泡、喷涂、滚涂或浇铸；沉积法包括化学法和物理法，化学法包括但不限于是化学气相沉积法、连续离子层吸附与反应法、阳极 氧化法、电解沉积法或共沉淀法，物理法包括但不限于是热蒸发镀膜法、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、原子层沉积法或脉冲激光沉积法。当采用溶液法制备膜层时，需增设干燥处理工序，以使湿膜转变为干膜。It should be noted that, in addition to the electron transport layer, the preparation methods of other film layers in the light-emitting device include but are not limited to solution methods and deposition methods. The solution methods include but are not limited to spin coating, coating, inkjet printing, Scratching, dipping, pulling, soaking, spraying, rolling or casting; deposition methods include chemical methods and physical methods. Chemical methods include but are not limited to chemical vapor deposition, continuous ion layer adsorption and reaction method, anodizing method, electrolysis Deposition method or co-precipitation method, physical method including but not limited to thermal evaporation coating method, electron beam evaporation coating method, magnetron sputtering method, multi-arc ion coating method, physical vapor deposition method, atomic layer deposition method or pulse laser deposition Law. When the solution method is used to prepare the film layer, a drying process needs to be added to convert the wet film into a dry film.
可以理解的是，发光器件的制备方法还可以包括其他步骤，例如：在制备完成发光器件的各个层之后，需对发光器件进行封装处理。It can be understood that the method for preparing a light-emitting device may also include other steps, for example: after each layer of the light-emitting device is prepared, the light-emitting device needs to be packaged.
本申请实施例还提供了一种显示装置，所述显示装置包括本申请实施例中任意一种所述的发光器件或任意一种所述发光器件的制备方法制得的发光器件。所述显示装置可以是任何具有显示功能的电子产品，包括但不限于是智能手机、平板电脑、笔记本电脑、数码相机、数码摄像机、智能可穿戴设备、智能称重电子秤、车载显示器、电视机或电子书阅读器，其中，智能可穿戴设备例如可以是智能手环、智能手表、虚拟现实(Virtual Reality,VR)头盔等。Embodiments of the present application also provide a display device, which includes a light-emitting device according to any one of the light-emitting devices described in the embodiments of the present application or a light-emitting device produced by any of the manufacturing methods of the light-emitting device. The display device can be any electronic product with a display function, including but not limited to smart phones, tablet computers, laptops, digital cameras, digital camcorders, smart wearable devices, smart electronic weighing scales, vehicle monitors, and televisions. Or an e-book reader, where the smart wearable device can be, for example, a smart bracelet, a smart watch, a virtual reality (Virtual Reality, VR) helmet, etc.
下面通过具体实施例、对比例和实验例对本申请的技术方案及技术效果进行详细说明，以下实施例仅仅是本申请的部分实施例，并非对本申请作出具体限定。The technical solutions and technical effects of the present application will be described in detail below through specific examples, comparative examples and experimental examples. The following examples are only some examples of the present application and do not specifically limit the present application.
实施例1Example 1
本实施例提供了一种发光器件及其制备方法，所述发光器件为正置型结构的量子点发光二极管，如图4所示，在由下至上的方向上，发光器件1包括依次设置的衬底10、阳极11、空穴注入层151、空穴传输层152、发光层13、电子传输层14以及阴极12。This embodiment provides a light-emitting device and a preparation method thereof. The light-emitting device is a quantum dot light-emitting diode with an upright structure. As shown in Figure 4, in the direction from bottom to top, the light-emitting device 1 includes linings arranged in sequence. Bottom 10, anode 11, hole injection layer 151, hole transport layer 152, light emitting layer 13, electron transport layer 14 and cathode 12.
发光器件1中各个层的材料与厚度如下：The materials and thicknesses of each layer in the light-emitting device 1 are as follows:
衬底10的材料为玻璃，衬底10的厚度为1mm；The material of the substrate 10 is glass, and the thickness of the substrate 10 is 1mm;
阳极11的材料为ITO，阳极11的厚度为25nm；The material of the anode 11 is ITO, and the thickness of the anode 11 is 25nm;
阴极12的材料为Ag，阴极12的厚度为35nm；The material of the cathode 12 is Ag, and the thickness of the cathode 12 is 35 nm;
发光层13的材料为ZnCdS/ZnS量子点(表面连接有辛硫醇配体)，发光层13的厚度为60nm；The material of the luminescent layer 13 is ZnCdS/ZnS quantum dots (octanethiol ligands are connected to the surface), and the thickness of the luminescent layer 13 is 60nm;
电子传输层14的材料由第一化合物和第二化合物组成，第一化合物为纳米ZnO(粒径为12nm)；第二化合物为二苄叉山梨醇，第一化合物：第二化合物的摩尔比为1：0.15，电子传输层14的厚度为60nm；The material of the electron transport layer 14 is composed of a first compound and a second compound. The first compound is nano-ZnO (particle size is 12 nm); the second compound is dibenzyl sorbitol. The molar ratio of the first compound to the second compound is 1:0.15, the thickness of the electron transport layer 14 is 60nm;
空穴注入层151的材料为PEDOT:PSS，厚度为50nm；The material of the hole injection layer 151 is PEDOT:PSS, and the thickness is 50nm;
空穴传输层152的材料为TFB，厚度为50nm。The hole transport layer 152 is made of TFB and has a thickness of 50 nm.
本实施例中发光器件的制备方法包括如下步骤：The preparation method of the light-emitting device in this embodiment includes the following steps:
S1.1、提供衬底，在衬底的一侧溅射ITO以获得ITO层，用棉签蘸取少量肥皂水擦拭ITO层表面以去除表面肉眼可见的杂质，然后将包括ITO的衬底依次采用去离子水超声清洗15min、丙酮超声清洗15min、乙醇超声清洗15min以及异丙醇超声清洗15min，烘干后采用紫外-臭氧表面处理15min，获得包括阳极的衬底；S1.1. Provide a substrate, sputter ITO on one side of the substrate to obtain the ITO layer, use a cotton swab to dip a small amount of soapy water to wipe the surface of the ITO layer to remove visible impurities on the surface, and then use the substrate including ITO in turn. Ultrasonic cleaning with deionized water for 15 minutes, ultrasonic cleaning with acetone for 15 minutes, ultrasonic cleaning with ethanol for 15 minutes, and ultrasonic cleaning with isopropyl alcohol for 15 minutes. After drying, use UV-ozone surface treatment for 15 minutes to obtain the substrate including the anode;
S1.2、在常温常压的大气环境下，在步骤S1.1的阳极远离衬底的一侧旋涂PEDOT：PSS水溶液，然后置于150℃下恒温热处理20min，获得空穴注入层；S1.2. In an atmospheric environment of normal temperature and pressure, spin-coat the PEDOT:PSS aqueous solution on the side of the anode away from the substrate in step S1.1, and then place it for constant temperature heat treatment at 150°C for 20 minutes to obtain a hole injection layer;
S1.3、在常温常压的氮气环境下，在步骤S1.2的空穴注入层远离阳极的一侧旋涂TFB-氯苯溶液，然后置于150℃下恒温热处理20min，获得空穴传输层；S1.3. In a nitrogen environment at normal temperature and pressure, spin-coat the TFB-chlorobenzene solution on the side of the hole injection layer away from the anode in step S1.2, and then place it at 150°C for constant temperature heat treatment for 20 minutes to obtain hole transport. layer;
S1.4、在常温常压的氮气环境下，在步骤S1.3的空穴传输层远离空穴注入层的一侧旋涂浓度为20mg/mL的ZnCdS/ZnS量子点-正辛烷溶液，然后置于100℃下恒温热处理10min，获得发光层；S1.4. In a nitrogen environment at normal temperature and pressure, spin-coat a ZnCdS/ZnS quantum dot-n-octane solution with a concentration of 20 mg/mL on the side of the hole transport layer away from the hole injection layer in step S1.3. Then place it for constant temperature heat treatment at 100°C for 10 minutes to obtain the luminescent layer;
S1.5、提供浓度为45mg/mL的纳米ZnO(粒径为12nm)-乙醇溶液，将1mL的二苄叉山梨醇溶于99mL的纳米ZnO(粒径为12nm)-乙醇溶液以制得混合液，在常温常压的氮气环境下，在步骤S1.4的发光层远离空穴传输层的一侧旋涂所述混合液，然后置于150℃下恒温热处理20min，获得电子传输层；S1.5. Provide a nano-ZnO (particle size: 12 nm)-ethanol solution with a concentration of 45 mg/mL, and dissolve 1 mL of dibenzylidene sorbitol in 99 mL of nano-ZnO (particle size: 12 nm)-ethanol solution to prepare a mixture. liquid, in a nitrogen environment at normal temperature and pressure, spin-coat the mixed liquid on the side of the light-emitting layer away from the hole transport layer in step S1.4, and then place it for constant temperature heat treatment at 150°C for 20 minutes to obtain the electron transport layer;
S1.6、在气压为4×10 -6mbar的真空环境下，在步骤S1.5的电子传输层远离发光层的一侧蒸镀Ag，获得阴极，然后采用紫外固化胶封装，获得发光器件。 S1.6. In a vacuum environment with an air pressure of 4×10 -6 mbar, evaporate Ag on the side of the electron transport layer away from the light-emitting layer in step S1.5 to obtain a cathode, which is then encapsulated with UV curing glue to obtain a light-emitting device. .
实施例2Example 2
本实施例提供了一种发光器件及其制备方法，相较于实施例1的发光器件，本实施例的发光器件的区别之处仅在于：第一化合物：第二化合物的摩尔比为1：0.1。This embodiment provides a light-emitting device and a preparation method thereof. Compared with the light-emitting device of Embodiment 1, the only difference between the light-emitting device of this embodiment is that: the molar ratio of the first compound: the second compound is 1: 0.1.
相较于实施例1中发光器件的制备方法，本实施例中发光器件的制备方法的区别之处仅在于：将步骤S1.5替换为“提供浓度为60mg/mL的纳米ZnO(粒 径为12nm)-乙醇溶液，将1mL的二苄叉山梨醇溶于99mL的纳米ZnO(粒径为12nm)-乙醇溶液以制得混合液，在常温常压的氮气环境下，在步骤S1.4的发光层远离空穴传输层的一侧旋涂所述混合液，然后置于150℃下恒温热处理20min，获得电子传输层”。Compared with the preparation method of the light-emitting device in Embodiment 1, the only difference between the preparation method of the light-emitting device in this embodiment is that step S1.5 is replaced with "Providing nano-ZnO with a concentration of 60 mg/mL (particle size: 12nm)-ethanol solution, dissolve 1mL of dibenzylidene sorbitol in 99mL of nano-ZnO (particle size 12nm)-ethanol solution to prepare a mixed solution, in a nitrogen environment at normal temperature and pressure, in step S1.4 The side of the light-emitting layer away from the hole transport layer is spin-coated with the mixed solution, and then placed in a constant temperature heat treatment at 150°C for 20 minutes to obtain the electron transport layer."
实施例3Example 3
本实施例提供了一种发光器件及其制备方法，相较于实施例1的发光器件，本实施例的发光器件的区别之处仅在于：第一化合物：第二化合物的摩尔比为1：0.2。This embodiment provides a light-emitting device and a preparation method thereof. Compared with the light-emitting device of Embodiment 1, the only difference between the light-emitting device of this embodiment is that: the molar ratio of the first compound: the second compound is 1: 0.2.
相较于实施例1中发光器件的制备方法，本实施例中发光器件的制备方法的区别之处仅在于：将步骤S1.5替换为“提供浓度为30mg/mL的纳米ZnO(粒径为12nm)-乙醇溶液，将1mL的二苄叉山梨醇溶于99mL的纳米ZnO(粒径为12nm)-乙醇溶液以制得混合液，在常温常压的氮气环境下，在步骤S1.4的发光层远离空穴传输层的一侧旋涂所述混合液，然后置于150℃下恒温热处理20min，获得电子传输层”。Compared with the preparation method of the light-emitting device in Embodiment 1, the only difference between the preparation method of the light-emitting device in this embodiment is that step S1.5 is replaced with "Providing nano-ZnO with a concentration of 30 mg/mL (particle size: 12nm)-ethanol solution, dissolve 1mL of dibenzylidene sorbitol in 99mL of nano-ZnO (particle size 12nm)-ethanol solution to prepare a mixed solution, in a nitrogen environment at normal temperature and pressure, in step S1.4 The side of the light-emitting layer away from the hole transport layer is spin-coated with the mixed solution, and then placed in a constant temperature heat treatment at 150°C for 20 minutes to obtain the electron transport layer."
实施例4Example 4
本实施例提供了一种发光器件及其制备方法，相较于实施例1的发光器件，本实施例的发光器件的区别之处仅在于：第一化合物：第二化合物的摩尔比为1：0.3。This embodiment provides a light-emitting device and a preparation method thereof. Compared with the light-emitting device of Embodiment 1, the only difference between the light-emitting device of this embodiment is that: the molar ratio of the first compound: the second compound is 1: 0.3.
相较于实施例1中发光器件的制备方法，本实施例中发光器件的制备方法的区别之处仅在于：将步骤S1.5替换为“提供浓度为15mg/mL的纳米ZnO(粒径为12nm)-乙醇溶液，将1mL的二苄叉山梨醇溶于99mL的纳米ZnO(粒径为12nm)-乙醇溶液以制得混合液，在常温常压的氮气环境下，在步骤S1.4的发光层远离空穴传输层的一侧旋涂所述混合液，然后置于150℃下恒温热处理20min，获得电子传输层”。Compared with the preparation method of the light-emitting device in Embodiment 1, the only difference between the preparation method of the light-emitting device in this embodiment is that step S1.5 is replaced with "Providing nano-ZnO with a concentration of 15 mg/mL (particle size: 12nm)-ethanol solution, dissolve 1mL of dibenzylidene sorbitol in 99mL of nano-ZnO (particle size 12nm)-ethanol solution to prepare a mixed solution, in a nitrogen environment at normal temperature and pressure, in step S1.4 The side of the light-emitting layer away from the hole transport layer is spin-coated with the mixed solution, and then placed in a constant temperature heat treatment at 150°C for 20 minutes to obtain the electron transport layer."
实施例5Example 5
本实施例提供了一种发光器件及其制备方法，相较于实施例1的发光器件，本实施例的发光器件的区别之处仅在于：第一化合物：第二化合物的摩尔比为1：0.05。This embodiment provides a light-emitting device and a preparation method thereof. Compared with the light-emitting device of Embodiment 1, the only difference between the light-emitting device of this embodiment is that: the molar ratio of the first compound: the second compound is 1: 0.05.
相较于实施例1中发光器件的制备方法，本实施例中发光器件的制备方法 的区别之处仅在于：将步骤S1.5替换为“提供浓度为120mg/mL的纳米ZnO(粒径为12nm)-乙醇溶液，将1mL的二苄叉山梨醇溶于99mL的纳米ZnO(粒径为12nm)-乙醇溶液以制得混合液，在常温常压的氮气环境下，在步骤S1.4的发光层远离空穴传输层的一侧旋涂所述混合液，然后置于150℃下恒温热处理20min，获得电子传输层”。Compared with the preparation method of the light-emitting device in Embodiment 1, the only difference between the preparation method of the light-emitting device in this embodiment is that step S1.5 is replaced with "Provide nano-ZnO with a concentration of 120 mg/mL (particle size is 12nm)-ethanol solution, dissolve 1mL of dibenzylidene sorbitol in 99mL of nano-ZnO (particle size 12nm)-ethanol solution to prepare a mixed solution, in a nitrogen environment at normal temperature and pressure, in step S1.4 The side of the light-emitting layer away from the hole transport layer is spin-coated with the mixed solution, and then placed in a constant temperature heat treatment at 150°C for 20 minutes to obtain the electron transport layer."
实施例6Example 6
本实施例提供了一种发光器件的制备方法及其制得的发光器件，相较于实施例1中发光器件的制备方法，本实施例中发光器件的制备方法的区别之处仅在于：将步骤S1.5替换为“提供浓度为45mg/mL的纳米ZnO(粒径为12nm)-乙醇溶液，将1mL的二苄叉山梨醇溶于99mL的纳米ZnO(粒径为12nm)-乙醇溶液以制得混合液，将所述混合液置于频率为50Hz、电压为负200V至正200V的矩形交流电场下反应1min，获得反应液；然后，在常温常压的氮气环境下，在步骤S1.4的发光层远离空穴传输层的一侧旋涂所述反应液，然后置于150℃下恒温热处理20min，获得电子传输层”。This embodiment provides a method for preparing a light-emitting device and the light-emitting device prepared therefrom. Compared with the method for preparing the light-emitting device in Embodiment 1, the only difference between the method for preparing the light-emitting device in this embodiment is that: Step S1.5 is replaced with "Provide a nano-ZnO (particle size of 12 nm)-ethanol solution with a concentration of 45 mg/mL, and dissolve 1 mL of dibenzyl sorbitol in 99 mL of nano-ZnO (particle size of 12 nm)-ethanol solution. Prepare a mixed liquid, and place the mixed liquid in a rectangular alternating current electric field with a frequency of 50Hz and a voltage of negative 200V to positive 200V to react for 1 min to obtain a reaction liquid; then, in a nitrogen environment at normal temperature and pressure, perform step S1. 4. Spin-coat the reaction solution on the side of the light-emitting layer away from the hole transport layer, and then place it for constant temperature heat treatment at 150°C for 20 minutes to obtain the electron transport layer."
实施例7Example 7
本实施例提供了一种发光器件的制备方法及其制得的发光器件，相较于实施例6中发光器件的制备方法，本实施例中发光器件的制备方法的区别之处仅在于：将混合液置于交流电场下的反应时间由“1min”替换为“2min”。This embodiment provides a method for preparing a light-emitting device and the light-emitting device prepared therefrom. Compared with the method for preparing the light-emitting device in Embodiment 6, the only difference between the method for preparing the light-emitting device in this embodiment is that: The reaction time of the mixed solution placed under an alternating electric field is replaced from "1min" to "2min".
实施例8Example 8
本实施例提供了一种发光器件的制备方法及其制得的发光器件，相较于实施例6中发光器件的制备方法，本实施例中发光器件的制备方法的区别之处仅在于：将混合液置于交流电场下的反应时间由“1min”替换为“3min”。This embodiment provides a method for preparing a light-emitting device and the light-emitting device prepared therefrom. Compared with the method for preparing the light-emitting device in Embodiment 6, the only difference between the method for preparing the light-emitting device in this embodiment is that: The reaction time when the mixed solution is placed under an AC electric field is replaced from "1min" to "3min".
实施例9Example 9
本实施例提供了一种发光器件的制备方法及其制得的发光器件，相较于实施例6中发光器件的制备方法，本实施例中发光器件的制备方法的区别之处仅在于：将混合液置于交流电场下的反应时间由“1min”替换为“4min”。This embodiment provides a method for preparing a light-emitting device and the light-emitting device prepared therefrom. Compared with the method for preparing the light-emitting device in Embodiment 6, the only difference between the method for preparing the light-emitting device in this embodiment is that: The reaction time of the mixed solution placed under an AC electric field is replaced from "1min" to "4min".
实施例10Example 10
本实施例提供了一种发光器件的制备方法及其制得的发光器件，相较于实施例6中发光器件的制备方法，本实施例中发光器件的制备方法的区别之处仅 在于：将混合液置于交流电场下的反应时间由“1min”替换为“5min”。This embodiment provides a method for preparing a light-emitting device and the light-emitting device prepared therefrom. Compared with the method for preparing the light-emitting device in Embodiment 6, the only difference between the method for preparing the light-emitting device in this embodiment is that: The reaction time of the mixed solution under AC electric field is replaced from "1min" to "5min".
实施例11Example 11
本实施例提供了一种发光器件的制备方法及其制得的发光器件，相较于实施例6中发光器件的制备方法，本实施例中发光器件的制备方法的区别之处仅在于：将混合液置于交流电场下的反应时间由“1min”替换为“6min”。This embodiment provides a method for preparing a light-emitting device and the light-emitting device prepared therefrom. Compared with the method for preparing the light-emitting device in Embodiment 6, the only difference between the method for preparing the light-emitting device in this embodiment is that: The reaction time of the mixed solution placed under an AC electric field is replaced from "1min" to "6min".
实施例12Example 12
本实施例提供了一种发光器件的制备方法及其制得的发光器件，相较于实施例6中发光器件的制备方法，本实施例中发光器件的制备方法的区别之处仅在于：将混合液置于交流电场下的反应时间由“1min”替换为“7min”。This embodiment provides a method for preparing a light-emitting device and the light-emitting device prepared therefrom. Compared with the method for preparing the light-emitting device in Embodiment 6, the only difference between the method for preparing the light-emitting device in this embodiment is that: The reaction time of the mixed solution placed under an AC electric field is replaced from "1min" to "7min".
实施例13Example 13
本实施例提供了一种发光器件的制备方法及其制得的发光器件，相较于实施例6中发光器件的制备方法，本实施例中发光器件的制备方法的区别之处仅在于：将混合液置于交流电场下的反应时间由“1min”替换为“8min”。This embodiment provides a method for preparing a light-emitting device and the light-emitting device prepared therefrom. Compared with the method for preparing the light-emitting device in Embodiment 6, the only difference between the method for preparing the light-emitting device in this embodiment is that: The reaction time of the mixed solution placed under an AC electric field is replaced from "1min" to "8min".
实施例14Example 14
本实施例提供了一种发光器件的制备方法及其制得的发光器件，相较于实施例1中发光器件的制备方法，本实施例中发光器件的制备方法的区别之处仅在于：将步骤S1.5替换为“提供浓度为45mg/mL的纳米ZnO(粒径为12nm)-乙醇溶液，将315mg的琥珀酸钠溶于100mL的纳米ZnO(粒径为12nm)-乙醇溶液以制得混合液，然后在常温常压的氮气环境下，在步骤S1.4的发光层远离空穴传输层的一侧旋涂所述混合液，然后置于150℃下恒温热处理20min，获得电子传输层”。This embodiment provides a method for preparing a light-emitting device and the light-emitting device prepared therefrom. Compared with the method for preparing the light-emitting device in Embodiment 1, the only difference between the method for preparing the light-emitting device in this embodiment is that: Step S1.5 is replaced with "Provide a nano-ZnO (particle size: 12 nm)-ethanol solution with a concentration of 45 mg/mL, and dissolve 315 mg of sodium succinate in 100 mL of nano-ZnO (particle size: 12 nm)-ethanol solution to prepare The mixed solution is then spin-coated on the side of the light-emitting layer away from the hole transport layer in step S1.4 under a nitrogen environment at normal temperature and pressure, and then placed in a constant temperature heat treatment of 150°C for 20 minutes to obtain an electron transport layer. ".
实施例15Example 15
本实施例提供了一种发光器件的制备方法及其制得的发光器件，相较于实施例1中发光器件的制备方法，本实施例中发光器件的制备方法的区别之处仅在于：将步骤S1.5替换为“提供浓度为45mg/mL的纳米ZnO(粒径为12nm)-乙醇溶液，将315mg的琥珀酸钠溶于100mL的纳米ZnO(粒径为12nm)-乙醇溶液以制得混合液，将所述混合液置于频率为50Hz、电压为负200V至正200V的矩形交流电场下反应5min，获得反应液；然后，在常温常压的氮气环境下，在步骤S1.4的发光层远离空穴传输层的一侧旋涂所述反应液，然后置于150℃ 下恒温热处理20min，获得电子传输层”。This embodiment provides a method for preparing a light-emitting device and the light-emitting device prepared therefrom. Compared with the method for preparing the light-emitting device in Embodiment 1, the only difference between the method for preparing the light-emitting device in this embodiment is that: Step S1.5 is replaced with "Provide a nano-ZnO (particle size: 12 nm)-ethanol solution with a concentration of 45 mg/mL, and dissolve 315 mg of sodium succinate in 100 mL of nano-ZnO (particle size: 12 nm)-ethanol solution to prepare Mixed liquid, the mixed liquid is placed in a rectangular AC electric field with a frequency of 50Hz and a voltage of negative 200V to positive 200V to react for 5 minutes to obtain a reaction liquid; then, in a nitrogen environment at normal temperature and pressure, in step S1.4 The side of the light-emitting layer away from the hole transport layer is spin-coated with the reaction solution, and then placed in a constant temperature heat treatment at 150°C for 20 minutes to obtain the electron transport layer."
实施例16Example 16
本实施例提供了一种发光器件的制备方法及其制得的发光器件，相较于实施例1中发光器件的制备方法，本实施例中发光器件的制备方法的区别之处仅在于：将步骤S1.5替换为“提供浓度为45mg/mL的纳米ZnO(粒径为12nm)-乙醇溶液，将1mL的β型聚丙烯溶于99mL的纳米ZnO(粒径为12nm)-乙醇溶液以制得混合液，然后在常温常压的氮气环境下，在步骤S1.4的发光层远离空穴传输层的一侧旋涂所述混合液，然后置于150℃下恒温热处理20min，获得电子传输层”。This embodiment provides a method for preparing a light-emitting device and the light-emitting device prepared therefrom. Compared with the method for preparing the light-emitting device in Embodiment 1, the only difference between the method for preparing the light-emitting device in this embodiment is that: Step S1.5 is replaced with "Provide a nano-ZnO (particle diameter of 12 nm)-ethanol solution with a concentration of 45 mg/mL, and dissolve 1 mL of β-type polypropylene in 99 mL of nano-ZnO (particle diameter of 12 nm)-ethanol solution to prepare Obtain a mixed solution, and then spin-coat the mixed solution on the side of the light-emitting layer away from the hole transport layer in step S1.4 under a nitrogen environment at normal temperature and pressure, and then place it for constant temperature heat treatment at 150°C for 20 minutes to obtain electron transmission. layer".
实施例17Example 17
本实施例提供了一种发光器件的制备方法及其制得的发光器件，相较于实施例1中发光器件的制备方法，本实施例中发光器件的制备方法的区别之处仅在于：将步骤S1.5替换为“提供浓度为45mg/mL的纳米ZnO(粒径为12nm)-乙醇溶液，将1mL的β型聚丙烯溶于99mL的纳米ZnO(粒径为12nm)-乙醇溶液以制得混合液，将所述混合液置于频率为50Hz、电压为负200V至正200V的矩形交流电场下反应5min，获得反应液；然后，在常温常压的氮气环境下，在步骤S1.4的发光层远离空穴传输层的一侧旋涂所述反应液，然后置于150℃下恒温热处理20min，获得电子传输层”。This embodiment provides a method for preparing a light-emitting device and the light-emitting device prepared therefrom. Compared with the method for preparing the light-emitting device in Embodiment 1, the only difference between the method for preparing the light-emitting device in this embodiment is that: Step S1.5 is replaced with "Provide a nano-ZnO (particle diameter of 12 nm)-ethanol solution with a concentration of 45 mg/mL, and dissolve 1 mL of β-type polypropylene in 99 mL of nano-ZnO (particle diameter of 12 nm)-ethanol solution to prepare A mixed liquid is obtained, and the mixed liquid is placed in a rectangular AC electric field with a frequency of 50Hz and a voltage of negative 200V to positive 200V for 5 minutes to obtain a reaction liquid; then, in a nitrogen environment at normal temperature and pressure, in step S1.4 The side of the light-emitting layer away from the hole transport layer is spin-coated with the reaction solution, and then placed in a constant temperature heat treatment at 150°C for 20 minutes to obtain the electron transport layer."
实施例18Example 18
本实施例提供了一种发光器件的制备方法及其制得的发光器件，相较于实施例1中发光器件的制备方法，本实施例中发光器件的制备方法的区别之处仅在于：将步骤S1.5替换为“提供浓度为45mg/mL的纳米ZnO(粒径为12nm)-乙醇溶液，将1575mg的云母溶于100mL的纳米ZnO(粒径为12nm)-乙醇溶液以制得混合液，然后在常温常压的氮气环境下，在步骤S1.4的发光层远离空穴传输层的一侧旋涂所述混合液，然后置于150℃下恒温热处理20min，获得电子传输层”。This embodiment provides a method for preparing a light-emitting device and the light-emitting device prepared therefrom. Compared with the method for preparing the light-emitting device in Embodiment 1, the only difference between the method for preparing the light-emitting device in this embodiment is that: Step S1.5 is replaced with "Provide a nano-ZnO (particle size: 12 nm)-ethanol solution with a concentration of 45 mg/mL, and dissolve 1575 mg of mica in 100 mL of nano-ZnO (particle size: 12 nm)-ethanol solution to prepare a mixed solution , and then spin-coat the mixed liquid on the side of the light-emitting layer away from the hole transport layer in step S1.4 under a nitrogen environment at normal temperature and pressure, and then place it for constant temperature heat treatment at 150°C for 20 minutes to obtain the electron transport layer."
实施例19Example 19
本实施例提供了一种发光器件的制备方法及其制得的发光器件，相较于实施例1中发光器件的制备方法，本实施例中发光器件的制备方法的区别之处仅 在于：将步骤S1.5替换为“提供浓度为45mg/mL的纳米ZnO(粒径为12nm)-乙醇溶液，将1575mg的云母溶于100mL的纳米ZnO(粒径为12nm)-乙醇溶液以制得混合液，将所述混合液置于频率为50Hz、电压为负200V至正200V的矩形交流电场下反应5min，获得反应液；然后，在常温常压的氮气环境下，在步骤S1.4的发光层远离空穴传输层的一侧旋涂所述反应液，然后置于150℃下恒温热处理20min，获得电子传输层”。This embodiment provides a method for preparing a light-emitting device and the light-emitting device prepared therefrom. Compared with the method for preparing the light-emitting device in Embodiment 1, the only difference between the method for preparing the light-emitting device in this embodiment is that: Step S1.5 is replaced with "Provide a nano-ZnO (particle size: 12 nm)-ethanol solution with a concentration of 45 mg/mL, and dissolve 1575 mg of mica in 100 mL of nano-ZnO (particle size: 12 nm)-ethanol solution to prepare a mixed solution , the mixed liquid was placed in a rectangular AC electric field with a frequency of 50Hz and a voltage of negative 200V to positive 200V to react for 5 minutes to obtain a reaction liquid; then, in a nitrogen environment at normal temperature and pressure, the luminescent layer in step S1.4 was Spin-coat the reaction solution on the side away from the hole transport layer, and then place it for constant temperature heat treatment at 150°C for 20 minutes to obtain the electron transport layer."
对比例Comparative ratio
本实施例提供了一种发光器件及其制备方法，相较于实施例1的发光器件，本对比例的发光器件的区别之处仅在于：电子传输层的材料为粒径是12nm的纳米ZnO。This embodiment provides a light-emitting device and a preparation method thereof. Compared with the light-emitting device of Example 1, the only difference between the light-emitting device of this comparative example is that the material of the electron transport layer is nano-ZnO with a particle size of 12 nm. .
较于实施例1的制备方法，本实施例的制备方法区别之处仅在于：将步骤S1.5替换为“在常温常压的氮气环境下，在步骤S1.4的发光层远离空穴传输层的一侧旋涂浓度为45mg/mL的纳米ZnO(粒径为12nm)-乙醇溶液，然后置于150℃下恒温热处理20min，获得电子传输层”。Compared with the preparation method of Embodiment 1, the only difference between the preparation method of this embodiment is that step S1.5 is replaced with "In a nitrogen environment at normal temperature and pressure, the light-emitting layer in step S1.4 is far away from hole transport." One side of the layer is spin-coated with a nano-ZnO (particle size: 12 nm)-ethanol solution with a concentration of 45 mg/mL, and then placed in a constant temperature heat treatment at 150°C for 20 minutes to obtain an electron transport layer."
实验例Experimental example
对实施例1至实施例19以及对比例的发光器件进行性能检测，采用弗士达FPD光学特性测量设备(由LabView控制QE-PRO光谱仪、Keithley 2400以及Keithley 6485搭建的效率测试***)检测获得各个发光器件的电压、电流、亮度、发光光谱等参数，然后计算获得外量子效率(External Quantum Efficiency,EQE)、功率效率等关键参数，并采用寿命测试设备测试上述的各个发光器件的使用寿命。其中，外量子效率的测试方法为积分球测试法；寿命测试采用恒流法，在恒定电流(2mA电流)的驱动下，采用硅光***测试各个发光器件的亮度变化，记录亮度由100％衰减至95％所需的时间(T95,h)，并计算获得各个发光器件在1000尼特(nit)的亮度下亮度由100％衰减至95％所需的时间(LT95@1000nit,h)。The performance of the light-emitting devices from Examples 1 to 19 and Comparative Examples was tested using FPD optical property measurement equipment (an efficiency test system built by LabView controlling QE-PRO spectrometer, Keithley 2400 and Keithley 6485) to detect and obtain various Parameters such as voltage, current, brightness, and luminescence spectrum of the light-emitting device are then calculated to obtain key parameters such as External Quantum Efficiency (EQE) and power efficiency, and life testing equipment is used to test the service life of each of the above-mentioned light-emitting devices. Among them, the external quantum efficiency test method is the integrating sphere test method; the life test uses the constant current method. Driven by a constant current (2mA current), a silicon photosystem is used to test the brightness changes of each light-emitting device, and the brightness is recorded to be attenuated from 100%. to 95% (T95, h), and calculate the time required for each light-emitting device to decay from 100% to 95% brightness at a brightness of 1000 nit (LT95@1000nit, h).
各个发光器件的最大发光效率(CE@max,cd/A)、1000nit亮度下的发光效率(CE@1knit,cd/A)以及LT95@1000nit的性能检测数据详见下表1：The maximum luminous efficiency of each light-emitting device (CE@max, cd/A), the luminous efficiency at 1000nit brightness (CE@1knit, cd/A), and the performance testing data of LT95@1000nit are detailed in Table 1 below:
表1实施例1至实施例19以及对比例的发光器件的性能检测数据一览表Table 1 List of performance test data of the light-emitting devices of Examples 1 to 19 and Comparative Examples
Figure PCTCN2022140025-appb-000001
Figure PCTCN2022140025-appb-000001
Figure PCTCN2022140025-appb-000002
Figure PCTCN2022140025-appb-000002
由表1可知，实施例1至实施例19中发光器件的综合性能均明显优越于对比例的发光器件，以实施例10为例，实施例10中发光器件的CE@max是对比例中CE@max的2.0倍，且实施例10中发光器件的CE@1knit是对比例中CE@1knit的2.4倍，且实施例10中发光器件的LT95@1000nit是对比例中LT95@1000nit的11.6倍，充分说明：采用包含形核剂和纳米金属氧化物的电子传输材料制备电子传输层，能够提高电子传输层的晶粒度，从而增大电子传输层的电阻，减少过量电子积累于发光层，提高电子注入水平与空穴注入水平之间的匹配度，促进发光器件的载流子平衡，进而提高发光器件的发光效率和工作寿命。It can be seen from Table 1 that the comprehensive performance of the light-emitting devices in Examples 1 to 19 is significantly better than that of the light-emitting devices in the comparative example. Taking Example 10 as an example, the CE@max of the light-emitting device in Example 10 is the CE of the comparative example. 2.0 times of @max, and the CE@1knit of the light-emitting device in Example 10 is 2.4 times that of CE@1knit in the comparative example, and the LT95@1000nit of the light-emitting device in Example 10 is 11.6 times that of LT95@1000nit in the comparative example, Full explanation: Using electron transport materials containing nucleating agents and nanometal oxides to prepare the electron transport layer can increase the grain size of the electron transport layer, thereby increasing the resistance of the electron transport layer, reducing the accumulation of excess electrons in the light-emitting layer, and improving The matching degree between the electron injection level and the hole injection level promotes the carrier balance of the light-emitting device, thereby improving the luminous efficiency and working life of the light-emitting device.
由实施例1至实施例5的性能检测数据可知，实施例1至实施例3中发光器件的综合性能均优于实施例4和实施例5的发光器件，因此，优选电子传输层中纳米金属氧化物：形核剂的摩尔比为1：(0.1～0.2)，形核剂的含量过高或过低均对发光器件的综合性能提升效果有限，若形核剂的含量过低(例如实施例5)，则对纳米金属氧化物非自发形核的促进效果有限，从而电子传输层的电阻的提高程度有限；若形核剂的含量过高(例如实施例4)，则对发光器件的电子注入水平与空穴注入水平之间匹配度的提升程度有限。It can be seen from the performance testing data of Examples 1 to 5 that the comprehensive performance of the light-emitting devices in Examples 1 to 3 is better than that of the light-emitting devices in Examples 4 and 5. Therefore, nanometallic materials in the electron transport layer are preferred. The molar ratio of oxide: nucleating agent is 1: (0.1~0.2). If the content of nucleating agent is too high or too low, it will have limited effect on improving the overall performance of the light-emitting device. If the content of nucleating agent is too low (such as implementing Example 5), the promotion effect on the non-spontaneous nucleation of nanometal oxides is limited, so the improvement in the resistance of the electron transport layer is limited; if the content of the nucleating agent is too high (for example, Example 4), the effect on the resistance of the light-emitting device will be limited. The degree of improvement in the matching between the electron injection level and the hole injection level is limited.
由实施例1以及实施例6至实施例13、实施例14与实施例15、实施例16与实施例17，以及实施例18与实施例19的性能检测数据可知，实施例6至实施例13中发光器件的综合性能均优于实施例1的发光器件，且实施例10的发光器件的综合性能最佳，充分说明：相较于未经交流电场处理的混合液制得的电子传输层，经交流电场处理的混合液制得的电子传输层晶粒度更大，从而更有利于提高发光器件的综合性能，尤其有利于提升发光器件在低亮度(1000nit)下的发光效率和工作寿命；由实施例6至实施例13可知，在特定的交流电场条件下，交流电场处理时间优选为1min至5min，且5min效果更佳，交流电场处理时间较长或较短均对发光器件的综合性能提升效果有限，交流电场处理时间较短(例如实施例6)，则对晶粒度的增大程度有限，从而对电子传输层的电阻提高程度有限；交流电场处理时间较长(例如实施例11至实施例 13)，则可能会因晶粒度过大而出现一定程度的位错，使得晶体缺陷增多。It can be seen from the performance test data of Example 1 and Example 6 to Example 13, Example 14 and Example 15, Example 16 and Example 17, and Example 18 and Example 19 that Example 6 to Example 13 The comprehensive performance of the light-emitting device in Example 1 is better than that of the light-emitting device of Example 1, and the comprehensive performance of the light-emitting device of Example 10 is the best, which fully demonstrates that: compared with the electron transport layer prepared from the mixed liquid without AC electric field treatment, The electron transport layer produced by the mixed liquid treated with AC electric field has a larger grain size, which is more conducive to improving the overall performance of the light-emitting device, especially conducive to improving the luminous efficiency and working life of the light-emitting device at low brightness (1000nit); From Example 6 to Example 13, it can be seen that under specific AC electric field conditions, the AC electric field treatment time is preferably 1 min to 5 min, and 5 min is more effective. A longer or shorter AC electric field treatment time will have an impact on the overall performance of the light-emitting device. The improvement effect is limited. If the AC electric field treatment time is short (for example, Example 6), the increase in the grain size will be limited, and thus the resistance improvement of the electron transport layer will be limited. The AC electric field treatment time will be long (for example, Example 11). To Example 13), a certain degree of dislocation may occur due to excessively large crystal grains, resulting in an increase in crystal defects.
由实施例10、实施例14至实施例19以及对比例的性能检测数据可知，无论加入何种形核剂，采用交流电场处理用于制备电子传输层的混合液都能达到优化晶粒度而提升发光器件的综合性能的目的，优选二苄叉山梨醇作为形核剂，原因在于：二苄叉山梨醇具有廉价易得、环境危害小的优点，并且因其为无色材料，所以不会影响电子传输层的透明度，从而不会对发光器件的发光效率造成负面影响。It can be seen from the performance testing data of Example 10, Example 14 to Example 19 and the comparative example that no matter what kind of nucleating agent is added, the mixed liquid used to prepare the electron transport layer by AC electric field treatment can achieve optimized grain size and For the purpose of improving the comprehensive performance of light-emitting devices, dibenzylsorbitol is preferred as the nucleating agent because: dibenzylsorbitol has the advantages of being cheap, easy to obtain, and less harmful to the environment, and because it is a colorless material, it does not Affects the transparency of the electron transport layer, thereby not negatively affecting the luminous efficiency of the light-emitting device.
在上述实施例中，对各个实施例的描述都各有侧重，某个实施例中没有详述的部分，可以参见其他实施例的相关描述。In the above embodiments, each embodiment is described with its own emphasis. For parts that are not described in detail in a certain embodiment, please refer to the relevant descriptions of other embodiments.
以上对本申请实施例所提供的一种发光器件、发光器件的制备方法以及显示装置进行了详细介绍，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 above is a detailed introduction to a light-emitting device, a method for preparing a light-emitting device and a display device provided by the embodiments of the present application. Specific examples are used in this article to illustrate the principles and implementation methods of the present application. The description of the above embodiments is only It is used to help understand the methods and core ideas of this application; at the same time, for those skilled in the art, there will be changes in the specific implementation and application scope based on the ideas of this application. In summary, this specification The contents should not be construed as limitations on this application.

Claims (20)

  1. 一种发光器件，其中，所述发光器件包括：A light-emitting device, wherein the light-emitting device includes:
    阳极；anode;
    阴极，与所述阳极相对设置；The cathode is arranged opposite to the anode;
    发光层，设置于所述阳极与所述阴极之间；以及a light-emitting layer disposed between the anode and the cathode; and
    电子传输层，设置于所述阴极与所述发光层之间；An electron transport layer is provided between the cathode and the light-emitting layer;
    其中，所述电子传输层的材料包括第一化合物和第二化合物，所述第一化合物为纳米金属氧化物，所述第二化合物为形核剂。Wherein, the material of the electron transport layer includes a first compound and a second compound, the first compound is a nanometal oxide, and the second compound is a nucleating agent.
  2. 根据权利要求1所述的发光器件，其中，所述第一化合物选自ZnO、TiO 2、SnO 2、BaO、Ta 2O 3、ZrO 2、TiLiO、ZnGaO、ZnAlO、ZnMgO、ZnSnO、ZnLiO、InSnO、AlZnO、ZnOCl或ZnOF中的至少一种。 The light-emitting device according to claim 1, wherein the first compound is selected from the group consisting of ZnO, TiO 2 , SnO 2 , BaO, Ta 2 O 3 , ZrO 2 , TiLiO, ZnGaO, ZnAlO, ZnMgO, ZnSnO, ZnLiO, InSnO , AlZnO, ZnOCl or at least one of ZnOF.
  3. 根据权利要求1或2所述的发光器件，其中，所述第一化合物的平均粒径为2nm至15nm。The light-emitting device according to claim 1 or 2, wherein the first compound has an average particle size of 2 nm to 15 nm.
  4. 根据权利要求1至3任一项中所述的发光器件，其中，所述形核剂选自有机形核剂以及无机形核剂中的一种或多种；The light-emitting device according to any one of claims 1 to 3, wherein the nucleating agent is selected from one or more of organic nucleating agents and inorganic nucleating agents;
    其中，所述有机形核剂选自羧酸金属盐类化合物、山梨醇类化合物、聚合物形核剂以及β晶型形核剂中的一种或多种；Wherein, the organic nucleating agent is selected from one or more of carboxylic acid metal salt compounds, sorbitol compounds, polymer nucleating agents and β crystal nucleating agents;
    所述无机形核剂选自炭黑、氧化钙、云母、滑石粉以及高岭土中的一种或多种。The inorganic nucleating agent is selected from one or more types of carbon black, calcium oxide, mica, talc and kaolin.
  5. 根据权利要求4所述的发光器件，其中，所述羧酸金属盐类化合物选自琥珀酸钠、戊二酸钠、己酸钠、4-甲基戊酸钠、己二酸、己二酸铝、特丁基苯甲酸铝、苯甲酸铝、苯甲酸钾、苯甲酸锂、肉桂酸钠以及β-萘甲酸钠中的一种或多种；The light-emitting device according to claim 4, wherein the carboxylic acid metal salt compound is selected from the group consisting of sodium succinate, sodium glutarate, sodium caproate, sodium 4-methylvalerate, adipic acid, and adipic acid. One or more of aluminum, tert-butyl aluminum benzoate, aluminum benzoate, potassium benzoate, lithium benzoate, sodium cinnamate and sodium beta-naphthoate;
    所述山梨醇类化合物选自二苄叉山梨醇、二(对一甲基苄叉)山梨醇以及二(对氯取代苄叉)山梨醇中的一种或多种；The sorbitol compound is selected from one or more of dibenzylidene sorbitol, di(p-monomethylbenzylidene) sorbitol, and di(p-chlorosubstituted benzylidene) sorbitol;
    所述聚合物形核剂选自聚乙烯基环己烷、聚乙烯戊烷以及乙烯/丙烯酸酯共聚物中的一种或多种；The polymer nucleating agent is selected from one or more of polyvinylcyclohexane, polyethylenepentane and ethylene/acrylate copolymer;
    所述β晶型形核剂选自β型聚丙烯。The β-crystalline nucleating agent is selected from β-type polypropylene.
  6. 根据权利要求1至5任一项中所述的发光器件，其中，在所述电子传输层中，所述第一化合物：所述第二化合物的摩尔比为1：(0.1～0.2)。The light-emitting device according to any one of claims 1 to 5, wherein in the electron transport layer, the molar ratio of the first compound:the second compound is 1: (0.1˜0.2).
  7. 根据权利要求1至6任一项中所述的发光器件，其中，所述发光层的材料为量子点，所述量子点选自单一组分量子点、核壳结构量子点、无机钙钛矿量子点以及有机-无机杂化钙钛矿量子点的一种或多种；The light-emitting device according to any one of claims 1 to 6, wherein the material of the light-emitting layer is quantum dots, and the quantum dots are selected from the group consisting of single-component quantum dots, core-shell structure quantum dots, and inorganic perovskite. One or more types of quantum dots and organic-inorganic hybrid perovskite quantum dots;
    当所述量子点选自单一组分量子点或核壳结构量子点时，所述单一组分量子点的材料、所述核壳结构量子点的核的材料以及所述核壳结构量子点的壳的材料彼此独立地选自II-VI族化合物、III-V族化合物、IV-VI族化合物或I-III-VI族化合物中的至少一种，其中，所述II-VI族化合物选自CdS、CdSe、CdTe、ZnS、ZnSe、ZnTe、ZnO、HgS、HgSe、HgTe、CdSeS、CdSeTe、CdSTe、ZnSeS、ZnSeTe、ZnSTe、HgSeS、HgSeTe、HgSTe、CdZnS、CdZnSe、CdZnTe、CdHgS、CdHgSe、CdHgTe、HgZnS、HgZnSe、HgZnTe、CdZnSeS、CdZnSeTe、CdZnSTe、CdHgSeS、CdHgSeTe、CdHgSTe、HgZnSeS、HgZnSeTe或HgZnSTe中的至少一种，所述III-V族化合物选自GaN、GaP、GaAs、GaSb、AlN、AlP、AlAs、AlSb、InN、InP、InAs、InSb、GaNP、GaNAs、GaNSb、GaPAs、GaPSb、AlNP、AlNAs、AlNSb、AlPAs、AlPSb、InNP、InNAs、InNSb、InPAs、InPSb、GaAlNP、GaAlNAs、GaAlNSb、GaAlPAs、GaAlPSb、GaInNP、GaInNAs、GaInNSb、GaInPAs、GaInPSb、InAlNP、InAlNAs、InAlNSb、InAlPAs或InAlPSb中的至少一种，所述IV-VI族化合物选自SnS、SnSe、SnTe、PbS、PbSe、PbTe、SnSeS、SnSeTe、SnSTe、PbSeS、PbSeTe、PbSTe、SnPbS、SnPbSe、SnPbTe、SnPbSSe、SnPbSeTe或SnPbSTe中的至少一种，所述I-III-VI族化合物选自CuInS、CuInSe或AgInS中的至少一种；When the quantum dots are selected from single-component quantum dots or core-shell structure quantum dots, the materials of the single-component quantum dots, the core materials of the core-shell structure quantum dots, and the core-shell structure quantum dots The materials of the shell are independently selected from at least one of II-VI compounds, III-V compounds, IV-VI compounds or I-III-VI compounds, wherein the II-VI compounds are selected from CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, At least one of HgZnS, HgZnSe, HgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe or HgZnSTe, and the III-V compound is selected from GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, At least one of GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs or InAlPSb, and the IV-VI compound is selected from SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, At least one of SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, SnPbSeTe or SnPbSTe, and the Group I-III-VI compound is selected from at least one of CuInS, CuInSe or AgInS;
    所述阳极和所述阴极的材料彼此独立地选自金属、碳材料以及金属氧化物中的一种或多种，其中，所述金属选自Al、Ag、Cu、Mo、Au、Ba、Ca以及Mg中的一种或多种；所述碳材料选自石墨、碳纳米管、石墨烯以及碳纤维中的一种或多种；所述金属氧化物选自氧化铟锡、氟掺杂氧化锡、氧化锡锑、铝掺杂的氧化锌、镓掺杂的氧化锌、铟掺杂的氧化锌以及镁掺杂的氧化锌中的一种或多种。The materials of the anode and the cathode are independently selected from one or more of metals, carbon materials and metal oxides, wherein the metal is selected from Al, Ag, Cu, Mo, Au, Ba, Ca and one or more of Mg; the carbon material is selected from one or more of graphite, carbon nanotubes, graphene and carbon fiber; the metal oxide is selected from indium tin oxide, fluorine-doped tin oxide , one or more of tin antimony oxide, aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, and magnesium-doped zinc oxide.
  8. 根据权利要求1至7任一项中所述的发光器件，其中，所述发光器件还包括空穴功能层，所述空穴功能层设置于所述阳极与所述发光层之间；The light-emitting device according to any one of claims 1 to 7, wherein the light-emitting device further includes a hole function layer, the hole function layer is disposed between the anode and the light-emitting layer;
    所述空穴功能层包括空穴注入层以及空穴传输层中的一种或多种，当所述空穴功能层包括层叠设置的空穴传输层和空穴注入层时，所述空穴传输层靠近所述发光层，且所述空穴注入层靠近所述阳极；The hole function layer includes one or more of a hole injection layer and a hole transport layer. When the hole function layer includes a hole transport layer and a hole injection layer arranged in a stack, the hole function layer The transport layer is close to the light-emitting layer, and the hole injection layer is close to the anode;
    所述空穴传输层的材料选自NiO、WO 3、MoO 3、CuO、聚(9,9-二辛基芴-CO-N-(4-丁基苯基)二苯胺)、3-己基取代聚噻吩、聚(9-乙烯咔唑)、聚[双(4-苯基)(4-丁基苯基)胺]、聚(N,N'-二(4-丁基苯基)-N,N'-二苯基-1,4-苯二胺-CO-9,9-二辛基芴)、4,4',4”-三(咔唑-9-基)三苯胺、4,4'-二(9-咔唑)联苯、N,N'-二苯基-N,N'-二(3-甲基苯基)-1,1'-联苯-4,4'-二胺以及N,N'-二苯基-N,N'-(1-萘基)-1,1'-联苯-4,4'-二胺的一种或多种； The material of the hole transport layer is selected from NiO, WO 3 , MoO 3 , CuO, poly(9,9-dioctylfluorene-CO-N-(4-butylphenyl)diphenylamine), 3-hexyl Substituted polythiophene, poly(9-vinylcarbazole), poly[bis(4-phenyl)(4-butylphenyl)amine], poly(N,N'-bis(4-butylphenyl)- N,N'-diphenyl-1,4-phenylenediamine-CO-9,9-dioctylfluorene), 4,4',4″-tris(carbazol-9-yl)triphenylamine, 4 ,4'-bis(9-carbazole)biphenyl, N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4' - One or more diamines and N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine;
    所述空穴注入层的材料选自聚(3,4-乙烯二氧基噻吩)：聚(苯乙烯磺酸)、酞菁铜、2,3,5,6-四氟-7,7',8,8'-四氰二甲基对苯醌、2,3,6,7,10,11-六氰基-1,4,5,8,9,12-六氮杂苯并菲、过渡金属氧化物以及过渡金属硫系化合物中的一种或多种，其中，所述过渡金属氧化物选自NiO x、MoO x、WO x以及CrO x中的一种或多种，所述过渡金属硫系化合物选自MoS x、MoSe x、WS x、WSe x以及CuS中的一种或多种。 The material of the hole injection layer is selected from poly(3,4-ethylenedioxythiophene): poly(styrenesulfonic acid), copper phthalocyanine, 2,3,5,6-tetrafluoro-7,7',8,8'-tetracyanodimethylp-benzoquinone, 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazabenzophenanthrene, One or more of transition metal oxides and transition metal chalcogenide compounds, wherein the transition metal oxide is selected from one or more of NiO x , MoO x , WO x and CrO x , and the transition metal oxide The metal chalcogenide compound is selected from one or more of MoS x , MoS x , WS x , WSe x and CuS.
  9. 一种发光器件的制备方法，其中，所述制备方法包括如下步骤：A method for preparing a light-emitting device, wherein the preparation method includes the following steps:
    提供叠层结构，在所述叠层结构的一侧施加包含第一化合物和第二化合物的混合液，干燥处理获得电子传输层；Provide a laminated structure, apply a mixed solution containing a first compound and a second compound on one side of the laminated structure, and dry it to obtain an electron transport layer;
    其中，所述第一化合物为纳米金属氧化物，所述第二化合物为形核剂；Wherein, the first compound is a nanometal oxide, and the second compound is a nucleating agent;
    当所述发光器件为正置型结构时，所述叠层结构为包含阳极和发光层的基板，所述电子传输层形成于所述发光层远离所述阳极的一侧；When the light-emitting device has an upright structure, the stacked structure is a substrate including an anode and a light-emitting layer, and the electron transport layer is formed on the side of the light-emitting layer away from the anode;
    当所述发光器件为倒置型结构时，所述叠层结构为包含阴极的基板，所述电子传输层形成于所述阴极的一侧。When the light-emitting device has an inverted structure, the stacked structure is a substrate including a cathode, and the electron transport layer is formed on one side of the cathode.
  10. 根据权利要求9所述的制备方法，其中，所述第一化合物选自ZnO、TiO 2、SnO 2、BaO、Ta 2O 3、ZrO 2、TiLiO、ZnGaO、ZnAlO、ZnMgO、ZnSnO、ZnLiO、InSnO、AlZnO、ZnOCl或ZnOF中的至少一种。 The preparation method according to claim 9, wherein the first compound is selected from the group consisting of ZnO, TiO 2 , SnO 2 , BaO, Ta 2 O 3 , ZrO 2 , TiLiO, ZnGaO, ZnAlO, ZnMgO, ZnSnO, ZnLiO, InSnO , AlZnO, ZnOCl or at least one of ZnOF.
  11. 根据权利要求9或10所述的制备方法，其中，所述第一化合物的平 均粒径为2nm至15nm。The preparation method according to claim 9 or 10, wherein the average particle size of the first compound is 2 nm to 15 nm.
  12. 根据权利要求9至11任一项中所述的制备方法，其中，所述形核剂选自有机形核剂以及无机形核剂中的一种或多种；The preparation method according to any one of claims 9 to 11, wherein the nucleating agent is selected from one or more of organic nucleating agents and inorganic nucleating agents;
    其中，所述有机形核剂选自羧酸金属盐类化合物、山梨醇类化合物、聚合物形核剂以及β晶型形核剂中的一种或多种；所述羧酸金属盐类化合物选自琥珀酸钠、戊二酸钠、己酸钠、4-甲基戊酸钠、己二酸、己二酸铝、特丁基苯甲酸铝、苯甲酸铝、苯甲酸钾、苯甲酸锂、肉桂酸钠以及β-萘甲酸钠中的一种或多种；所述山梨醇类化合物选自二苄叉山梨醇、二(对一甲基苄叉)山梨醇以及二(对氯取代苄叉)山梨醇中的一种或多种；所述聚合物形核剂选自聚乙烯基环己烷、聚乙烯戊烷以及乙烯/丙烯酸酯共聚物中的一种或多种；所述β晶型形核剂选自β型聚丙烯；Wherein, the organic nucleating agent is selected from one or more of carboxylic acid metal salt compounds, sorbitol compounds, polymer nucleating agents and beta crystal nucleating agents; the carboxylic acid metal salt compound Selected from sodium succinate, sodium glutarate, sodium caproate, sodium 4-methylvalerate, adipic acid, aluminum adipate, tert-butyl aluminum benzoate, aluminum benzoate, potassium benzoate, lithium benzoate , sodium cinnamate and sodium β-naphthoate, one or more; the sorbitol compound is selected from dibenzyl sorbitol, di(p-monomethylbenzyl) sorbitol and di(p-chloro substituted benzyl sorbitol) ) one or more of sorbitol; the polymer nucleating agent is selected from one or more of polyvinylcyclohexane, polyethylene pentane and ethylene/acrylate copolymer; the β crystal Type nucleating agent is selected from β-type polypropylene;
    所述无机形核剂选自炭黑、氧化钙、云母、滑石粉以及高岭土中的一种或多种。The inorganic nucleating agent is selected from one or more types of carbon black, calcium oxide, mica, talc and kaolin.
  13. 根据权利要求9至12任一项中所述的制备方法，其中，在所述电子传输层中，所述第一化合物：所述第二化合物的摩尔比为1：(0.1～0.2)。The preparation method according to any one of claims 9 to 12, wherein in the electron transport layer, the molar ratio of the first compound: the second compound is 1: (0.1 to 0.2).
  14. 根据权利要求9至13任一项中所述的制备方法，其中，所述第二化合物为固体，且在所述混合液中，所述第一化合物：所述第二化合物的质量比为1：(0.02～0.05)。The preparation method according to any one of claims 9 to 13, wherein the second compound is a solid, and in the mixed liquid, the mass ratio of the first compound: the second compound is 1 (0.02～0.05).
  15. 根据权利要求9至13任一项中所述的制备方法，其中，所述第二化合物为液体，所述混合液的制备方法包括步骤：提供包含第一化合物的溶液，将所述第二化合物与所述包含第一化合物的溶液混合制得所述混合液；The preparation method according to any one of claims 9 to 13, wherein the second compound is a liquid, and the preparation method of the mixed liquid includes the steps of: providing a solution containing the first compound, and adding the second compound Mix with the solution containing the first compound to prepare the mixed solution;
    其中，在所述包含第一化合物的溶液中，所述第一化合物的浓度为30mg/mL至60mg/mL；Wherein, in the solution containing the first compound, the concentration of the first compound is 30 mg/mL to 60 mg/mL;
    所述包含第一化合物的溶液：所述第二化合物的体积比为1：(0.01～0.0125)。The volume ratio of the solution containing the first compound: the second compound is 1: (0.01~0.0125).
  16. 根据权利要求9至15任一项中所述的制备方法，其中，所述在所述叠层结构的一侧施加包含第一化合物和第二化合物的混合液，包括步骤：提供包含第一化合物和第二化合物的混合液，将所述混合液置于交流电场处理预设时间。The preparation method according to any one of claims 9 to 15, wherein applying a mixed liquid containing the first compound and the second compound on one side of the laminated structure includes the step of: providing a liquid containing the first compound. and a second compound, and subject the mixed liquid to an alternating current electric field for a preset time.
  17. 根据权利要求16所述的制备方法，其中，所述交流电场的强度为100v/m至500v/m，所述交流电场的频率为50Hz至100Hz，所述交流电场的有效电压值为100V至200V。The preparation method according to claim 16, wherein the intensity of the AC electric field is 100v/m to 500v/m, the frequency of the AC electric field is 50Hz to 100Hz, and the effective voltage value of the AC electric field is 100V to 200V .
  18. 根据权利要求16或17所述的制备方法，其中，所述预设时间为1min至5min。The preparation method according to claim 16 or 17, wherein the preset time is 1 min to 5 min.
  19. 一种显示装置，其中，所述显示装置包括发光器件，所述发光器件包括：A display device, wherein the display device includes a light-emitting device, and the light-emitting device includes:
    阳极；anode;
    阴极，与所述阳极相对设置；The cathode is arranged opposite to the anode;
    发光层，设置于所述阳极与所述阴极之间；以及a light-emitting layer disposed between the anode and the cathode; and
    电子传输层，设置于所述阴极与所述发光层之间；An electron transport layer is provided between the cathode and the light-emitting layer;
    其中，所述电子传输层的材料包括第一化合物和第二化合物，所述第一化合物为纳米金属氧化物，所述第二化合物为形核剂。Wherein, the material of the electron transport layer includes a first compound and a second compound, the first compound is a nanometal oxide, and the second compound is a nucleating agent.
  20. 根据权利要求19所述的显示装置，其中，所述第一化合物选自ZnO、TiO 2、SnO 2、BaO、Ta 2O 3、ZrO 2、TiLiO、ZnGaO、ZnAlO、ZnMgO、ZnSnO、ZnLiO、InSnO、AlZnO、ZnOCl或ZnOF中的至少一种； The display device of claim 19, wherein the first compound is selected from the group consisting of ZnO, TiO2 , SnO2 , BaO, Ta2O3 , ZrO2 , TiLiO, ZnGaO, ZnAlO, ZnMgO, ZnSnO, ZnLiO, InSnO , at least one of AlZnO, ZnOCl or ZnOF;
    所述形核剂选自有机形核剂以及无机形核剂中的一种或多种；所述有机形核剂选自羧酸金属盐类化合物、山梨醇类化合物、聚合物形核剂以及β晶型形核剂中的一种或多种，所述羧酸金属盐类化合物选自琥珀酸钠、戊二酸钠、己酸钠、4-甲基戊酸钠、己二酸、己二酸铝、特丁基苯甲酸铝、苯甲酸铝、苯甲酸钾、苯甲酸锂、肉桂酸钠以及β-萘甲酸钠中的一种或多种，所述山梨醇类化合物选自二苄叉山梨醇、二(对一甲基苄叉)山梨醇以及二(对氯取代苄叉)山梨醇中的一种或多种，所述聚合物形核剂选自聚乙烯基环己烷、聚乙烯戊烷以及乙烯/丙烯酸酯共聚物中的一种或多种，所述β晶型形核剂选自β型聚丙烯；所述无机形核剂选自炭黑、氧化钙、云母、滑石粉以及高岭土中的一种或多种；The nucleating agent is selected from one or more organic nucleating agents and inorganic nucleating agents; the organic nucleating agent is selected from carboxylic acid metal salt compounds, sorbitol compounds, polymer nucleating agents, and One or more beta crystal nucleating agents, the carboxylic acid metal salt compound is selected from the group consisting of sodium succinate, sodium glutarate, sodium hexanoate, sodium 4-methylvalerate, adipic acid, and adipic acid. One or more of aluminum diphosphate, tert-butyl aluminum benzoate, aluminum benzoate, potassium benzoate, lithium benzoate, sodium cinnamate and sodium β-naphthoate, and the sorbitol compound is selected from dibenzylidene One or more of sorbitol, di(p-monomethylbenzyl) sorbitol and di(p-chlorosubstituted benzylidene) sorbitol, the polymer nucleating agent is selected from polyvinylcyclohexane, poly One or more of ethylene pentane and ethylene/acrylate copolymer, the β crystalline nucleating agent is selected from β-type polypropylene; the inorganic nucleating agent is selected from carbon black, calcium oxide, mica, talc One or more of powder and kaolin;
    在所述电子传输层中，所述第一化合物：所述第二化合物的摩尔比为1：(0.1～0.2)。In the electron transport layer, the molar ratio of the first compound:the second compound is 1: (0.1˜0.2).
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