WO2023197659A1 - Manufacturing method for light emitting device, light emitting device, and display apparatus - Google Patents

Manufacturing method for light emitting device, light emitting device, and display apparatus Download PDF

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Publication number
WO2023197659A1
WO2023197659A1 PCT/CN2022/140059 CN2022140059W WO2023197659A1 WO 2023197659 A1 WO2023197659 A1 WO 2023197659A1 CN 2022140059 W CN2022140059 W CN 2022140059W WO 2023197659 A1 WO2023197659 A1 WO 2023197659A1
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Prior art keywords
treatment
light
layer
emitting device
annealing treatment
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PCT/CN2022/140059
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French (fr)
Chinese (zh)
Inventor
马兴远
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Tcl科技集团股份有限公司
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Priority claimed from CN202210393991.9A external-priority patent/CN116981310A/en
Priority claimed from CN202210394651.8A external-priority patent/CN116981311A/en
Application filed by Tcl科技集团股份有限公司 filed Critical Tcl科技集团股份有限公司
Publication of WO2023197659A1 publication Critical patent/WO2023197659A1/en

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting layers

Definitions

  • the present application relates to the field of optoelectronic technology, and specifically to a method for preparing a light-emitting device, a 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.
  • the present application provides a method for preparing a light-emitting device, a light-emitting device and a display device to improve the photoelectric performance and stability of the light-emitting device.
  • this application provides a method for preparing a light-emitting device, which method includes the following steps:
  • the solution located on one side of the prefabricated device is annealed and electrically treated to form an electron transport layer;
  • the prefabricated device when the light-emitting device has a positive structure, includes a bottom electrode and a light-emitting layer arranged in a stack, and the solution is applied to the side of the light-emitting layer away from the bottom electrode, and the bottom electrode is anode;
  • the prefabricated device includes a bottom electrode, the solution is applied to one side of the bottom electrode, and the bottom electrode is a cathode.
  • the time period of the annealing treatment at least partially overlaps the time period of the electrical treatment
  • the annealing treatment method and the electrical treatment method are any of the following:
  • the annealing treatment is intermittent, and the electrical treatment is intermittent.
  • the time period of the annealing treatment does not overlap with the time period of the electrical treatment
  • the annealing treatment method and the electrical treatment method are any of the following:
  • the temperature of the annealing treatment is 80°C to 250°C;
  • the time of the annealing treatment is 5 min to 120 min.
  • the electrical treatment is a charging treatment, and the charging treatment is to make the electron transport precursor layer carry positive charge or negative charge, or to make the electron transport precursor layer carry positive charge and negative charge alternately.
  • the charging process includes the steps of: providing an external power supply, a first end of the external power supply is connected to the bottom electrode, and a second end of the external power supply is grounded; turning on the external power supply so that the There is a potential difference between the first end and the second end.
  • the external power supply applies a constant voltage or an alternating voltage to the electron transport precursor layer
  • the voltage value of the constant voltage is 10V to 30V;
  • the frequency of the AC voltage is 10Hz to 200Hz, and the effective voltage is 10V to 30V.
  • the charging treatment time is 5 min to 120 min;
  • the charging treatment is continuous; or, the charging treatment is intermittent, the time of a single charging treatment is 5 min to 20 min, and the interval between adjacent charging treatments is 5 min to 20 min.
  • the overlap time of the annealing process and the charging process is any of the following situations:
  • the annealing treatment is intermittent and the charging treatment is continuous, the interval between adjacent annealing treatments is 5 min to 10 min, and the time for a single annealing treatment is 10 min to 30 min. , the overlap time of the annealing treatment and the charging treatment is 5min to 115min;
  • the annealing treatment is intermittent and the charging treatment is intermittent
  • the interval between adjacent annealing treatments is 5 min to 10 min
  • the time for a single annealing treatment is 10 min to 30 min.
  • the overlap time of the annealing treatment and the charging treatment is 5min to 115min.
  • the electrical treatment is an electrification treatment
  • the electrification treatment is to connect the solution between the cathode and the anode of an external power supply to form a closed loop.
  • the electrification process includes the steps of: fixing the prefabricated device containing the solution on a fixture, and then connecting the anode and cathode of an external power supply to opposite sides of the wet film formed by the solution. connected.
  • the energization treatment is a constant current energization treatment, a constant voltage energization treatment or an alternating energization treatment;
  • the current density of the solution located on one side of the prefabricated device is 100 mA/cm 2 to 300 mA/cm 2 .
  • the time period of the annealing process and the time period of the electrification process at least partially overlap, and the processing time of the annealing process and the electrification process is any one of the following situations:
  • the annealing treatment is intermittent, and when the energization treatment is intermittent, the interval between adjacent annealing treatments is 5 min to 20 min, and the time for a single annealing treatment is 5 min to 20 min; The interval time between adjacent energization treatments is 5 min to 20 min, and the time of a single energization treatment is 5 min to 20 min.
  • the total time of the energization treatment is 5 min to 120 min, and the total overlap time of the annealing treatment and the energization treatment is 5 min to 120 min.
  • the annealing treatment and the electrification treatment are performed alternately;
  • the total time of the annealing treatment is 5min to 60min, and the total time of the energization treatment is 5min to 60min; the time of a single energization treatment is 5min to 20min, and the time of a single annealing treatment is 5min to 20min.
  • the preparation method further includes the step of: after forming an electron transport layer on the side of the prefabricated device, moving the electron transport layer away from the light-emitting layer One side forms the cathode;
  • the preparation method further includes the following steps:
  • An anode is formed on a side of the light-emitting layer away from the electron transport layer.
  • the preparation method further includes the step of: forming a hole functional layer between the anode and the light-emitting layer, the hole functional layer including one of a hole injection layer and a hole transport layer, or Various, when the hole functional 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 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 transition metal oxides and transition metal chalcogenide compounds the transition metal oxide is selected from one or more NiO x , MoO x , WO x and CrO x , the transition metal sulfur
  • the system compound is selected from one or more of MoS x , MoS x , WS x , WSe x and CuS.
  • the present application provides a light-emitting device.
  • the preparation method of the light-emitting device includes the following steps:
  • the prefabricated device when the light-emitting device has a positive structure, includes a bottom electrode and a light-emitting layer arranged in a stack, and the solution is applied to the side of the light-emitting layer away from the bottom electrode, and the bottom electrode is anode;
  • the prefabricated device includes a bottom electrode, the solution is applied to one side of the bottom electrode, and the bottom electrode is a cathode.
  • the material of the light-emitting layer is an organic light-emitting material or quantum dots
  • the organic light-emitting material is selected from one of diarylanthracene derivatives, stilbene aromatic derivatives, pyrene derivatives, fluorene derivatives, TBPe fluorescent materials, TTPA fluorescent materials, TBRb fluorescent materials and DBP fluorescent materials, or variety;
  • the quantum dots are selected from one or more of single component quantum dots, core-shell structure quantum dots, inorganic perovskite quantum dots, and organic-inorganic hybrid perovskite quantum dots; when the quantum dots are selected from In the case of single-component quantum dots or core-shell structure quantum dots, the material of the single-component quantum dot, the material of the core of the core-shell structure quantum dot, and the material of the shell of the core-shell structure quantum dot are selected independently of each other.
  • Group II-VI compounds Group III-V compounds, Group IV-VI compounds and Group I-III-VI compounds
  • the Group 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, HgZnSe ,HgZnTe , one or more of CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, CdHg
  • 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 present application provides a display device.
  • the display device includes a light-emitting device.
  • the preparation method of the light-emitting device includes the following steps:
  • the prefabricated device when the light-emitting device has a positive structure, includes a bottom electrode and a light-emitting layer arranged in a stack, and the solution is applied to the side of the light-emitting layer away from the bottom electrode, and the bottom electrode is anode;
  • the prefabricated device includes a bottom electrode, the solution is applied to one side of the bottom electrode, and the bottom electrode is a cathode.
  • the electrical treatment is any of the following:
  • the electrical treatment is a charging treatment, which causes the electron transport precursor layer to carry positive charges or negative charges, or causes the electron transport precursor layer to alternately carry positive charges and negative charges;
  • the electrical treatment is an electrification treatment, in which the solution is connected between the cathode and the anode of an external power supply to form a closed loop.
  • Figure 1 is a schematic flow chart of a method for preparing a light-emitting device provided by the present application
  • Figure 2 is a schematic flow chart of a method for manufacturing a light-emitting device according to some embodiments of the present application
  • Figure 3 is a schematic flow chart of another method for preparing a light-emitting device according to some embodiments of the present application.
  • FIG. 4 is a schematic structural diagram of a first light-emitting device provided by an embodiment of the present application.
  • FIG. 5 is a schematic structural diagram of a second light-emitting device provided by an embodiment of the present application.
  • FIG. 6 is a schematic structural diagram of a third light-emitting device provided by an embodiment of the present application.
  • Embodiments of the present application provide a method for preparing a light-emitting device, a light-emitting device and a display device. 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 terms “at least one” and “any one of the following situations” refer 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.
  • an electron transport layer is usually provided between the cathode and the light-emitting layer.
  • Metal oxide nanoparticles are one of the materials used to prepare the electron transport layer.
  • Nano-metal oxides have the characteristics of high electron mobility and wide bandgap.
  • defect states on the surface of nano-metal oxides which makes the stability of nano-metal oxides not ideal, and the external environmental conditions have a negative impact on nano-metal oxidation.
  • the defect density and conductive properties of the object have a great impact, which leads to large fluctuations in the performance of the electron transport layer, which in turn adversely affects the photoelectric performance and working life of the light-emitting device. Therefore, how to improve the performance stability of electron transport layers containing nanometal oxides is of great significance to the application and development of light-emitting devices.
  • the embodiment of the present application provides a method for preparing a light-emitting device, as shown in Figure 1.
  • the preparation method includes the following steps:
  • the prefabricated device when the light-emitting device has a positive structure, includes a bottom electrode and a light-emitting layer arranged in a stack, and the solution is applied to the side of the light-emitting layer away from the bottom electrode, and the bottom electrode is anode;
  • the prefabricated device includes a bottom electrode, the solution is applied to one side of the bottom electrode, and the bottom electrode is a cathode.
  • the time period of the annealing treatment and the time period of the electrical treatment at least partially overlap, and the annealing treatment method and the electrical treatment method are any of the following situations:
  • the annealing treatment is intermittent, and the electrical treatment is intermittent.
  • the time period of the annealing treatment and the time period of the electrical treatment do not overlap, and the annealing treatment method and the electrical treatment method are any of the following situations:
  • a method for preparing a light-emitting device includes the following steps:
  • annealing treatment includes all steps that can enable the solution located on one side of the prefabricated device to obtain higher energy and remove at least part of the solvent, including but not limited to isothermal heat treatment Process or non-isothermal heat treatment (for example, temperature changes in a gradient) process.
  • annealing treatment refers to constant temperature heat treatment at 80°C to 250°C for 5 minutes to 120 minutes.
  • the temperature of the annealing treatment can be, for example, Is 80°C to 100°C, 100°C to 120°C, 120°C to 140°C, 140°C to 160°C, 160°C to 180°C, 180°C to 200°C, 200°C to 220°C, 220°C to 240°C, or 240°C to 250°C
  • the annealing treatment time can be, for example, 5min to 10min, 10min to 20min, 20min to 30min, 30min to 40min, 40min to 50min, 50min to 60min, 60min to 70min, 70min to 80min, 80min to 90min, 90min to 100min, 100min to 110min, or 110min to 120min.
  • the solution located on one side of the prefabricated device can form a film layer in a wet film state or a dry film state after annealing treatment.
  • “energization treatment” is to connect a solution containing nanometal oxides between the cathode and anode of an external power supply to form a closed loop.
  • the solution is equivalent to the resistance in the closed loop.
  • the embodiments of this application are for external
  • the type and model of the power supply are not specifically limited, and can be selected according to the scale of different light-emitting devices. It should be noted that the solution can only be connected between the cathode and the anode of the external power supply, or the prefabricated device including the solution can be connected between the cathode and the anode of the external power supply.
  • the "power treatment” includes the steps of: fixing the prefabricated device including the solution on a fixture, and then placing the anode and cathode of the external power supply opposite to the wet film formed by the solution. The two sides of the setting are connected.
  • the temperature of the heat treatment should not be too high to avoid Causes damage to the light-emitting layer and other functional layers, so the nanometal oxide cannot be completely annealed, resulting in the inability to fully remove the ligands located on the surface of the nanometal oxide, thus failing to effectively shorten the gap between adjacent nanoparticles. Therefore, in the formed film layer, the nanocrystal array formed by the nanometal oxide has the characteristics of loose arrangement, and the film layer has the problem of low density.
  • the gap between adjacent nanoparticles forms a potential barrier for electronic conduction, and the nanometal oxide itself has a large specific surface area and relatively active properties, resulting in poor conductivity of the film layer made of nanometal oxide. ideal and less stable.
  • the technical means of "annealing and electrifying the solution within a preset time range" is adopted to promote film formation of the solution under the action of electric energy and high temperature.
  • the electron transport layer (the material of the electron transport layer is nanometer metal oxide) of the light-emitting device in this application is more dense, that is, adjacent nanometer The gaps between particles are smaller, making the electron transport layer more conductive and stable, so that the overall performance of the light-emitting device in this application is better.
  • the annealing treatment and the electrification treatment are carried out in an inert gas atmosphere.
  • "Inert gas” refers to a gas that is chemically inactive, does not react with the electron transport precursor layer and other functional layers, and has the characteristics of isolating oxygen and water.
  • Gas-like, inert gas for example, is selected from at least one of nitrogen, helium, neon, argon, krypton or xenon.
  • the application method of the solution containing nanometal oxides includes but is not limited to spin coating, coating, inkjet printing, blade coating, dipping and pulling, soaking, spraying, roller coating or casting. at least one of them.
  • the prefabricated device includes a stacked anode and a light-emitting layer, and the solution is applied to the side of the light-emitting layer away from the anode.
  • the prefabricated device consists of a substrate, an anode, and anode that are stacked in sequence. and a light-emitting layer.
  • the prefabricated device consists of a substrate, anode, a hole functional layer and a light-emitting layer that are stacked in sequence; when the light-emitting device has an inverted structure, the prefabricated device includes a cathode, and the solution is applied to the cathode.
  • a prefabricated device consists of a substrate and a cathode arranged in a stack, and the solution is applied to the side of the cathode away from the substrate.
  • the nanometal oxide may be an undoped nanometal oxide or a doped nanometal oxide.
  • the nanometal oxide 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 size of the nanometal oxide can be, for example, 2nm to 15nm.
  • the average particle size of the nanometal oxide can be, for example, 2nm to 4nm, 2nm to 6nm, 2nm to 8nm, 2nm to 10nm, 4nm to 10nm, or 10nm to 15nm.
  • the average particle size of the nanometal oxide may be, for example, 5 nm, 6 nm, 7 nm, 8 nm, 9 nm, or 10 nm.
  • the solution containing nanometal oxides can be, for example, a product containing nanometal oxides prepared by a solution method, wherein the solvents include but are not limited to water, ethanol, propanol, butanol, hexanol, n-octane, At least one of n-hexane or ethylene glycol monomethyl ether.
  • the "preset time range” refers to the time range set by the operator. This time range can be obtained by repeated experiments multiple times, and the time range will be different depending on the type of the light-emitting device. In some embodiments of the present application, the “preset time range” refers to 5 minutes to 120 minutes.
  • the electrification treatment is a constant current electrification treatment, a constant voltage electrification treatment or an alternating electrification treatment; during the electrification treatment, the current density of the solution located on one side of the prefabricated device It is 100mA/cm 2 to 300mA/cm 2 , for example, it can be 100mA/cm 2 to 150mA/cm 2 , 150mA/cm 2 to 200mA/cm 2 , 200mA/cm 2 to 250mA/cm 2 , or 250mA/cm 2 to 300mA/cm 2 .
  • the time period of the annealing process and the time period of the power-on process at least partially overlap.
  • the annealing process is continuous, and the energization process is continuous. It can be understood that the time period of the annealing process and the time period of the energization process may only partially overlap or may completely overlap.
  • the annealing process is continuous, and the power-on process is intermittent.
  • the interval time between adjacent energization treatments can be 5min to 10min, and the time of a single energization treatment can be 10min to 15min.
  • the interval time between adjacent energization treatments can be, for example, 5min to 6min, 6min to 7min, 7min to 8min, 8min to 9min. , or 9min to 10min.
  • the time of a single power-on treatment may be, for example, 10min to 11min, 11min to 12min, 12min to 13min, 13min to 14min, or 14min to 15min.
  • the annealing process is intermittent, and the energization process is continuous.
  • the interval time of adjacent annealing treatments is 5min to 10min
  • the time of a single annealing treatment is 10min to 30min.
  • the interval time of adjacent annealing treatments can be, for example, 5min to 6min, 6min to 7min, 7min to 8min, 8min to 9min, or 9min to 10min.
  • the time of a single annealing treatment may be, for example, 10min to 15min, 15min to 20min, 20min to 25min, or 25min to 30min.
  • the annealing treatment is intermittent, and the power-on treatment is intermittent.
  • the interval time between adjacent annealing treatments is 5 min to 20 min, and the time of a single annealing treatment is 5 min to 20 min;
  • the interval time of power treatment is 5min to 20min, and the time of single power treatment is 5min to 20min.
  • the total time of the annealing process is 5min to 120min
  • the total time of the energization process is 5min to 120min
  • the total overlap time of the annealing process and the energization process is 5min to 120min.
  • the total time of the annealing treatment can be, for example, 5min to 10min, 10min to 20min, 20min to 30min, 30min to 40min, 40min to 50min, 50min to 60min, 60min to 70min, 70min to 80min, 80min to 90min, 90min to 100min, 100min to 110min, or 110min to 120min
  • the total time of the energization treatment can be, for example, 5min to 10min, 10min to 20min, 20min to 30min, 30min to 40min, 40min to 50min, 50min to 60min, 60min to 70min, 70min to 80min, 80min to 90min , 90min to 100min, 100min to 110min, or 110min to 120min.
  • the total overlap time of the annealing treatment and the energization treatment can be, for example, 5min to 10min, 10min to 20min, 20min to 30min, 30min to 40min, 40min to 50min, 50min to 60min, 60min to 70min, 70min to 80min, 80min to 90min, 90min to 100min, 100min to 110min, or 110min to 120min.
  • the annealing process is alternated with the energization process.
  • the total time of the annealing treatment is 5min to 60min
  • the total time of the energization treatment is 5min to 60min.
  • the total time of the annealing treatment is, for example, 5min to 10min, 10min to 20min, 20min to 30min, 30min to 40min, 40min to 50min, Or 50min to 60min.
  • the total time of the energization treatment is, for example, 5min to 10min, 10min to 20min, 20min to 30min, 30min to 40min, 40min to 50min, or 50min to 60min.
  • the time of a single energization treatment is 5min to 20min
  • the time of a single annealing treatment is 5min to 20min
  • the time of a single energization treatment is, for example, 5min to 8min, 8min to 10min, 10min to 15min, or 15min to 20min
  • the time of a single annealing treatment is, for example, 5 min to 8 min, 8 min to 10 min, 10 min to 15 min, or 15 min to 20 min.
  • the preparation method when the light-emitting device has an upright structure, the preparation method further includes the step of: after forming an electron transport layer on the side of the prefabricated device, preparing a side of the electron transport layer away from the light-emitting layer. form the cathode.
  • the prefabricated device when the light-emitting device has a positive structure, the prefabricated device can be a stacked structure including an anode, a hole functional layer and a light-emitting layer. Therefore, the preparation method further includes the step of: providing an anode, one side of the anode.
  • the hole functional layer and the light-emitting layer are sequentially prepared on the side, wherein the hole functional layer includes a hole transport layer and/or a hole injection layer.
  • the hole functional layer includes a hole transport layer and a hole injection layer
  • the hole injection layer The layer is close to the anode, and the hole transport layer is close to the light-emitting layer.
  • the preparation method further includes the following steps:
  • the preparation method further includes the following steps:
  • a light-emitting layer is formed on the side of the electron transport layer away from the cathode.
  • An anode is prepared on the side of the light-emitting layer away from the electron transport layer.
  • the preparation method further includes the steps of: forming a hole function layer between the anode and the light-emitting layer, the hole function layer including 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
  • the hole injection layer is close to the anode.
  • forming the hole functional layer between the anode and the light-emitting layer means first preparing and forming the hole functional layer on the side of the light-emitting layer away from the electron transport layer, and then forming the hole functional layer on the side far from the light-emitting layer.
  • An anode is prepared and formed; in addition, when the hole functional layer includes a hole injection layer and a hole transport layer, a hole transport layer, a hole injection layer and a light-emitting layer are sequentially prepared on the side of the light-emitting layer away from the electron transport layer.
  • the preparation method includes the following steps:
  • a method for preparing a light-emitting device includes the following steps:
  • the electron transport precursor layer can be in a wet film state, and the electron transport precursor layer can also be in a dry film state.
  • the electron transport precursor layer can be a solution containing nanometal oxides applied to the prefabricated device.
  • the wet film formed on one side of the prefabricated device the electron transport precursor layer may be a dry film layer obtained by drying the wet film formed by applying a solution containing nanometal oxides to one side of the prefabricated device.
  • the preparation method may also include other processing steps, for example: when the electron transport precursor layer is a wet film, the electron transport precursor layer is subjected to a charging process. Afterwards, the preparation method may further include a drying process to obtain the electron transport layer in a dry film state.
  • the electron transport precursor layer is prepared from a solution containing nanometal oxides. If the electron transport precursor layer is only dried to form the electron transport layer, the temperature of the drying process should not be too high to avoid damage to the light-emitting layer and other functional layers. Causes damage, therefore, the ligands located on the surface of the nanometal oxide cannot be sufficiently removed, so that the gap between adjacent nanoparticles cannot be effectively shortened, so that in the formed electron transport layer, the nanocrystals formed by the nanometal oxide The array has the characteristics of loose arrangement, which leads to the problem of low density of the electron transport layer.
  • the gap between adjacent nanoparticles forms a potential barrier for electron conduction, and the nanometal oxide itself has a large specific surface area and relatively active properties, resulting in unsatisfactory conductivity of the electron transport layer made of nanometal oxide. , and the stability is poor.
  • the technical means of "charging the electron transport precursor layer” is used to cause the ligands connected to the surface of the nanometal oxide to fall off under the action of electrical energy and high temperature, thereby shortening the adjacent
  • the gaps between nanoparticles can thereby improve the crystallinity, conductivity and stability of the electron transport layer, which is beneficial to improving the photoelectric performance and working life of the light-emitting device.
  • the application method of the solution containing nanometal oxides includes but is not limited to spin coating, coating, inkjet printing, blade coating, dipping and pulling, soaking, spraying, roller coating or casting. at least one of them.
  • the prefabricated device includes a stacked bottom electrode and a light-emitting layer.
  • the electron transport precursor layer is formed on the side of the light-emitting layer away from the bottom electrode.
  • the bottom electrode is an anode.
  • the prefabricated device is composed of a stacked bottom electrode and a light-emitting layer. It consists of a substrate, anode and a light-emitting layer.
  • a prefabricated device consists of a substrate, anode, a hole functional layer and a light-emitting layer that are stacked in sequence; when the light-emitting device has an inverted structure, the prefabricated device includes a bottom electrode for electron transmission.
  • the precursor layer is formed on one side of the bottom electrode, which is the cathode.
  • a prefabricated device consists of a stacked substrate and a cathode, and the electron transport precursor layer is formed on the side of the cathode away from the substrate.
  • the nanometal oxide may be an undoped nanometal oxide or a doped nanometal oxide.
  • the nanometal oxide 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 size of the nanometal oxide can be, for example, 2nm to 15nm.
  • the average particle size of the nanometal oxide can be, for example, 2nm to 4nm, 2nm to 6nm, 2nm to 8nm, 2nm to 10nm, 4nm to 10nm, or 10nm to 15nm.
  • the average particle size of the nanometal oxide may be, for example, 5 nm, 6 nm, 7 nm, 8 nm, 9 nm, or 10 nm.
  • the solution containing nanometal oxides can be, for example, a product containing nanometal oxides prepared by a solution method, wherein the solvents include but are not limited to water, ethanol, propanol, butanol, hexanol, n-octane, At least one of n-hexane or ethylene glycol monomethyl ether.
  • the charging process is performed within a preset time range.
  • the “preset time range” refers to the time range set by the operator. This time range can be obtained by repeated experiments multiple times, and the light emitting This time range will vary depending on the type of device.
  • the time of the charging treatment is 5min to 120min.
  • the time of the charging treatment can be, for example, 5min to 10min, 10min to 20min, 20min to 30min, 30min to 40min, 40min to 50min, 50min to 60min, 60min. to 70min, 70min to 80min, 80min to 90min, 90min to 100min, 100min to 110min, or 110min to 120min.
  • the charging treatment can be continuous, or the charging treatment can be intermittent.
  • the charging treatment is intermittent, the time of a single charging treatment is 5min to 20min, the interval time between adjacent charging treatments is 5min to 20min, and the time of a single charging treatment is 5min to 20min.
  • the treatment time can be, for example, 5min to 8min, 8min to 10min, 10min to 15min, or 15min to 20min, and the interval time between adjacent charging treatments can be, for example, 5min to 8min, 8min to 10min, 10min to 12min, 12min to 15min, or 15min to 20min.
  • charging treatment includes all processes that can make the electron transport precursor layer carry positive or negative charges, or make the electron transport precursor layer alternately carry positive charges and negative charges. It can be understood that , the charging treatment can make only the electron transport precursor layer carry a charge, it can also make the entire prefabricated device containing the electron transport precursor layer carry a charge, or it can make some layers (including the electron transport precursor layer) in the prefabricated device containing the electron transport precursor layer carry a charge. Carry charge.
  • the charging process includes the steps of: providing an external power supply, the first end of the external power supply is connected to the bottom electrode, and the second end of the external power supply is connected to ground, turning on the external power supply, connecting the first end to the second section There is a potential difference between them, so that the entire prefabricated device including the electron transport precursor layer carries positive or negative charges, or the entire prefabricated device including the electron transport precursor layer alternately carries positive charges and negative charges.
  • the embodiment of the present application does not specifically limit the type and model of the external power supply, and it can be selected according to the scale of different light-emitting devices.
  • the "charged treatment” includes the steps of: fixing the prefabricated device containing the electron transport precursor layer on the fixture, and then connecting the first end of the external power supply to the bottom electrode located on one side of the prefabricated device, And connect the second terminal of the external power supply to the ground, turn on the external power supply, and there will be a potential difference between the first terminal and the second terminal.
  • an external power supply applies a constant voltage or an alternating voltage to the electron transport precursor layer.
  • the first terminal can be the positive electrode and the second terminal can be the negative electrode, so that the entire prefabricated device including the electron transport precursor layer carries a positive charge; or the first electrode can be the negative electrode,
  • the second electrode is a positive electrode, so that the entire prefabricated device including the electron transport precursor layer carries a negative charge.
  • an external power supply applies an AC voltage to the electron transport precursor layer, the entire prefabricated device including the electron transport precursor layer alternately carries positive and negative charges.
  • the voltage value of the constant voltage is 10V to 30V.
  • the voltage value of the constant voltage is, for example, 10V to 15V, 15V to 20V, 20V to 25V, or 25V to 30V.
  • “voltage value” only refers to the specific magnitude of the voltage, but does not indicate the direction of the voltage. It can be understood that, under the premise that the charging treatment time is constant, the constant voltage value that is too high or too low will have limited effect on improving the overall performance of the light-emitting device. If the voltage value is too low, it will have a negative effect on the surface of the nanometal oxide.
  • the ligand removal effect is limited, so the gap between adjacent nanoparticles is limited, and the improvement effect on the conductivity and stability of the electron transport layer is limited; if the voltage value is too high, it may affect the organic functional layer and/or luminescence. layer causing some degree of damage.
  • the frequency of the AC voltage is 10Hz to 200Hz
  • the effective voltage value is 10V to 30V
  • the frequency of the AC voltage is, for example, 10Hz to 30Hz, 30Hz to 50Hz, 50Hz. to 80Hz, 80Hz to 100Hz, 100Hz to 120Hz, 120Hz to 150Hz, 150Hz to 180Hz, or 180Hz to 200Hz
  • the effective voltage value is, for example, 10V to 15V, 15V to 20V, 20V to 25V, or 25V to 30V.
  • the electron transport precursor layer is a wet film
  • the preparation method further includes the step of: annealing the electron transport precursor layer.
  • Annealing treatment includes all processes that can enable the electron transport precursor layer in the wet film state to obtain higher energy and remove at least part of the solvent, including but not limited to isothermal heat treatment processes or non-isothermal heat treatments (such as temperature gradient changes) Process, in some embodiments of the present application, “annealing treatment” refers to constant temperature heat treatment at 80°C to 250°C for 5 minutes to 120 minutes.
  • the temperature of the annealing treatment can be, for example, 80°C to 100°C, 100°C to 120°C, 120°C °C to 140 °C, 140 °C to 160 °C, 160 °C to 180 °C, 180 °C to 200 °C, 200 °C to 220 °C, 220 °C to 240 °C, or 240 °C to 250 °C
  • the annealing treatment time can be, for example, 5 minutes to 10min, 10min to 20min, 20min to 30min, 30min to 40min, 40min to 50min, 50min to 60min, 60min to 70min, 70min to 80min, 80min to 90min, 90min to 100min, 100min to 110min, or 110min to 120min.
  • the annealing treatment is continuous, and the charging treatment is continuous.
  • the overlap time of the annealing treatment and the charging treatment is 5 min to 120 min.
  • the overlap time of the annealing treatment and the charging treatment is, for example, 5 min to 120 min. 10min, 10min to 20min, 20min to 30min, 30min to 40min, 40min to 50min, 50min to 60min, 60min to 70min, 70min to 80min, 80min to 90min, 90min to 100min, 100min to 110min, or 110min to 120min.
  • the time of the annealing treatment is, for example, 5 min to 120 min
  • the temperature of the annealing treatment is, for example, 80°C to 250°C
  • the time of the charging treatment is, for example, 5 min to 120 min.
  • the annealing treatment is continuous, and the charging treatment is intermittent.
  • the overlap time of the annealing treatment and the charging treatment is 5 min to 115 min.
  • the overlap time of the annealing treatment and the charging treatment is, for example, 5 min to 115 min. 10min, 10min to 20min, 20min to 30min, 30min to 40min, 40min to 50min, 50min to 60min, 60min to 70min, 70min to 80min, 80min to 90min, 90min to 100min, 100min to 115min.
  • the time of the annealing treatment is, for example, 5min to 120min
  • the temperature of the annealing treatment is, for example, 80°C to 250°C
  • the time of the charging treatment is, for example, 5min to 120min
  • the time of a single charging treatment is, for example, 5min to 20min
  • the interval between adjacent charging treatments The time is, for example, 5 min to 20 min.
  • the annealing treatment is intermittent, and the charging treatment is continuous.
  • the interval between adjacent annealing treatments is 5 min to 10 min, and the time of a single annealing treatment is 10 min to 30 min.
  • the overlap time with the charging treatment is 5 min to 115 min, and the temperature of the annealing treatment is, for example, 80°C to 250°C.
  • the interval time of the annealing treatment is, for example, 5min to 6min, 6min to 7min, 7min to 8min, 8min to 9min, or 9min to 10min.
  • the time of a single annealing treatment is, for example, 10min to 15min, 15min to 20min, 20min to 25min, or 25min.
  • the overlap time of annealing treatment and charging treatment is, for example, 5min to 10min, 10min to 20min, 20min to 30min, 30min to 40min, 40min to 50min, 50min to 60min, 60min to 70min, 70min to 80min, 80min to 90min, 90min to 100min, 100min to 115min.
  • the charging treatment time is, for example, 5 min to 120 min.
  • the annealing treatment is intermittent, and the charging treatment is intermittent.
  • the interval between adjacent annealing treatments is 5 min to 10 min, and the time of a single annealing treatment is 10 min to 30 min.
  • the overlap time with the charging treatment is 5 min to 115 min, and the temperature of the annealing treatment is, for example, 80°C to 250°C.
  • the time of the charging treatment is, for example, 5 min to 120 min
  • the time of a single charging treatment is, for example, 5 min to 20 min
  • the interval time between adjacent charging treatments is, for example, 5 min to 20 min.
  • the time period of the annealing process does not overlap with the time period of the charging process.
  • annealing treatment and charging treatment are performed alternately. Both annealing treatment and charging treatment are intermittent.
  • the time of charging treatment is, for example, 5min to 120min.
  • the time of single charging treatment is, for example, 5min to 20min.
  • the time of annealing treatment is, for example, 5min. to 120 min, and the time of a single annealing treatment is, for example, 5 min to 20 min.
  • the charging treatment can be continuous or intermittent. In the same way, the annealing treatment can also be continuous or intermittent.
  • the charging treatment time is, for example, 5 min to 120 min, and the annealing treatment time is, for example, 5 min to 120 min.
  • the annealing treatment and charging treatment are carried out in an inert gas atmosphere.
  • “Inert gas” means that it is chemically inactive, does not react with the electron transport precursor layer and other functional layers, and has the ability to isolate oxygen and water.
  • the inert gas is, for example, at least one selected from nitrogen, helium, neon, argon, krypton or xenon.
  • the preparation method when the light-emitting device has a positive structure, the preparation method further includes the step of forming a top electrode on the side of the electron transport layer away from the light-emitting layer, and the top electrode is a cathode.
  • the prefabricated device when the light-emitting device has a positive structure, the prefabricated device can be a stacked structure including an anode, a hole functional layer and a light-emitting layer. Therefore, the preparation method further includes the step of: providing an anode, one side of the anode.
  • the hole functional layer and the light-emitting layer are sequentially prepared on the side, wherein the hole functional layer includes a hole transport layer and/or a hole injection layer.
  • the hole functional layer includes a hole transport layer and a hole injection layer
  • the hole injection layer The layer is close to the anode, and the hole transport layer is close to the light-emitting layer.
  • the preparation method includes the following steps:
  • S101 Provide a substrate, and prepare and form an anode on one side of the substrate;
  • the preparation method further includes the following steps:
  • a light-emitting layer is formed on a side of the electron transport layer away from the bottom electrode
  • a top electrode is prepared on the side of the light-emitting layer away from the electron transport layer, and the top electrode is the anode.
  • the preparation method further includes the steps of: forming a hole function layer between the anode and the light-emitting layer, the hole function layer including 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
  • the hole injection layer is close to the anode.
  • forming the hole functional layer between the anode and the light-emitting layer means first preparing and forming the hole functional layer on the side of the light-emitting layer away from the electron transport layer, and then forming the hole functional layer on the side far from the light-emitting layer.
  • An anode is prepared and formed; in addition, when the hole functional layer includes a hole injection layer and a hole transport layer, a hole transport layer, a hole injection layer and a light-emitting layer are sequentially prepared on the side of the light-emitting layer away from the electron transport layer.
  • the preparation method includes the following steps:
  • S101' provide a substrate, prepare and form a cathode on one side of the substrate;
  • 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, scraping, dipping, soaking, spraying, roller coating 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, electrolytic deposition method or co-precipitation method.
  • Physical methods include but are 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 pulsed laser deposition method.
  • thermal evaporation coating method electron beam evaporation coating method
  • magnetron sputtering method magnetron sputtering method
  • multi-arc ion coating method physical vapor deposition method
  • atomic layer deposition method or pulsed laser deposition method.
  • 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.
  • the embodiment of the present application also provides a light-emitting device.
  • the light-emitting device is produced by any one of the above preparation methods.
  • the light-emitting device 1 includes an anode 11, a cathode 12, a light-emitting layer 13 and an electron Transport layer 14, in which the anode 11 and the cathode 12 are arranged oppositely, the luminescent layer 13 is arranged between the anode 11 and the cathode 12, and the electron transport layer 14 is arranged between the cathode 12 and the luminescent layer 13.
  • the light-emitting device includes but is not limited to OLED or QLED, and the light-emitting device may have an upright structure, or the light-emitting device may also have an inverted structure.
  • the electron transport layer of the light-emitting device in the embodiment of the present application is denser, that is, the gap between adjacent nanoparticles is smaller, so that The electron transport layer has higher conductivity and stability, so that the overall performance of the light-emitting device in the embodiment of the present application is better.
  • 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 selected from organic light-emitting materials or quantum dots.
  • the thickness of the light-emitting layer 13 may be, for example, 20 nm to 60 nm.
  • Organic light-emitting materials include, but are not limited to, at least one of diarylanthracene derivatives, stilbene aromatic derivatives, pyrene derivatives, fluorene derivatives, TBPe fluorescent materials, TTPA fluorescent materials, TBRb fluorescent materials or DBP fluorescent materials. kind.
  • 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 material of the single-component quantum dot, the material of the core of the core-shell structure quantum dot, and the material of the shell of the core-shell structure quantum dot are independently selected from each other.
  • Group II-VI compounds At least one of Group II-VI compounds, Group III-V compounds, Group IV-VI compounds or Group I-III-VI compounds, wherein the Group II-VI compounds are selected from the group consisting of 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, At least one of CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSe
  • 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 further includes a hole function layer 15 , and the hole function layer 15 is disposed between 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 100 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 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.
  • Embodiments of the present application also provide a display device.
  • the display device includes a light-emitting device produced by any one of the preparation methods described in the embodiments of this application, or a light-emitting device described in any one of the embodiments of this application.
  • 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, televisions machine or e-book reader, wherein the smart wearable device can be, for example, a smart bracelet, a smart watch, a virtual reality (Virtual Reality, VR) helmet, etc.
  • VR Virtual Reality
  • This embodiment provides a method for preparing a light-emitting device and the prepared light-emitting device.
  • the preparation method includes the following steps:
  • step S1.2 In an atmospheric environment at normal temperature and pressure, spin-coat the PEDOT:PSS aqueous solution on the side of the anode away from the glass substrate in step S1.1, and then place it for constant temperature heat treatment at 150°C for 15 minutes to obtain an air layer with a thickness of 20nm. 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 for constant temperature heat treatment at 150°C for 30 minutes to obtain a thickness of 30nm. hole transport layer;
  • step S1.4 In a nitrogen environment at normal temperature and pressure, spin-coat CdZnSe/CdZnS/ZnS quantum dots-n-octane with a concentration of 10 mg/mL on the side of the hole transport layer away from the hole injection layer in step S1.3. The solution is then placed in a constant temperature heat treatment at 100°C for 5 minutes to obtain a luminescent layer with a thickness of 20nm;
  • step S1.5 In a nitrogen environment at normal temperature and pressure, spin-coat a nano-ZnO (particle size: 5 nm)-ethanol solution with a concentration of 30 mg/mL on the side of the light-emitting layer away from the hole transport layer in step S1.4 to obtain Wet film, use a clamp to fix the prefabricated device containing the wet film, connect the anode of the external power supply to the first side (left side) of the wet film, and connect the cathode of the external power supply to the second side (right side) of the wet film, The first side and the second side are set opposite each other, and then placed at a constant temperature of 150°C for continuous annealing treatment for 60 minutes.
  • a nano-ZnO (particle size: 5 nm)-ethanol solution with a concentration of 30 mg/mL
  • an external power supply is used to continuously energize the wet film with constant current for 60 minutes.
  • the current density of the wet film is 200mA/cm 2 , and an electron transport layer with a thickness of 50nm is obtained;
  • 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 with a thickness of 100nm, and then use epoxy resin and Glass plate packaging is used to obtain a light-emitting device with the structure shown in Figure 4.
  • the light-emitting device 1 includes a glass substrate 10, an anode 11, a hole functional layer 15, a light-emitting layer 13, an electron transport layer 14 and a cathode 12 which are stacked in sequence, wherein,
  • the hole functional layer 15 is composed of a stacked hole injection layer 151 and a hole transport layer 152 .
  • the hole injection layer 151 is close to the anode 11 and the hole transport layer 152 is close to the light-emitting layer 13 .
  • This embodiment provides a method for preparing a light-emitting device and the prepared light-emitting device.
  • step S1 is .5 is replaced with "In a nitrogen environment at normal temperature and pressure, spin-coat a nano-ZnO (particle size: 5 nm)-ethanol solution with a concentration of 30 mg/mL on the side of the light-emitting layer away from the hole transport layer in step S1.4.
  • the wet film use a clamp to fix the prefabricated device containing the wet film, connect the anode of the external power supply to the first side (left side) of the wet film, and connect the cathode of the external power supply to the second side (right side) of the wet film , and the first side and the second side are set opposite each other, and then placed at a constant temperature of 150°C for continuous constant temperature heat treatment for 60 minutes, and during the annealing process, an external power supply is used to continuously conduct 200mA/200mA/ cm 2 rectangle was treated with alternating current for 60 minutes to obtain an electron transport layer with a thickness of 50nm.”
  • This embodiment provides a method for preparing a light-emitting device and the prepared light-emitting device.
  • step S1 is .5 is replaced with "In a nitrogen environment at normal temperature and pressure, spin-coat a nano-ZnO (particle size: 5 nm)-ethanol solution with a concentration of 30 mg/mL on the side of the light-emitting layer away from the hole transport layer in step S1.4.
  • the wet film use a clamp to fix the prefabricated device containing the wet film, connect the anode of the external power supply to the first side (left side) of the wet film, and connect the cathode of the external power supply to the second side (right side) of the wet film , and the first side and the second side are set opposite each other, and then placed at a constant temperature of 150°C for continuous annealing treatment for 60 minutes.
  • an external power supply is used to intermittently energize the wet film with constant current for 60 minutes.
  • the current density of the wet film is 200mA/cm 2
  • the interval between adjacent current treatments is 10 minutes
  • the time for a single electrical treatment is 10 minutes, to obtain an electron transport layer with a thickness of 50nm.”
  • This embodiment provides a method for preparing a light-emitting device and the prepared light-emitting device.
  • step S1 is .5 is replaced with "In a nitrogen environment at normal temperature and pressure, spin-coat a nano-ZnO (particle size: 5 nm)-ethanol solution with a concentration of 30 mg/mL on the side of the light-emitting layer away from the hole transport layer in step S1.4.
  • This embodiment provides a method for preparing a light-emitting device and the prepared light-emitting device.
  • step S1 is .5 is replaced with "In a nitrogen environment at normal temperature and pressure, spin-coat a nano-ZnO (particle size: 5 nm)-ethanol solution with a concentration of 30 mg/mL on the side of the light-emitting layer away from the hole transport layer in step S1.4.
  • the wet film use a clamp to fix the prefabricated device containing the wet film, connect the anode of the external power supply to the first side (left side) of the wet film, and connect the cathode of the external power supply to the second side (right side) of the wet film , and the first side and the second side are set opposite each other, and the wet film is continuously energized with constant current for 60 minutes using an external power supply.
  • the current density of the electron transmission precursor layer is 200mA/cm 2 , and during the energization treatment During the process, the wet film was subjected to intermittent annealing for 60 minutes, the annealing temperature was 150°C, the interval between adjacent annealing treatments was 5 minutes, and the single annealing treatment time was 15 minutes to obtain an electron transport layer with a thickness of 50nm.”
  • This embodiment provides a method for preparing a light-emitting device and the prepared light-emitting device.
  • step S1 is .5 is replaced with "In a nitrogen environment at normal temperature and pressure, spin-coat a nano-ZnO (particle size: 5 nm)-ethanol solution with a concentration of 30 mg/mL on the side of the light-emitting layer away from the hole transport layer in step S1.4.
  • the wet film use a clamp to fix the prefabricated device containing the wet film, connect the anode of the external power supply to the first side (left side) of the wet film, and connect the cathode of the external power supply to the second side (right side) of the wet film , and the first side and the second side are set opposite each other, use an external power supply to continuously treat the wet film with a rectangular alternating current of 200mA/ cm2 with a frequency of 50Hz for 60 minutes, and perform intermittent annealing treatment on the wet film during the power-on treatment process. 60 minutes, the annealing temperature is 150°C, the interval between adjacent annealing treatments is 5 minutes, the time of a single annealing treatment is 15 minutes, and an electron transport layer with a thickness of 50nm is obtained.”
  • This embodiment provides a method for preparing a light-emitting device and the prepared light-emitting device.
  • step S1 is .5 is replaced with "In a nitrogen environment at normal temperature and pressure, spin-coat a nano-ZnO (particle size: 5 nm)-ethanol solution with a concentration of 30 mg/mL on the side of the light-emitting layer away from the hole transport layer in step S1.4.
  • the wet film uses a clamp to fix the prefabricated device containing the wet film, connect the anode of the external power supply to the first side (left side) of the wet film, and connect the cathode of the external power supply to the second side (right side) of the wet film , and the first side and the second side are set opposite each other.
  • the wet film is intermittently energized with constant current for 60 minutes using an external power supply. During the energization process, the current density of the wet film is 200mA/cm 2 and the wet film is intermittently energized.
  • the annealing treatment is 60 minutes, the temperature of the annealing treatment is 150°C, and the energization treatment and the annealing treatment are performed alternately.
  • the interval between adjacent energization treatments is 15 minutes, the time of a single energization treatment is 5 minutes, and the interval between adjacent annealing treatments is 5 minutes.
  • the time of a single annealing treatment is 15 minutes, and an electron transport layer with a thickness of 50nm is obtained.”
  • This embodiment provides a method for preparing a light-emitting device and the prepared light-emitting device.
  • step S1 is .5 is replaced with "In a nitrogen environment at normal temperature and pressure, spin-coat a nano-ZnO (particle size: 5 nm)-ethanol solution with a concentration of 30 mg/mL on the side of the light-emitting layer away from the hole transport layer in step S1.4.
  • the wet film use a clamp to fix the prefabricated device containing the wet film, connect the anode of the external power supply to the first side (left side) of the wet film, and connect the cathode of the external power supply to the second side (right side) of the wet film , and the first side and the second side are set opposite each other, use an external power supply to intermittently treat the wet film with a rectangular alternating current of 200 mA/ cm2 with a frequency of 50 Hz for 60 minutes, and perform intermittent annealing treatment on the wet film for 60 minutes.
  • the temperature of the annealing treatment is 150°C, and the annealing treatment and the energizing treatment are carried out alternately.
  • the interval between adjacent energizing treatments is 15 minutes, and the time of a single energizing treatment is 5 minutes.
  • the interval between adjacent annealing treatments is 5 minutes, and the time of a single annealing treatment is 15 minutes.
  • This embodiment provides a method for preparing a light-emitting device and the prepared light-emitting device.
  • step S1 is .5 is replaced with "In a nitrogen environment at normal temperature and pressure, spin-coat a nano-ZnO (particle size: 5 nm)-ethanol solution with a concentration of 30 mg/mL on the side of the light-emitting layer away from the hole transport layer in step S1.4.
  • the wet film use a clamp to fix the prefabricated device containing the wet film, connect the anode of the external power supply to the first side (left side) of the wet film, and connect the cathode of the external power supply to the second side (right side) of the wet film , and the first side and the second side are set opposite each other, and then placed at a constant temperature of 150°C for continuous annealing treatment for 60 minutes.
  • an external power supply is used to continuously energize the wet film with constant current for 60 minutes.
  • the current density of the electron transport precursor layer during the electrification process is 400mA/cm 2 , and an electron transport layer with a thickness of 50nm is obtained.”
  • This embodiment provides a method for preparing a light-emitting device and the prepared light-emitting device.
  • step S1 is .5 is replaced with "Under normal temperature and normal pressure in a nitrogen environment, spin-coat a nano-ZnO (particle size: 5 nm)-ethanol solution with a concentration of 30 mg/mL on the side of the light-emitting layer away from the hole transport layer in step S1.4 to obtain Wet film, use a clamp to fix the prefabricated device containing the wet film, connect the anode of the external power supply to the first side (left side) of the wet film, and connect the cathode of the external power supply to the second side (right side) of the wet film, The first side and the second side are set opposite each other, and then placed at a constant temperature of 150°C for continuous annealing treatment for
  • This embodiment provides a method for preparing a light-emitting device and the prepared light-emitting device.
  • the preparation method includes the following steps:
  • step S11.2 In an atmospheric environment at normal temperature and pressure, spin-coat the PEDOT:PSS aqueous solution on the side of the anode away from the glass substrate in step S11.1, and then place it for constant temperature heat treatment at 150°C for 15 minutes to obtain an air layer with a thickness of 20 nm. hole injection layer;
  • step S11.3 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 S11.2, and then place it for constant temperature heat treatment at 150°C for 30 minutes to obtain a thickness of 30nm. hole transport layer;
  • step S11.4 In a nitrogen environment at normal temperature and pressure, spin-coat CdZnSe/CdZnS/ZnS quantum dots-n-octane with a concentration of 10 mg/mL on the side of the hole transport layer away from the hole injection layer in step S11.3. The solution is then placed in a constant temperature heat treatment at 100°C for 5 minutes to obtain a luminescent layer with a thickness of 20nm;
  • step S11.7 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 S11.6 to obtain a cathode with a thickness of 100nm, and then use epoxy resin and Glass plate packaging is used to obtain a light-emitting device with a structure as shown in Figure 6.
  • This embodiment provides a method for preparing a light-emitting device and the prepared light-emitting device.
  • step S11 is .6 is replaced with "In a nitrogen environment at normal temperature and pressure, use a clamp to fix the laminated structure containing the electron transmission precursor layer, provide an external power supply, connect the first end of the external power supply to the anode, and the second end of the external power supply to the ground , and then placed at a constant temperature of 150°C for continuous annealing for 60 minutes.
  • an external power supply applied a constant voltage of -25V to the electron transport precursor layer for continuous charging for 60 minutes, so that the electron transport precursor layer contained
  • the entire prefabricated device of the precursor layer carries negative charges during the heating and annealing process to obtain an electron transport layer with a thickness of 50nm.”
  • This embodiment provides a method for preparing a light-emitting device and the prepared light-emitting device.
  • step S11 is .6 is replaced with "In a nitrogen environment at normal temperature and pressure, use a clamp to fix the laminated structure containing the electron transmission precursor layer, provide an external power supply, connect the first end of the external power supply to the anode, and the second end of the external power supply to the ground , and then placed at a constant temperature of 150°C for continuous annealing for 60 minutes.
  • an external power supply applied a constant voltage of 8V to the electron transport precursor layer for continuous charging for 60 minutes, so that the electron transport precursor layer contained
  • the entire prefabricated device of the layer carries a positive charge, obtaining an electron transport layer with a thickness of 50nm.”
  • This embodiment provides a method for preparing a light-emitting device and the prepared light-emitting device.
  • step S11 is .6 is replaced with "In a nitrogen environment at normal temperature and pressure, use a clamp to fix the laminated structure containing the electron transmission precursor layer, provide an external power supply, connect the first end of the external power supply to the anode, and the second end of the external power supply to the ground , and then placed at a constant temperature of 150°C for continuous annealing for 60 minutes.
  • an external power supply applied a constant voltage of 40V to the electron transport precursor layer for continuous charging for 60 minutes, so that the electron transport precursor layer contained
  • the entire prefabricated device of the layer carries a positive charge, obtaining an electron transport layer with a thickness of 50nm.”
  • This embodiment provides a method for preparing a light-emitting device and the prepared light-emitting device.
  • step S11 is .6 is replaced with "In a nitrogen environment at normal temperature and pressure, use a clamp to fix the laminated structure containing the electron transmission precursor layer, provide an external power supply, connect the first end of the external power supply to the anode, and the second end of the external power supply to the ground , and then placed at a constant temperature of 150°C for continuous annealing for 60 minutes, and during the annealing process, an external power supply applied a rectangular AC voltage (frequency 50Hz) from negative 25V to positive 25V to the electron transport precursor layer for continuous The charge treatment was performed for 60 minutes, so that the prefabricated device containing the electron transport precursor layer alternately carries positive and negative charges, and an electron transport layer with a thickness of 50nm was obtained.”
  • This embodiment provides a method for preparing a light-emitting device and the prepared light-emitting device.
  • step S11 is .6 is replaced with "In a nitrogen environment at normal temperature and pressure, use a clamp to fix the laminated structure containing the electron transmission precursor layer, provide an external power supply, connect the first end of the external power supply to the anode, and the second end of the external power supply to the ground , and then placed at a constant temperature of 150°C for continuous annealing treatment for 60 minutes, and during the annealing treatment process, turn on the external power supply to perform intermittently constant voltage (voltage is positive 25V) charging treatment on the electron transmission precursor layer for 60 minutes, the charging treatment process
  • the prefabricated device containing the electron transport precursor layer carries a positive charge as a whole, the interval between adjacent charging treatments is 10 minutes, and the time for a single charging
  • This embodiment provides a method for preparing a light-emitting device and the prepared light-emitting device.
  • step S11 is .6 is replaced with "In a nitrogen environment at normal temperature and pressure, use a clamp to fix the laminated structure containing the electron transmission precursor layer, provide an external power supply, connect the first end of the external power supply to the anode, and the second end of the external power supply to the ground , and then placed at a constant temperature of 150°C for continuous annealing for 60 minutes.
  • the annealing process During the annealing process, turn on the external power supply and apply a rectangular AC voltage to the electron transport precursor layer (frequency is 50Hz, voltage is negative 25V to positive 25V) Perform intermittently charging treatment for 60 minutes. During the charging process, the entire prefabricated device including the electron transport precursor layer alternately carries positive and negative charges. The interval between adjacent charging treatments is 10 minutes, and the time for a single charging treatment is 10 minutes. Obtain an electron transport layer with a thickness of 50nm.”
  • This embodiment provides a method for preparing a light-emitting device and the prepared light-emitting device.
  • step S11 is .6 is replaced with "In a nitrogen environment at normal temperature and pressure, use a clamp to fix the laminated structure containing the electron transmission precursor layer, provide an external power supply, connect the first end of the external power supply to the anode, and the second end of the external power supply to the ground , turn on the external power supply, apply a constant voltage of positive 25V to the electron transport precursor layer for continuous charging treatment for 60 minutes, so that the entire prefabricated device containing the electron transport precursor layer carries a positive charge, and during the charging process, the electrons
  • the transmission precursor layer is subjected to intermittent constant temperature (150°C) annealing for 60 minutes to perform the heating annealing process. The interval between adjacent annealing treatments is 5 minutes, and the
  • This embodiment provides a method for preparing a light-emitting device and the prepared light-emitting device.
  • step S11 is .6 is replaced with "In a nitrogen environment at normal temperature and pressure, use a clamp to fix the laminated structure containing the electron transmission precursor layer, provide an external power supply, connect the first end of the external power supply to the anode, and the second end of the external power supply to the ground , turn on the external power supply, apply a rectangular AC voltage (frequency is 50Hz, voltage is negative 25V to positive 25V) to the electron transmission precursor layer for continuous charging treatment for 60 minutes, so that the entire prefabricated device including the electron transmission precursor layer alternately carries positive energy and negative charges, and during the charging process, the electron transport precursor layer is subjected to intermittent constant temperature (150°C) annealing treatment for 60 minutes to perform the heating annealing process, so
  • step S11 is .6 is replaced with "In a nitrogen environment at normal temperature and pressure, use a clamp to fix the laminated structure containing the electron transmission precursor layer
  • This embodiment provides a method for preparing a light-emitting device and the prepared light-emitting device.
  • step S11 is .6 is replaced with "In a nitrogen environment at normal temperature and pressure, use a clamp to fix the laminated structure containing the electron transmission precursor layer, provide an external power supply, connect the first end of the external power supply to the anode, and the second end of the external power supply to the ground , turn on the external power supply, apply a constant voltage of positive 25V to the electron transport precursor layer for intermittently charging treatment for 60 minutes.
  • the entire prefabricated device containing the electron transport precursor layer carries a positive charge, and the electron transport precursor layer is charged.
  • This embodiment provides a method for preparing a light-emitting device and the prepared light-emitting device.
  • step S11 is .6 is replaced with "In a nitrogen environment at normal temperature and pressure, use a clamp to fix the laminated structure containing the electron transmission precursor layer, provide an external power supply, connect the first end of the external power supply to the anode, and the second end of the external power supply to the ground , turn on the external power supply, apply a rectangular AC voltage (frequency is 50Hz, voltage is negative 25V to positive 25V) to the electron transmission precursor layer for intermittently charging treatment for 60 minutes.
  • the entire prefabricated device including the electron transmission precursor layer is alternately transformed
  • the ground carries positive and negative charges
  • the electron transport precursor layer is subjected to intermittent constant temperature (150°C) annealing treatment for 60 minutes.
  • the charging treatment and annealing treatment are performed alternately.
  • the time of a single charging treatment is 5 minutes, and the time of a single annealing treatment is In 15 minutes, an electron transport layer with a thickness of 50nm was obtained.”
  • This embodiment provides a method for preparing a light-emitting device and the prepared light-emitting device.
  • step S11 is .6 is replaced by "Under a nitrogen environment at normal temperature and pressure, the electron transport precursor layer is continuously annealed at a constant temperature (150°C) for 60 minutes to form a dry film, and then a clamp is used to fix the stacked structure containing the dry film, and an external power supply is provided , connect the first end of the external power supply to the anode, and connect the second end of the external power supply to ground.
  • This embodiment provides a method for preparing a light-emitting device and the prepared light-emitting device.
  • step S11 is .6 is replaced by "In a nitrogen environment at normal temperature and pressure, use a clamp to fix the laminated structure containing the electron transmission precursor layer (wet film), provide an external power supply, and connect the first end of the external power supply to the anode.
  • the second end is grounded, the external power supply is turned on, and a rectangular AC voltage (frequency is 50Hz, voltage is negative 25V to positive 25V) is applied to the electron transmission precursor layer for continuous charging treatment for 60 minutes.
  • the charging process includes the prefabrication of the electron transmission precursor layer
  • the entire device alternately carries positive and negative charges.
  • the prefabricated device is continuously annealed at a constant temperature (150°C) for 60 minutes to form an electron transport layer with a thickness of 50nm.”
  • This comparative example provides a method for preparing a light-emitting device and the prepared light-emitting device.
  • step S1 is .5 is replaced with "In a nitrogen environment at normal temperature and pressure, spin-coat a nano-ZnO (particle size: 5 nm)-ethanol solution with a concentration of 30 mg/mL on the side of the light-emitting layer away from the hole transport layer in step S1.4.
  • a wet film was obtained and then continuously annealed at a constant temperature of 150°C for 60 minutes to obtain an electron transport layer with a thickness of 50nm.”
  • This comparative example provides a method for preparing a light-emitting device and the prepared light-emitting device. Compared with the method for preparing a light-emitting device provided in Embodiment 11, the difference between the method for preparing a light-emitting device in this comparative example is that step S11 is .6 is replaced by "Under a nitrogen environment at normal temperature and pressure, the electron transport precursor layer is continuously annealed at a constant temperature (150°C) for 60 minutes to obtain an electron transport layer with a thickness of 50nm.”
  • FPD optical characteristic measurement equipment efficiency test system built by LabView to control QE-PRO spectrometer, Keithley 2400 and Keithley 6485
  • Quantum efficiency, power efficiency and other key parameters, and use life testing equipment to test the service life of each of the above-mentioned light-emitting devices.
  • the life test uses the constant current method. Driven by a constant current (2mA current), a silicon photonic system is used to test the brightness changes of each light-emitting device, and the time required for the brightness to decay from 100% to 95% is recorded (T95, h ), and calculate the LT95@1000nit of each light-emitting device.
  • the experimental results are detailed in Table 1 below:
  • the comprehensive performance of the light-emitting devices in Examples 1 to 10 is significantly better than that of the light-emitting devices in Comparative Example 1.
  • the EQE max of the light-emitting devices in Example 2 is The EQE max of the light-emitting device in Example 1 is 2.2 times, and the LT95@1000nit of the light-emitting device in Example 5 is 3.7 times the LT95@1000nit of the light-emitting device in Comparative Example 1; after the package is placed for 30 days, the EQE max of the light-emitting device in Example 5 The EQE max is 3.7 times that of the light-emitting device in Comparative Example 1, and the LT95@1000nit of the light-emitting device in Example 5 is 15.2 times that of the light - emitting device in Comparative Example 1.
  • the EQE of the light-emitting device in Example 15 max is 3.7 times that of the EQE max of the light-emitting device in Comparative Example 2
  • the LT95@1000nit of the light-emitting device in Example 15 is 14.7 times that of the light-emitting device in Comparative Example 2.

Abstract

The present application discloses a manufacturing method for a light emitting device, a light emitting device, and a display apparatus. The manufacturing method comprises the following steps: providing a prefabricated device, and applying a solution containing a nano metal oxide to one side of the prefabricated device; and within a preset time range, performing annealing treatment and electrical treatment on the solution located at one side of the prefabricated device, so as to form an electron transfer layer. The present application effectively improves the crystallinity, conductivity, and stability of the electron transfer layer.

Description

发光器件的制备方法、发光器件与显示装置Preparation method of light-emitting device, 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202210393991.9、申请名称为“发光器件的制备方法、发光器件与显示装置”的中国专利申请，以及2022年04月14日在中国专利局提交的、申请号为202210394651.8、申请名称为“发光器件的制备方法、发光器件与显示装置”的两项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 requires a Chinese patent application with the application number 202210393991.9 and the application name "Preparation method of light-emitting device, light-emitting device and display device" submitted to the China Patent Office on April 14, 2022, and on April 14, 2022 Priority rights are granted to two Chinese patent applications filed with the China Patent Office with application number 202210394651.8 and application names "Preparation method of light-emitting device, light-emitting device and display device", the entire contents of which are incorporated into this application by reference.
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的制备方法、发光器件与显示装置。The present application relates to the field of optoelectronic technology, and specifically to a method for preparing a light-emitting device, a 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.
技术解决方案Technical solutions
鉴于此，本申请提供了一种发光器件的制备方法、发光器件与显示装置，以改善发光器件的光电性能和稳定性。In view of this, the present application provides a method for preparing a light-emitting device, a light-emitting device and a display device to improve the photoelectric performance and stability of the light-emitting device.
第一方面，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 first aspect, this application provides a method for preparing a light-emitting device, which method includes the following steps:
提供预制器件，在所述预制器件的一侧施加包含纳米金属氧化物的溶液；以及providing a prefabricated device, applying a solution containing nanometal oxides to one side of the prefabricated device; and
在预设的时间范围内，对位于所述预制器件的一侧的所述溶液进行退火处 理和电处理，以用于形成电子传输层；Within a preset time range, the solution located on one side of the prefabricated device is annealed and electrically treated to form an electron transport layer;
其中，当所述发光器件为正置型结构时，所述预制器件包括层叠设置的底电极和发光层，所述溶液施加于所述发光层远离所述底电极的一侧，所述底电极为阳极；Wherein, when the light-emitting device has a positive structure, the prefabricated device includes a bottom electrode and a light-emitting layer arranged in a stack, and the solution is applied to the side of the light-emitting layer away from the bottom electrode, and the bottom electrode is anode;
当所述发光器件为倒置型结构时，所述预制器件包括底电极，所述溶液施加于所述底电极的一侧，所述底电极为阴极。When the light-emitting device has an inverted structure, the prefabricated device includes a bottom electrode, the solution is applied to one side of the bottom electrode, and the bottom electrode is a cathode.
可选地，所述退火处理的时间段与所述电处理的时间段至少部分重叠，所述退火处理的方式和所述电处理的方式为下列任意一种情况：Optionally, the time period of the annealing treatment at least partially overlaps the time period of the electrical treatment, and the annealing treatment method and the electrical treatment method are any of the following:
(a1)所述退火处理为连续式的，且所述电处理为连续式的；(a1) The annealing treatment is continuous, and the electrical treatment is continuous;
(a2)所述退火处理为连续式的，且所述电处理为间断式的；(a2) The annealing treatment is continuous, and the electrical treatment is intermittent;
(a3)所述退火处理为间断式的，且所述电处理为连续式的；(a3) The annealing treatment is intermittent, and the electrical treatment is continuous;
(a4)所述退火处理为间断式的，且所述电处理为间断式的。(a4) The annealing treatment is intermittent, and the electrical treatment is intermittent.
可选地，所述退火处理的时间段与所述电处理的时间段不发生重叠，所述退火处理的方式和所述电处理的方式为下列任意一种情况：Optionally, the time period of the annealing treatment does not overlap with the time period of the electrical treatment, and the annealing treatment method and the electrical treatment method are any of the following:
(b1)所述退火处理与所述电处理交替进行；(b1) The annealing treatment and the electrical treatment are performed alternately;
(b2)对位于所述预制器件的一侧的所述溶液完成所述电处理之后，再进行所述退火处理。(b2) After completing the electrical treatment on the solution located on one side of the prefabricated device, perform the annealing treatment.
可选地，所述退火处理的温度为80℃至250℃；Optionally, the temperature of the annealing treatment is 80°C to 250°C;
所述退火处理的时间为5min至120min。The time of the annealing treatment is 5 min to 120 min.
可选地，所述电处理为带电处理，所述带电处理是使所述电子传输前驱层携带正电荷或负电荷，或使所述电子传输前驱层交替变换地携带正电荷和负电荷。Optionally, the electrical treatment is a charging treatment, and the charging treatment is to make the electron transport precursor layer carry positive charge or negative charge, or to make the electron transport precursor layer carry positive charge and negative charge alternately.
可选地，所述带电处理包括步骤：提供外接电源，所述外接电源的第一端与所述底电极相连，且所述外接电源的第二端接地；开启所述外接电源，以使所述第一端与所述第二端之间具有电位差。Optionally, the charging process includes the steps of: providing an external power supply, a first end of the external power supply is connected to the bottom electrode, and a second end of the external power supply is grounded; turning on the external power supply so that the There is a potential difference between the first end and the second end.
可选地，在所述带电处理的过程中，所述外接电源向所述电子传输前驱层施加恒压或交流电压；Optionally, during the charging process, the external power supply applies a constant voltage or an alternating voltage to the electron transport precursor layer;
其中，所述恒压的电压数值为10V至30V；Wherein, the voltage value of the constant voltage is 10V to 30V;
所述交流电压的频率为10Hz至200Hz，有效电压的数值为10V至30V。The frequency of the AC voltage is 10Hz to 200Hz, and the effective voltage is 10V to 30V.
可选地，所述带电处理的时间为5min至120min；Optionally, the charging treatment time is 5 min to 120 min;
所述带电处理为连续式的；或者，所述带电处理为间断式的，单次所述带电处理的时间为5min至20min，相邻所述带电处理的间隔时间为5min至20min。The charging treatment is continuous; or, the charging treatment is intermittent, the time of a single charging treatment is 5 min to 20 min, and the interval between adjacent charging treatments is 5 min to 20 min.
可选地，所述退火处理与所述带电处理的重叠时间为下列任意一种情况：Optionally, the overlap time of the annealing process and the charging process is any of the following situations:
(a11)当所述退火处理为连续式的，且所述带电处理为连续式的时，所述退火处理与所述带电处理的重叠时间为5min至120min；(a11) When the annealing treatment is continuous and the charging treatment is continuous, the overlap time of the annealing treatment and the charging treatment is 5 min to 120 min;
(a12)所述退火处理为连续式的，且所述带电处理为间断式的时，所述退火处理与所述带电处理的重叠时间为5min至115min；(a12) When the annealing treatment is continuous and the charging treatment is intermittent, the overlap time of the annealing treatment and the charging treatment is 5 min to 115 min;
(a13)当所述退火处理为间断式的，且所述带电处理为连续式的时，相邻所述退火处理的间隔时间为5min至10min，单次所述退火处理的时间为10min至30min，所述退火处理与所述带电处理的重叠时间为5min至115min；(a13) When the annealing treatment is intermittent and the charging treatment is continuous, the interval between adjacent annealing treatments is 5 min to 10 min, and the time for a single annealing treatment is 10 min to 30 min. , the overlap time of the annealing treatment and the charging treatment is 5min to 115min;
(a14)当所述退火处理为间断式的，且所述带电处理为间断式的时，相邻所述退火处理的间隔时间为5min至10min，单次所述退火处理的时间为10min至30min，所述退火处理与所述带电处理的重叠时间为5min至115min。(a14) When the annealing treatment is intermittent and the charging treatment is intermittent, the interval between adjacent annealing treatments is 5 min to 10 min, and the time for a single annealing treatment is 10 min to 30 min. , the overlap time of the annealing treatment and the charging treatment is 5min to 115min.
可选地，所述电处理为通电处理，所述通电处理是将所述溶液接入外接电源的阴极与阳极之间以形成闭合回路。Optionally, the electrical treatment is an electrification treatment, and the electrification treatment is to connect the solution between the cathode and the anode of an external power supply to form a closed loop.
可选地，所述通电处理包括步骤：将包含所述溶液的所述预制器件固定于夹具上，然后将外接电源的阳极和阴极分别与所述溶液所形成的湿膜中相对设置的两侧相连。Optionally, the electrification process includes the steps of: fixing the prefabricated device containing the solution on a fixture, and then connecting the anode and cathode of an external power supply to opposite sides of the wet film formed by the solution. connected.
可选地，所述通电处理为恒流式通电处理、恒压式通电处理或交变式通电处理；Optionally, the energization treatment is a constant current energization treatment, a constant voltage energization treatment or an alternating energization treatment;
在所述通电处理的过程中，位于所述预制器件的一侧的所述溶液的电流密度为100mA/cm 2至300mA/cm 2。 During the electrification treatment, the current density of the solution located on one side of the prefabricated device is 100 mA/cm 2 to 300 mA/cm 2 .
可选地，所述退火处理的时间段与所述通电处理的时间段至少部分交叠，所述退火处理与所述带电处理的处理时间为下述任意一种情况：Optionally, the time period of the annealing process and the time period of the electrification process at least partially overlap, and the processing time of the annealing process and the electrification process is any one of the following situations:
(a111)当所述退火处理为连续式的，且所述通电处理为间断式的时，相邻所述通电处理的间隔时间为5min至10min，单次所述通电处理的时间为10min至15min；(a111) When the annealing treatment is continuous and the energization treatment is intermittent, the interval time between adjacent energization treatments is 5 min to 10 min, and the time of a single energization treatment is 10 min to 15 min. ;
(a112)当所述退火处理为间断式的，且所述通电处理为连续式的时，相邻所述退火处理的间隔时间为5min至10min，单次所述退火处理的时间为10min至30min；(a112) When the annealing treatment is intermittent and the energization treatment is continuous, the interval between adjacent annealing treatments is 5 min to 10 min, and the time of a single annealing treatment is 10 min to 30 min. ;
(a113)所述退火处理为间断式的，且所述通电处理为间断式的时，相邻所述退火处理的间隔时间为5min至20min，单次所述退火处理的时间为5min至20min；相邻所述通电处理的间隔时间为5min至20min，单次所述通电处理的时间为5min至20min。(a113) The annealing treatment is intermittent, and when the energization treatment is intermittent, the interval between adjacent annealing treatments is 5 min to 20 min, and the time for a single annealing treatment is 5 min to 20 min; The interval time between adjacent energization treatments is 5 min to 20 min, and the time of a single energization treatment is 5 min to 20 min.
可选地，所述通电处理的总时间为5min至120min，所述退火处理与所述通电处理的交叠总时间为5min至120min。Optionally, the total time of the energization treatment is 5 min to 120 min, and the total overlap time of the annealing treatment and the energization treatment is 5 min to 120 min.
可选地，所述退火处理与所述通电处理交替进行；Optionally, the annealing treatment and the electrification treatment are performed alternately;
所述退火处理的总时间为5min至60min，所述通电处理的总时间为5min至60min；单次所述通电处理的时间为5min至20min，单次所述退火处理的时间为5min至20min。The total time of the annealing treatment is 5min to 60min, and the total time of the energization treatment is 5min to 60min; the time of a single energization treatment is 5min to 20min, and the time of a single annealing treatment is 5min to 20min.
可选地，当所述发光器件为正置型结构时，所述制备方法还包括步骤：在所述预制器件的所述一侧形成电子传输层之后，在所述电子传输层远离所述发光层的一侧形成阴极；Optionally, when the light-emitting device has an upright structure, the preparation method further includes the step of: after forming an electron transport layer on the side of the prefabricated device, moving the electron transport layer away from the light-emitting layer One side forms the cathode;
当所述发光器件为倒置型结构时，所述制备方法还包括如下步骤：When the light-emitting device has an inverted structure, the preparation method further includes the following steps:
在所述预制器件的所述一侧形成电子传输层之后，在所述电子传输层远离所述阴极的一侧形成发光层；以及After forming an electron transport layer on the side of the prefabricated device, forming a light-emitting layer on a side of the electron transport layer away from the cathode; and
在所述发光层远离所述电子传输层的一侧形成阳极。An anode is formed on a side of the light-emitting layer away from the electron transport layer.
可选地，所述制备方法还包括步骤：在所述阳极与所述发光层之间形成空穴功能层，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；Optionally, the preparation method further includes the step of: forming a hole functional layer between the anode and the light-emitting layer, the hole functional layer including one of a hole injection layer and a hole transport layer, or Various, when the hole functional 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 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'-二胺中的一种或多种； 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' -diamine and one or more of 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，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 transition metal oxides and transition metal chalcogenide compounds, the transition metal oxide is selected from one or more NiO x , MoO x , WO x and CrO x , the transition metal sulfur The system 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，所述发光器件的制备方法包括如下步骤：In a second aspect, the present application provides a light-emitting device. The preparation method of the light-emitting device includes the following steps:
提供预制器件，在所述预制器件的一侧施加包含纳米金属氧化物的溶液；以及providing a prefabricated device, applying a solution containing nanometal oxides to one side of the prefabricated device; and
在预设的时间范围内，对位于所述预制器件的一侧的所述溶液进行退火处理和电处理，以用于形成电子传输层；Within a preset time range, perform annealing treatment and electrical treatment on the solution located on one side of the prefabricated device to form an electron transport layer;
其中，当所述发光器件为正置型结构时，所述预制器件包括层叠设置的底电极和发光层，所述溶液施加于所述发光层远离所述底电极的一侧，所述底电极为阳极；Wherein, when the light-emitting device has a positive structure, the prefabricated device includes a bottom electrode and a light-emitting layer arranged in a stack, and the solution is applied to the side of the light-emitting layer away from the bottom electrode, and the bottom electrode is anode;
当所述发光器件为倒置型结构时，所述预制器件包括底电极，所述溶液施加于所述底电极的一侧，所述底电极为阴极。When the light-emitting device has an inverted structure, the prefabricated device includes a bottom electrode, the solution is applied to one side of the bottom electrode, and the bottom electrode is a cathode.
可选地，所述发光层的材料为有机发光材料或量子点；Optionally, the material of the light-emitting layer is an organic light-emitting material or quantum dots;
所述有机发光材料选自二芳香基蒽衍生物、二苯乙烯芳香族衍生物、芘衍生物、芴衍生物、TBPe荧光材料、TTPA荧光材料、TBRb荧光材料以及DBP荧光材料中的一种或多种；The organic light-emitting material is selected from one of diarylanthracene derivatives, stilbene aromatic derivatives, pyrene derivatives, fluorene derivatives, TBPe fluorescent materials, TTPA fluorescent materials, TBRb fluorescent materials and DBP fluorescent materials, or variety;
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中的一种或多种；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族化合物以及I-III-VI族化合物中的一种或多种，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以及HgZnSTe中的一种或多种，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以及InAlPSb中的一种或多种，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以及SnPbSTe中的一种或多种，所述I-III-VI族化合物选自CuInS、CuInSe以及AgInS中的一种或多种；The quantum dots are selected from one or more of single component quantum dots, core-shell structure quantum dots, inorganic perovskite quantum dots, and organic-inorganic hybrid perovskite quantum dots; when the quantum dots are selected from In the case of single-component quantum dots or core-shell structure quantum dots, the material of the single-component quantum dot, the material of the core of the core-shell structure quantum dot, and the material of the shell of the core-shell structure quantum dot are selected independently of each other. One or more of Group II-VI compounds, Group III-V compounds, Group IV-VI compounds and Group I-III-VI compounds, wherein the Group 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, HgZnSe ,HgZnTe , one or more of CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe and 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 , one or more of GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs and InAlPSb, the IV-VI compound is selected from SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, SnSeTe , one or more of SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, SnPbSeTe and SnPbSTe, the I-III-VI compound is selected from one or more of CuInS, CuInSe and AgInS kind;
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.
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，所述发光器件的制备方法包括如下步骤：In a third aspect, the present application provides a display device. The display device includes a light-emitting device. The preparation method of the light-emitting device includes the following steps:
提供预制器件，在所述预制器件的一侧施加包含纳米金属氧化物的溶液；以及providing a prefabricated device, applying a solution containing nanometal oxides to one side of the prefabricated device; and
在预设的时间范围内，对位于所述预制器件的一侧的所述溶液进行退火处理和电处理，以用于形成电子传输层；Within a preset time range, perform annealing treatment and electrical treatment on the solution located on one side of the prefabricated device to form an electron transport layer;
其中，当所述发光器件为正置型结构时，所述预制器件包括层叠设置的底电极和发光层，所述溶液施加于所述发光层远离所述底电极的一侧，所述底电极为阳极；Wherein, when the light-emitting device has a positive structure, the prefabricated device includes a bottom electrode and a light-emitting layer arranged in a stack, and the solution is applied to the side of the light-emitting layer away from the bottom electrode, and the bottom electrode is anode;
当所述发光器件为倒置型结构时，所述预制器件包括底电极，所述溶液施加于所述底电极的一侧，所述底电极为阴极。When the light-emitting device has an inverted structure, the prefabricated device includes a bottom electrode, the solution is applied to one side of the bottom electrode, and the bottom electrode is a cathode.
可选地，所述电处理为下述任意一种情况：Optionally, the electrical treatment is any of the following:
(C1)所述电处理为带电处理，所述带电处理是使所述电子传输前驱层携带正电荷或负电荷，或使所述电子传输前驱层交替变换地携带正电荷和负电荷；(C1) The electrical treatment is a charging treatment, which causes the electron transport precursor layer to carry positive charges or negative charges, or causes the electron transport precursor layer to alternately carry positive charges and negative charges;
(C2)所述电处理为通电处理，所述通电处理是将所述溶液接入外接电源的阴极与阳极之间以形成闭合回路。(C2) The electrical treatment is an electrification treatment, in which the solution is connected between the cathode and the anode of an external power supply to form a closed loop.
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为本申请提供的一种发光器件的制备方法的流程示意图；Figure 1 is a schematic flow chart of a method for preparing a light-emitting device provided by the present application;
图2为本申请的一些实施例提供的一种发光器件的制备方法的流程示意图；Figure 2 is a schematic flow chart of a method for manufacturing a light-emitting device according to some embodiments of the present application;
图3为本申请的一些实施例提供的另一种发光器件的制备方法的流程示意图；Figure 3 is a schematic flow chart of another method for preparing a light-emitting device according to some embodiments of the present application;
图4为本申请实施例提供的第一种发光器件的结构示意图。FIG. 4 is a schematic structural diagram of a first light-emitting device provided by an embodiment of the present application.
图5为本申请实施例提供的第二种发光器件的结构示意图。FIG. 5 is a schematic structural diagram of a second light-emitting device provided by an embodiment of the present application.
图6为本申请实施例提供的第三种发光器件的结构示意图。FIG. 6 is a schematic structural diagram of a third light-emitting device provided by 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发光器件的制备方法、发光器件与显示装置。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 method for preparing a light-emitting device, a light-emitting device and a display device. 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)”、“下述任意一种情况”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 terms "at least one" and "any one of the following situations" refer 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.
在发光器件中，阴极与发光层之间通常还会设置电子传输层，金属氧化物纳米颗粒是用于制备电子传输层的材料之一。纳米金属氧化物具有电子迁移率较高、宽带隙的特性，但是纳米金属氧化物的表面存在较多的缺陷态，使得纳米金属氧化物的稳定性并不理想，并且外界环境条件对纳米金属氧化物的缺陷密度和导电性能影响较大，从而导致电子传输层的性能波动较大，进而对发光器件的光电性能和工作寿命造成不利影响。因此，如何提高包含纳米金属氧化物的电子传输层的性能稳定性对发光器件的应用与发展具有重要意义。In light-emitting devices, an electron transport layer is usually provided between the cathode and the light-emitting layer. Metal oxide nanoparticles are one of the materials used to prepare the electron transport layer. Nano-metal oxides have the characteristics of high electron mobility and wide bandgap. However, there are many defect states on the surface of nano-metal oxides, which makes the stability of nano-metal oxides not ideal, and the external environmental conditions have a negative impact on nano-metal oxidation. The defect density and conductive properties of the object have a great impact, which leads to large fluctuations in the performance of the electron transport layer, which in turn adversely affects the photoelectric performance and working life of the light-emitting device. Therefore, how to improve the performance stability of electron transport layers containing nanometal oxides is of great significance to the application and development of light-emitting devices.
本申请实施例提供了一种发光器件的制备方法，如图1所示，所述制备方法包括如下步骤：The embodiment of the present application provides a method for preparing a light-emitting device, as shown in Figure 1. The preparation method includes the following steps:
S1、提供预制器件，在预制器件的一侧施加包含纳米金属氧化物的溶液；S1. Provide a prefabricated device, and apply a solution containing nanometal oxides to one side of the prefabricated device;
S2、在预设的时间范围内，对位于预制器件的一侧的所述溶液进行退火处理和电处理，以用于形成电子传输层。S2. Within a preset time range, perform annealing treatment and electrical treatment on the solution located on one side of the prefabricated device to form an electron transport layer.
其中，当所述发光器件为正置型结构时，所述预制器件包括层叠设置的底电极和发光层，所述溶液施加于所述发光层远离所述底电极的一侧，所述底电极为阳极；Wherein, when the light-emitting device has a positive structure, the prefabricated device includes a bottom electrode and a light-emitting layer arranged in a stack, and the solution is applied to the side of the light-emitting layer away from the bottom electrode, and the bottom electrode is anode;
当所述发光器件为倒置型结构时，所述预制器件包括底电极，所述溶液施加于所述底电极的一侧，所述底电极为阴极。When the light-emitting device has an inverted structure, the prefabricated device includes a bottom electrode, the solution is applied to one side of the bottom electrode, and the bottom electrode is a cathode.
在本申请的一些实施例中，退火处理的时间段与电处理的时间段至少部分重叠，所述退火处理的方式和所述电处理的方式为下列任意一种情况：In some embodiments of the present application, the time period of the annealing treatment and the time period of the electrical treatment at least partially overlap, and the annealing treatment method and the electrical treatment method are any of the following situations:
(a1)所述退火处理为连续式的，且所述电处理为连续式的；(a1) The annealing treatment is continuous, and the electrical treatment is continuous;
(a2)所述退火处理为连续式的，且所述电处理为间断式的；(a2) The annealing treatment is continuous, and the electrical treatment is intermittent;
(a3)所述退火处理为间断式的，且所述电处理为连续式的；(a3) The annealing treatment is intermittent, and the electrical treatment is continuous;
(a4)所述退火处理为间断式的，且所述电处理为间断式的。(a4) The annealing treatment is intermittent, and the electrical treatment is intermittent.
在本申请的一些实施例中，退火处理的时间段与电处理的时间段不发生重叠，退火处理的方式和电处理的方式为下列任意一种情况：In some embodiments of the present application, the time period of the annealing treatment and the time period of the electrical treatment do not overlap, and the annealing treatment method and the electrical treatment method are any of the following situations:
(b1)所述退火处理与所述电处理交替进行；(b1) The annealing treatment and the electrical treatment are performed alternately;
(b2)对位于所述预制器件的一侧的所述溶液完成所述电处理之后，再进行所述退火处理。(b2) After completing the electrical treatment on the solution located on one side of the prefabricated device, perform the annealing treatment.
在本申请的一些实施例中，如图2所示，发光器件的制备方法包括如下步骤：In some embodiments of the present application, as shown in Figure 2, a method for preparing a light-emitting device includes the following steps:
S10、提供预制器件，在预制器件的一侧施加包含纳米金属氧化物的溶液；S10. Provide a prefabricated device, and apply a solution containing nanometal oxides to one side of the prefabricated device;
S20、在预设的时间范围内，对位于预制器件的一侧的所述溶液进行退火处理和通电处理，以用于形成电子传输层。S20. Within a preset time range, perform annealing treatment and energization treatment on the solution located on one side of the prefabricated device to form an electron transport layer.
在图2所示发光器件的制备方法中，“退火处理”包括所有能使位于预制器件的一侧的所述溶液获得更高能量而至少去除部分溶剂的工序，包括但不限于是恒温式热处理工序或非恒温式热处理(例如温度呈梯度式变化)工序，在本申请的一些实施例中，“退火处理”是指在80℃至250℃下恒温热处理5min至120min，退火处理的温度例如可以是80℃至100℃、100℃至120℃、120℃至140℃、140℃至160℃、160℃至180℃、180℃至200℃、200℃至220℃、220℃至240℃、或者240℃至250℃，退火处理的时间例如可以是5min至10min、10min至20min、20min至30min、30min至40min、40min至50min、50min 至60min、60min至70min、70min至80min、80min至90min、90min至100min、100min至110min、或者110min至120min。可以理解的是，位于预制器件的一侧的所述溶液经退火处理可以形成湿膜状态或干膜状态的膜层。In the preparation method of the light-emitting device shown in Figure 2, "annealing treatment" includes all steps that can enable the solution located on one side of the prefabricated device to obtain higher energy and remove at least part of the solvent, including but not limited to isothermal heat treatment Process or non-isothermal heat treatment (for example, temperature changes in a gradient) process. In some embodiments of the present application, "annealing treatment" refers to constant temperature heat treatment at 80°C to 250°C for 5 minutes to 120 minutes. The temperature of the annealing treatment can be, for example, Is 80℃ to 100℃, 100℃ to 120℃, 120℃ to 140℃, 140℃ to 160℃, 160℃ to 180℃, 180℃ to 200℃, 200℃ to 220℃, 220℃ to 240℃, or 240°C to 250°C, the annealing treatment time can be, for example, 5min to 10min, 10min to 20min, 20min to 30min, 30min to 40min, 40min to 50min, 50min to 60min, 60min to 70min, 70min to 80min, 80min to 90min, 90min to 100min, 100min to 110min, or 110min to 120min. It can be understood that the solution located on one side of the prefabricated device can form a film layer in a wet film state or a dry film state after annealing treatment.
如本申请所用，“通电处理”是将包含纳米金属氧化物的溶液接入外接电源的阴极与阳极之间以形成闭合回路，所述溶液等同于闭合回路中的电阻，本申请实施例对外接电源的种类及型号不作具体限定，可根据不同的发光器件规模选定即可。需要说明的是，可以仅将所述溶液接入外接电源的阴极与阳极之间，也可以将包括所述溶液的预制器件接入外接电源的阴极与阳极之间。在本申请的至少一个实施例中，“通电处理”包括步骤：将包括所述溶液的预制器件固定于夹具上，然后将外接电源的阳极和阴极分别与所述溶液所形成的湿膜中相对设置的两侧相连。As used in this application, "energization treatment" is to connect a solution containing nanometal oxides between the cathode and anode of an external power supply to form a closed loop. The solution is equivalent to the resistance in the closed loop. The embodiments of this application are for external The type and model of the power supply are not specifically limited, and can be selected according to the scale of different light-emitting devices. It should be noted that the solution can only be connected between the cathode and the anode of the external power supply, or the prefabricated device including the solution can be connected between the cathode and the anode of the external power supply. In at least one embodiment of the present application, the "power treatment" includes the steps of: fixing the prefabricated device including the solution on a fixture, and then placing the anode and cathode of the external power supply opposite to the wet film formed by the solution. The two sides of the setting are connected.
对上述制备方法需要说明的是，当仅对位于预制器件的一侧的所述溶液进行退火处理时，由于一般采用热处理的方式对所述溶液进行退火处理，而热处理的温度不宜过高以避免对发光层和其他功能层造成损伤，所以无法对纳米金属氧化物进行彻底地退火，导致无法充分去除位于纳米金属氧化物表面的配体，从而无法有效地缩短相邻纳米颗粒之间的间隙，使得在形成的膜层中，由纳米金属氧化物形成的纳米晶体阵列具有排列疏松的特性，所述膜层存在致密性较低的问题。基于相邻纳米颗粒之间的间隙形成了电子传导的势垒，而纳米金属氧化物本身的比表面积较大且性质较为活泼，导致由纳米金属氧化物制得的所述膜层的导电性不理想，并且稳定性较差。基于此，在上述制备方法中，通过采用“在预设的时间范围内，对所述溶液进行退火处理和通电处理”的技术手段，以在电能和高温的作用下，促进所述溶液成膜的同时，使得连接于纳米金属氧化物表面的配体更易脱落，从而缩短相邻纳米颗粒之间的间隙，进而提高电子传输层的结晶度、导电性以及稳定性，有利于提高发光器件的光电性能和工作寿命。It should be noted about the above preparation method that when only the solution located on one side of the prefabricated device is annealed, since the solution is generally annealed by heat treatment, the temperature of the heat treatment should not be too high to avoid Causes damage to the light-emitting layer and other functional layers, so the nanometal oxide cannot be completely annealed, resulting in the inability to fully remove the ligands located on the surface of the nanometal oxide, thus failing to effectively shorten the gap between adjacent nanoparticles. Therefore, in the formed film layer, the nanocrystal array formed by the nanometal oxide has the characteristics of loose arrangement, and the film layer has the problem of low density. The gap between adjacent nanoparticles forms a potential barrier for electronic conduction, and the nanometal oxide itself has a large specific surface area and relatively active properties, resulting in poor conductivity of the film layer made of nanometal oxide. ideal and less stable. Based on this, in the above preparation method, the technical means of "annealing and electrifying the solution within a preset time range" is adopted to promote film formation of the solution under the action of electric energy and high temperature. At the same time, it makes it easier for the ligands connected to the surface of the nanometal oxide to fall off, thereby shortening the gap between adjacent nanoparticles, thereby improving the crystallinity, conductivity and stability of the electron transport layer, which is beneficial to improving the optoelectronic performance of the light-emitting device. performance and operating life.
相较于现有的发光器件(电子传输层的材料为纳米金属氧化物)，本申请中发光器件的电子传输层(材料为同种类的纳米金属氧化物)致密性更高，即相邻纳米颗粒之间的间隙更小，使得电子传输层的导电性和稳定性更高，从而本申请中发光器件的综合性能更佳。Compared with existing light-emitting devices (the material of the electron transport layer is nanometer metal oxide), the electron transport layer (the material of the electron transport layer is nanometer metal oxide) of the light-emitting device in this application is more dense, that is, adjacent nanometer The gaps between particles are smaller, making the electron transport layer more conductive and stable, so that the overall performance of the light-emitting device in this application is better.
此外，退火处理和通电处理是在惰性气体氛围下进行，“惰性气体”是指化学性质不活泼，且不会与电子传输前驱层和其他功能层发生反应，且具有隔绝氧气和水特性的一类气体，惰性气体例如选自氮气、氦气、氖气、氩气、氪气或氙气中的至少一种。在预设的时间范围内进行退火处理和通电处理之后，还可以进行其他的处理工序，例如还可以进行干燥处理，以形成干膜状态的电子传输层。In addition, the annealing treatment and the electrification treatment are carried out in an inert gas atmosphere. "Inert gas" refers to a gas that is chemically inactive, does not react with the electron transport precursor layer and other functional layers, and has the characteristics of isolating oxygen and water. Gas-like, inert gas, for example, is selected from at least one of nitrogen, helium, neon, argon, krypton or xenon. After performing the annealing treatment and the energizing treatment within a preset time range, other processing steps may also be performed, such as drying processing to form an electron transport layer in a dry film state.
具体的，在步骤S10中，所述包含纳米金属氧化物的溶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。当发光器件为正置型结构时，预制器件包括层叠设置的阳极和发光层，所述溶液施加于所述发光层远离所述阳极的一侧，例如：预制器件由依次层叠设置的衬底、阳极和发光层组成，又如：预制器件由依次层叠设置的衬底、阳极、空穴功能层和发光层组成；当发光器件为倒置型结构时，预制器件包括阴极，所述溶液施加于阴极的一侧，例如：预制器件由层叠设置的衬底和阴极组成，所述溶液施加于阴极远离衬底的一侧。Specifically, in step S10, the application method of the solution containing nanometal oxides includes but is not limited to spin coating, coating, inkjet printing, blade coating, dipping and pulling, soaking, spraying, roller coating or casting. at least one of them. When the light-emitting device has an upright structure, the prefabricated device includes a stacked anode and a light-emitting layer, and the solution is applied to the side of the light-emitting layer away from the anode. For example, the prefabricated device consists of a substrate, an anode, and anode that are stacked in sequence. and a light-emitting layer. Another example: the prefabricated device consists of a substrate, anode, a hole functional layer and a light-emitting layer that are stacked in sequence; when the light-emitting device has an inverted structure, the prefabricated device includes a cathode, and the solution is applied to the cathode. On one side, for example, a prefabricated device consists of a substrate and a cathode arranged in a stack, and the solution is applied to the side of the cathode away from the substrate.
纳米金属氧化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，纳米金属氧化物选自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。纳米金属氧化物的平均粒径例如可以是2nm至15nm，纳米金属氧化物的平均粒径例如可以是2nm至4nm、2nm至6nm、2nm至8nm、2nm至10nm、4nm至10nm、或者10nm至15nm，纳米金属氧化物的平均粒径例如可以是5nm、6nm、7nm、8nm、9nm、或者10nm。 The nanometal oxide may be an undoped nanometal oxide or a doped nanometal oxide. In some embodiments of the present application, the nanometal oxide 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 size of the nanometal oxide can be, for example, 2nm to 15nm. The average particle size of the nanometal oxide can be, for example, 2nm to 4nm, 2nm to 6nm, 2nm to 8nm, 2nm to 10nm, 4nm to 10nm, or 10nm to 15nm. , the average particle size of the nanometal oxide may be, for example, 5 nm, 6 nm, 7 nm, 8 nm, 9 nm, or 10 nm.
所述包含纳米金属氧化物的溶液例如可以是采用溶液法制得的包含纳米金属氧化物的产物，其中，溶剂包括但不限于是水、乙醇、丙醇、丁醇、已醇、正辛烷、正己烷或乙二醇单甲醚中的至少一种。The solution containing nanometal oxides can be, for example, a product containing nanometal oxides prepared by a solution method, wherein the solvents include but are not limited to water, ethanol, propanol, butanol, hexanol, n-octane, At least one of n-hexane or ethylene glycol monomethyl ether.
在步骤S20中，“预设的时间范围”是指操作者自行设定的时间范围，该时间范围可由多次重复实验获得，并且发光器件的类型不相同，该时间范围也会有所区别。在本申请的一些实施例中，“预设的时间范围”是指5min至120min。In step S20, the "preset time range" refers to the time range set by the operator. This time range can be obtained by repeated experiments multiple times, and the time range will be different depending on the type of the light-emitting device. In some embodiments of the present application, the "preset time range" refers to 5 minutes to 120 minutes.
在本申请的一些实施例中，通电处理为恒流式通电处理、恒压式通电处理或交变式通电处理；在通电处理的过程中，位于预制器件的一侧的所述溶液的 电流密度为100mA/cm 2至300mA/cm 2，例如可以是100mA/cm 2至150mA/cm 2、150mA/cm 2至200mA/cm 2、200mA/cm 2至250mA/cm 2、或者250mA/cm 2至300mA/cm 2。 In some embodiments of the present application, the electrification treatment is a constant current electrification treatment, a constant voltage electrification treatment or an alternating electrification treatment; during the electrification treatment, the current density of the solution located on one side of the prefabricated device It is 100mA/cm 2 to 300mA/cm 2 , for example, it can be 100mA/cm 2 to 150mA/cm 2 , 150mA/cm 2 to 200mA/cm 2 , 200mA/cm 2 to 250mA/cm 2 , or 250mA/cm 2 to 300mA/cm 2 .
可以理解的是，在通电处理的时间恒定的前提下，适当地提升位于预制器件的一侧的所述溶液的电流密度，能够提高对纳米金属氧化物表面的配体去除效果，从而提升相邻纳米颗粒之间的间隙缩小程度，进而提升电子传输层的导电性和稳定性。It can be understood that, under the premise that the time of the energization treatment is constant, appropriately increasing the current density of the solution located on one side of the prefabricated device can improve the ligand removal effect on the surface of the nanometal oxide, thereby improving the adjacent The gap between nanoparticles is reduced, thereby improving the conductivity and stability of the electron transport layer.
在本申请的一些实施例中，退火处理的时间段与通电处理的时间段至少部分交叠。In some embodiments of the present application, the time period of the annealing process and the time period of the power-on process at least partially overlap.
在本申请的至少一个实施例中，退火处理为连续式的，且通电处理为连续式的。可以理解的是，退火处理的时间段与通电处理的时间段可以仅部分交叠，可以完全重叠。In at least one embodiment of the present application, the annealing process is continuous, and the energization process is continuous. It can be understood that the time period of the annealing process and the time period of the energization process may only partially overlap or may completely overlap.
在本申请的至少一个实施例中，退火处理为连续式的，且通电处理为间断式的。相邻通电处理的间隔时间可以为5min至10min，单次通电处理的时间可以为10min至15min，相邻通电处理的间隔时间例如可以是5min至6min、6min至7min、7min至8min、8min至9min、或者9min至10min，单次通电处理的时间例如可以是10min至11min、11min至12min、12min至13min、13min至14min、或者14min至15min。In at least one embodiment of the present application, the annealing process is continuous, and the power-on process is intermittent. The interval time between adjacent energization treatments can be 5min to 10min, and the time of a single energization treatment can be 10min to 15min. The interval time between adjacent energization treatments can be, for example, 5min to 6min, 6min to 7min, 7min to 8min, 8min to 9min. , or 9min to 10min. The time of a single power-on treatment may be, for example, 10min to 11min, 11min to 12min, 12min to 13min, 13min to 14min, or 14min to 15min.
在本申请的至少一个实施例中，退火处理为间断式的，且通电处理为连续式的。相邻退火处理的间隔时间为5min至10min，单次退火处理的时间为10min至30min，相邻退火处理的间隔时间例如可以是5min至6min、6min至7min、7min至8min、8min至9min、或者9min至10min，单次退火处理的时间例如可以是10min至15min、15min至20min、20min至25min、或者25min至30min。In at least one embodiment of the present application, the annealing process is intermittent, and the energization process is continuous. The interval time of adjacent annealing treatments is 5min to 10min, and the time of a single annealing treatment is 10min to 30min. The interval time of adjacent annealing treatments can be, for example, 5min to 6min, 6min to 7min, 7min to 8min, 8min to 9min, or 9min to 10min. The time of a single annealing treatment may be, for example, 10min to 15min, 15min to 20min, 20min to 25min, or 25min to 30min.
在本申请的至少一个实施例中，退火处理为间断式的，且通电处理为间断式的，相邻退火处理的间隔时间为5min至20min，单次退火处理的时间为5min至20min；相邻通电处理的间隔时间为5min至20min，单次通电处理的时间为5min至20min。In at least one embodiment of the present application, the annealing treatment is intermittent, and the power-on treatment is intermittent. The interval time between adjacent annealing treatments is 5 min to 20 min, and the time of a single annealing treatment is 5 min to 20 min; The interval time of power treatment is 5min to 20min, and the time of single power treatment is 5min to 20min.
在本申请的至少一个实施例中，退火处理的总时间为5min至120min，通 电处理的总时间为5min至120min，退火处理与所述通电处理的交叠总时间为5min至120min。退火处理的总时间例如可以是5min至10min、10min至20min、20min至30min、30min至40min、40min至50min、50min至60min、60min至70min、70min至80min、80min至90min、90min至100min、100min至110min、或者110min至120min，通电处理的总时间例如可以是5min至10min、10min至20min、20min至30min、30min至40min、40min至50min、50min至60min、60min至70min、70min至80min、80min至90min、90min至100min、100min至110min、或者110min至120min，退火处理与所述通电处理的交叠总时间例如可以是5min至10min、10min至20min、20min至30min、30min至40min、40min至50min、50min至60min、60min至70min、70min至80min、80min至90min、90min至100min、100min至110min、或者110min至120min。In at least one embodiment of the present application, the total time of the annealing process is 5min to 120min, the total time of the energization process is 5min to 120min, and the total overlap time of the annealing process and the energization process is 5min to 120min. The total time of the annealing treatment can be, for example, 5min to 10min, 10min to 20min, 20min to 30min, 30min to 40min, 40min to 50min, 50min to 60min, 60min to 70min, 70min to 80min, 80min to 90min, 90min to 100min, 100min to 110min, or 110min to 120min, the total time of the energization treatment can be, for example, 5min to 10min, 10min to 20min, 20min to 30min, 30min to 40min, 40min to 50min, 50min to 60min, 60min to 70min, 70min to 80min, 80min to 90min , 90min to 100min, 100min to 110min, or 110min to 120min. The total overlap time of the annealing treatment and the energization treatment can be, for example, 5min to 10min, 10min to 20min, 20min to 30min, 30min to 40min, 40min to 50min, 50min to 60min, 60min to 70min, 70min to 80min, 80min to 90min, 90min to 100min, 100min to 110min, or 110min to 120min.
作为替代性实施例方案，在本申请的至少一个实施例中，退火处理与通电处理交替进行。As an alternative embodiment, in at least one embodiment of the present application, the annealing process is alternated with the energization process.
进一步地，退火处理的总时间为5min至60min，通电处理的总时间为5min至60min，退火处理的总时间例如为5min至10min、10min至20min、20min至30min、30min至40min、40min至50min、或者50min至60min，通电处理的总时间例如为5min至10min、10min至20min、20min至30min、30min至40min、40min至50min、或者50min至60min。Further, the total time of the annealing treatment is 5min to 60min, and the total time of the energization treatment is 5min to 60min. The total time of the annealing treatment is, for example, 5min to 10min, 10min to 20min, 20min to 30min, 30min to 40min, 40min to 50min, Or 50min to 60min. The total time of the energization treatment is, for example, 5min to 10min, 10min to 20min, 20min to 30min, 30min to 40min, 40min to 50min, or 50min to 60min.
进一步地，单次通电处理的时间为5min至20min，单次退火处理的时间为5min至20min，单次通电处理的时间例如为5min至8min、8min至10min、10min至15min、或15min至20min，单次退火处理的时间例如为5min至8min、8min至10min、10min至15min、或15min至20min。Further, the time of a single energization treatment is 5min to 20min, the time of a single annealing treatment is 5min to 20min, and the time of a single energization treatment is, for example, 5min to 8min, 8min to 10min, 10min to 15min, or 15min to 20min, The time of a single annealing treatment is, for example, 5 min to 8 min, 8 min to 10 min, 10 min to 15 min, or 15 min to 20 min.
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：在预制器件的所述一侧形成电子传输层之后，在电子传输层远离发光层的一侧制备形成阴极。可以理解的是，当发光器件为正置型结构时，预制器件可以是包含阳极、空穴功能层和发光层的叠层结构，因此，所述制备方法还包括步骤：提供阳极，在阳极的一侧依次制备形成空穴功能层和发光层，其中，空穴功能层包括空穴传输层和/或空穴注入层，当空穴功能层包括空穴传输层和空穴注入层时，空穴注入层靠近阳极，空穴传输层靠近发光层。In some embodiments of the present application, when the light-emitting device has an upright structure, the preparation method further includes the step of: after forming an electron transport layer on the side of the prefabricated device, preparing a side of the electron transport layer away from the light-emitting layer. form the cathode. It can be understood that when the light-emitting device has a positive structure, the prefabricated device can be a stacked structure including an anode, a hole functional layer and a light-emitting layer. Therefore, the preparation method further includes the step of: providing an anode, one side of the anode. The hole functional layer and the light-emitting layer are sequentially prepared on the side, wherein the hole functional layer includes a hole transport layer and/or a hole injection layer. When the hole functional layer includes a hole transport layer and a hole injection layer, the hole injection layer The layer is close to the anode, and the hole transport layer is close to the light-emitting layer.
在本申请的一个实施例中，当发光器件为正置型结构时，所述制备方法还包括如下步骤：In one embodiment of the present application, when the light-emitting device has an upright structure, the preparation method further includes the following steps:
S11、提供衬底，在衬底的一侧制备形成阳极；S11. Provide a substrate, and prepare and form an anode on one side of the substrate;
S12、在阳极远离衬底的一侧制备形成空穴注入层；S12. Prepare and form a hole injection layer on the side of the anode away from the substrate;
S13、在空穴注入层远离阳极的一侧制备形成空穴传输层；S13. Prepare and form a hole transport layer on the side of the hole injection layer away from the anode;
S14、在空穴传输层远离空穴注入层的一侧制备形成发光层；S14. Prepare and form a light-emitting layer on the side of the hole transport layer away from the hole injection layer;
S15、在发光层远离空穴传输层的一侧施加包含纳米金属氧化物的溶液，在预设的时间范围内，对位于预制器件的一侧的所述溶液进行退火处理和通电处理，获得电子传输层；S15. Apply a solution containing nanometal oxides to the side of the light-emitting layer away from the hole transport layer. Within a preset time range, perform annealing and energization on the solution located on the side of the prefabricated device to obtain electrons. transport layer;
S16、在电子传输层远离发光层的一侧制备形成阴极。S16. 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:
在预制器件的所述一侧形成电子传输层之后，在电子传输层远离阴极的一侧形成发光层；以及After the electron transport layer is formed on the side of the prefabricated device, a light-emitting layer is formed 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，所述制备方法还包括步骤：在阳极与发光层之间形成空穴功能层，空穴功能层包括空穴注入层和/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，空穴传输层靠近所述发光层，且所述空穴注入层靠近所述阳极。可以理解的是，“在阳极与发光层之间形成空穴功能层”是在发光层远离电子传输层的一侧先制备形成空穴功能层，然后在空穴功能层远离发光层的一侧制备形成阳极；此外，当空穴功能层包括空穴注入层和空穴传输层时，在发光层远离电子传输层的一侧依次制备形成空穴传输层、空穴注入层和发光层。Further, when the light-emitting device has an inverted structure, the preparation method further includes the steps of: forming a hole function layer between the anode and the light-emitting layer, the hole function layer including 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 is close to the anode. It can be understood that "forming the hole functional layer between the anode and the light-emitting layer" means first preparing and forming the hole functional layer on the side of the light-emitting layer away from the electron transport layer, and then forming the hole functional layer on the side far from the light-emitting layer. An anode is prepared and formed; in addition, when the hole functional layer includes a hole injection layer and a hole transport layer, a hole transport layer, a hole injection layer and a light-emitting layer are sequentially prepared on the side of the light-emitting layer away from the electron transport 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:
S11’、提供衬底，在衬底的一侧制备形成阴极；S11', provide a substrate, prepare and form a cathode on one side of the substrate;
S12’、在阴极远离衬底的一侧施加包含纳米金属氧化物的溶液，然后在预设的时间范围内，对位于预制器件的一侧的所述溶液进行退火处理和通电处理，然后干燥处理获得电子传输层；S12'. Apply a solution containing nanometal oxides to the side of the cathode away from the substrate, and then perform annealing and electrification treatment on the solution located on the side of the prefabricated device within a preset time range, and then dry it. Obtain electron transport layer;
S13’、在电子传输层远离阴极的一侧制备形成发光层；S13', prepare and form a light-emitting layer on the side of the electron transport layer away from the cathode;
S14’、在发光层远离电子传输层的一侧制备形成空穴传输层；S14', prepare and form a hole transport layer on the side of the light-emitting layer away from the electron transport layer;
S15’、在空穴传输层远离发光层的一侧制备形成空穴注入层；S15', prepare and form a hole injection layer on the side of the hole transport layer away from the light-emitting layer;
S16’、在空穴注入层远离空穴传输层的一侧制备形成阳极。S16', prepare and form an anode on the side of the hole injection layer away from the hole transport layer.
作为替代性实施方案，在本申请的另一些实施例中，如图3所示，发光器件的制备方法包括如下步骤：As an alternative embodiment, in other embodiments of the present application, as shown in Figure 3, a method for preparing a light-emitting device includes the following steps:
S100、提供预制器件，在预制器件的一侧施加包含纳米金属氧化物的溶液，以用于形成电子传输前驱层；S100. Provide a prefabricated device, and apply a solution containing nanometal oxides on one side of the prefabricated device to form an electron transport precursor layer;
S200、对电子传输前驱层进行带电处理，以用于形成电子传输层。S200. Perform charging treatment on the electron transport precursor layer to form the electron transport layer.
对上述制备方法需要说明的是，电子传输前驱层可以是湿膜状态，电子传输前驱层也可以是干膜状态，电子传输前驱层例如可以是包含纳米金属氧化物的溶液施加于预制器件的一侧而形成的湿膜，电子传输前驱层又如可以是包含纳米金属氧化物的溶液施加于预制器件的一侧而形成的湿膜干燥处理后获得的干燥膜层。可以理解的是，对电子传输前驱层进行带电处理的过程中或之后，所述制备方法还可以包括其他处理工序，例如：当电子传输前驱层为湿膜时，对电子传输前驱层进行带电处理之后，所述制备方法还可以包括干燥处理工序，以获得干膜状态的电子传输层。It should be noted about the above preparation method that the electron transport precursor layer can be in a wet film state, and the electron transport precursor layer can also be in a dry film state. For example, the electron transport precursor layer can be a solution containing nanometal oxides applied to the prefabricated device. For example, the wet film formed on one side of the prefabricated device, the electron transport precursor layer may be a dry film layer obtained by drying the wet film formed by applying a solution containing nanometal oxides to one side of the prefabricated device. It can be understood that during or after the charging treatment of the electron transport precursor layer, the preparation method may also include other processing steps, for example: when the electron transport precursor layer is a wet film, the electron transport precursor layer is subjected to a charging process. Afterwards, the preparation method may further include a drying process to obtain the electron transport layer in a dry film state.
电子传输前驱层是采用包含纳米金属氧化物的溶液制备而成，若仅对电子传输前驱层进行干燥处理以形成电子传输层，则干燥处理的温度不宜过高以避免对发光层和其他功能层造成损伤，因此，无法充分去除位于纳米金属氧化物表面的配体，从而无法有效地缩短相邻纳米颗粒之间的间隙，使得在形成的电子传输层中，由纳米金属氧化物形成的纳米晶体阵列具有排列疏松的特性，导致电子传输层存在致密性较低的问题。基于相邻纳米颗粒之间的间隙形成了电子传导的势垒，而纳米金属氧化物本身的比表面积较大且性质较为活泼，导致由纳米金属氧化物制得的电子传输层的导电性不理想，并且稳定性较差。基于此，在上述制备方法中，通过采用“对电子传输前驱层进行带电处理”的技术手段，以使连接于纳米金属氧化物表面的配体在电能和高温的作用下脱落，从而缩短相邻纳米颗粒之间的间隙，进而提高电子传输层的结晶度、导电性以及稳定性，有利于提高发光器件的光电性能和工作寿命。The electron transport precursor layer is prepared from a solution containing nanometal oxides. If the electron transport precursor layer is only dried to form the electron transport layer, the temperature of the drying process should not be too high to avoid damage to the light-emitting layer and other functional layers. Causes damage, therefore, the ligands located on the surface of the nanometal oxide cannot be sufficiently removed, so that the gap between adjacent nanoparticles cannot be effectively shortened, so that in the formed electron transport layer, the nanocrystals formed by the nanometal oxide The array has the characteristics of loose arrangement, which leads to the problem of low density of the electron transport layer. The gap between adjacent nanoparticles forms a potential barrier for electron conduction, and the nanometal oxide itself has a large specific surface area and relatively active properties, resulting in unsatisfactory conductivity of the electron transport layer made of nanometal oxide. , and the stability is poor. Based on this, in the above preparation method, the technical means of "charging the electron transport precursor layer" is used to cause the ligands connected to the surface of the nanometal oxide to fall off under the action of electrical energy and high temperature, thereby shortening the adjacent The gaps between nanoparticles can thereby improve the crystallinity, conductivity and stability of the electron transport layer, which is beneficial to improving the photoelectric performance and working life of the light-emitting device.
具体的，在步骤S100中，所述包含纳米金属氧化物的溶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。当发光器件为正置型结构时，预制器件包括层叠设置的底电极和发光层，电子传输前驱层形成于发光层远离底电极的一侧，底电极为阳极，例如：预制器件由依次层叠设置的衬底、阳极和发光层组成，又如：预制器件由依次层叠设置的衬底、阳极、空穴功能层和发光层组成；当发光器件为倒置型结构时，预制器件包括底电极，电子传输前驱层形成于底电极的一侧，底电极为阴极，例如：预制器件由层叠设置的衬底和阴极组成，电子传输前驱层形成于阴极远离衬底的一侧。Specifically, in step S100, the application method of the solution containing nanometal oxides includes but is not limited to spin coating, coating, inkjet printing, blade coating, dipping and pulling, soaking, spraying, roller coating or casting. at least one of them. When the light-emitting device has a positive structure, the prefabricated device includes a stacked bottom electrode and a light-emitting layer. The electron transport precursor layer is formed on the side of the light-emitting layer away from the bottom electrode. The bottom electrode is an anode. For example, the prefabricated device is composed of a stacked bottom electrode and a light-emitting layer. It consists of a substrate, anode and a light-emitting layer. Another example: a prefabricated device consists of a substrate, anode, a hole functional layer and a light-emitting layer that are stacked in sequence; when the light-emitting device has an inverted structure, the prefabricated device includes a bottom electrode for electron transmission. The precursor layer is formed on one side of the bottom electrode, which is the cathode. For example, a prefabricated device consists of a stacked substrate and a cathode, and the electron transport precursor layer is formed on the side of the cathode away from the substrate.
纳米金属氧化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，纳米金属氧化物选自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。纳米金属氧化物的平均粒径例如可以是2nm至15nm，纳米金属氧化物的平均粒径例如可以是2nm至4nm、2nm至6nm、2nm至8nm、2nm至10nm、4nm至10nm、或者10nm至15nm，纳米金属氧化物的平均粒径例如可以是5nm、6nm、7nm、8nm、9nm、或者10nm。 The nanometal oxide may be an undoped nanometal oxide or a doped nanometal oxide. In some embodiments of the present application, the nanometal oxide 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 size of the nanometal oxide can be, for example, 2nm to 15nm. The average particle size of the nanometal oxide can be, for example, 2nm to 4nm, 2nm to 6nm, 2nm to 8nm, 2nm to 10nm, 4nm to 10nm, or 10nm to 15nm. , the average particle size of the nanometal oxide may be, for example, 5 nm, 6 nm, 7 nm, 8 nm, 9 nm, or 10 nm.
所述包含纳米金属氧化物的溶液例如可以是采用溶液法制得的包含纳米金属氧化物的产物，其中，溶剂包括但不限于是水、乙醇、丙醇、丁醇、已醇、正辛烷、正己烷或乙二醇单甲醚中的至少一种。The solution containing nanometal oxides can be, for example, a product containing nanometal oxides prepared by a solution method, wherein the solvents include but are not limited to water, ethanol, propanol, butanol, hexanol, n-octane, At least one of n-hexane or ethylene glycol monomethyl ether.
具体的，在步骤S200中，带电处理是在预设的时间范围下进行，“预设的时间范围”是指操作者自行设定的时间范围，该时间范围可由多次重复实验获得，并且发光器件的类型不相同，该时间范围也会有所区别。在本申请的一些实施例中，带电处理的时间为5min至120min，带电处理的时间例如可以是5min至10min、10min至20min、20min至30min、30min至40min、40min至50min、50min至60min、60min至70min、70min至80min、80min至90min、90min至100min、100min至110min、或者110min至120min。Specifically, in step S200, the charging process is performed within a preset time range. The "preset time range" refers to the time range set by the operator. This time range can be obtained by repeated experiments multiple times, and the light emitting This time range will vary depending on the type of device. In some embodiments of the present application, the time of the charging treatment is 5min to 120min. The time of the charging treatment can be, for example, 5min to 10min, 10min to 20min, 20min to 30min, 30min to 40min, 40min to 50min, 50min to 60min, 60min. to 70min, 70min to 80min, 80min to 90min, 90min to 100min, 100min to 110min, or 110min to 120min.
可以理解的是，在预设的时间范围下，带电处理可以是连续式的，带电处理也可以是间断式的。在本申请的一些实施例中，在预设的时间范围下，带电处理为间断式的，单次带电处理的时间为5min至20min，相邻带电处理的间 隔时间为5min至20min，单次带电处理的时间例如可以是5min至8min、8min至10min、10min至15min、或15min至20min，相邻带电处理的间隔时间例如可以是5min至8min、8min至10min、10min至12min、12min至15min、或15min至20min。It can be understood that within a preset time range, the charging treatment can be continuous, or the charging treatment can be intermittent. In some embodiments of the present application, within the preset time range, the charging treatment is intermittent, the time of a single charging treatment is 5min to 20min, the interval time between adjacent charging treatments is 5min to 20min, and the time of a single charging treatment is 5min to 20min. The treatment time can be, for example, 5min to 8min, 8min to 10min, 10min to 15min, or 15min to 20min, and the interval time between adjacent charging treatments can be, for example, 5min to 8min, 8min to 10min, 10min to 12min, 12min to 15min, or 15min to 20min.
在本申请的一些实施例中，“带电处理”包括所有能使电子传输前驱层携带正电荷或负电荷，或使电子传输前驱层交替变换地携带正电荷和负电荷的工序，可以理解的是，带电处理可以仅使电子传输前驱层携带电荷，也可以使包含电子传输前驱层的预制器件整体携带电荷，也可以使包含电子传输前驱层的预制器件中的部分层(包括电子传输前驱层)携带电荷。In some embodiments of the present application, "charging treatment" includes all processes that can make the electron transport precursor layer carry positive or negative charges, or make the electron transport precursor layer alternately carry positive charges and negative charges. It can be understood that , the charging treatment can make only the electron transport precursor layer carry a charge, it can also make the entire prefabricated device containing the electron transport precursor layer carry a charge, or it can make some layers (including the electron transport precursor layer) in the prefabricated device containing the electron transport precursor layer carry a charge. Carry charge.
在本申请的一些实施例中，带电处理包括步骤：提供外接电源，外接电源的第一端与底电极相连，且外接电源的第二端接地，开启外接电源，第一端与第二段之间具有电位差，使得包含电子传输前驱层的预制器件整体携带正电荷或负电荷，或包含电子传输前驱层的预制器件整体交替变换地携带正电荷和负电荷。本申请实施例对外接电源的种类及型号不作具体限定，可根据不同的发光器件规模选定即可。In some embodiments of the present application, the charging process includes the steps of: providing an external power supply, the first end of the external power supply is connected to the bottom electrode, and the second end of the external power supply is connected to ground, turning on the external power supply, connecting the first end to the second section There is a potential difference between them, so that the entire prefabricated device including the electron transport precursor layer carries positive or negative charges, or the entire prefabricated device including the electron transport precursor layer alternately carries positive charges and negative charges. The embodiment of the present application does not specifically limit the type and model of the external power supply, and it can be selected according to the scale of different light-emitting devices.
在本申请的至少一个实施例中，“带电处理”包括步骤：将包含电子传输前驱层的预制器件固定于夹具上，然后将外接电源的第一端与位于预制器件一侧的底电极相连，且将外接电源的第二端接地，开启外接电源，第一端与第二端之间具有电位差。In at least one embodiment of the present application, the "charged treatment" includes the steps of: fixing the prefabricated device containing the electron transport precursor layer on the fixture, and then connecting the first end of the external power supply to the bottom electrode located on one side of the prefabricated device, And connect the second terminal of the external power supply to the ground, turn on the external power supply, and there will be a potential difference between the first terminal and the second terminal.
进一步地，在带电处理的过程中，外接电源向电子传输前驱层施加恒压或交流电压。当外接电源向电子传输前驱层施加恒压时，可以是第一端为正极，第二端为负极，使得包含电子传输前驱层的预制器件整体携带正电荷；也可以是第一电极为负极，第二电极为正极，使得包含电子传输前驱层的预制器件整体携带负电荷。当外接电源向电子传输前驱层施加交流电压时，使得包含电子传输前驱层的预制器件整体交替变换地携带正电荷和负电荷。Further, during the charging process, an external power supply applies a constant voltage or an alternating voltage to the electron transport precursor layer. When an external power supply applies a constant voltage to the electron transport precursor layer, the first terminal can be the positive electrode and the second terminal can be the negative electrode, so that the entire prefabricated device including the electron transport precursor layer carries a positive charge; or the first electrode can be the negative electrode, The second electrode is a positive electrode, so that the entire prefabricated device including the electron transport precursor layer carries a negative charge. When an external power supply applies an AC voltage to the electron transport precursor layer, the entire prefabricated device including the electron transport precursor layer alternately carries positive and negative charges.
可选地，当外接电源向电子传输前驱层施加恒压时，恒压的电压数值为10V至30V，恒压的电压数值例如为10V至15V、15V至20V、20V至25V、或25V至30V。如本申请所用，“电压数值”仅指电压的具体大小值，而不表示电压的方向。可以理解的是，在带电处理的时间恒定的前提下，恒压的电压数 值过高或过低均对发光器件的综合性能提升效果有限，若电压数值过低，则对纳米金属氧化物表面的配体去除效果有限，从而相邻纳米颗粒之间的间隙缩小程度有限，进而电子传输层的导电性和稳定性的提升效果有限；若电压数值过高，则可能对有机功能层和/或发光层造成一定程度的损伤。Optionally, when an external power supply applies a constant voltage to the electron transport precursor layer, the voltage value of the constant voltage is 10V to 30V. The voltage value of the constant voltage is, for example, 10V to 15V, 15V to 20V, 20V to 25V, or 25V to 30V. . As used in this application, "voltage value" only refers to the specific magnitude of the voltage, but does not indicate the direction of the voltage. It can be understood that, under the premise that the charging treatment time is constant, the constant voltage value that is too high or too low will have limited effect on improving the overall performance of the light-emitting device. If the voltage value is too low, it will have a negative effect on the surface of the nanometal oxide. The ligand removal effect is limited, so the gap between adjacent nanoparticles is limited, and the improvement effect on the conductivity and stability of the electron transport layer is limited; if the voltage value is too high, it may affect the organic functional layer and/or luminescence. layer causing some degree of damage.
可选地，当外接电源向电子传输前驱层施加交流电压时，交流电压的频率为10Hz至200Hz，有效电压的数值为10V至30V，交流电压的频率例如为10Hz至30Hz、30Hz至50Hz、50Hz至80Hz、80Hz至100Hz、100Hz至120Hz、120Hz至150Hz、150Hz至180Hz、或180Hz至200Hz，有效电压的数值例如为10V至15V、15V至20V、20V至25V、或25V至30V。Optionally, when an external power supply applies an AC voltage to the electron transmission precursor layer, the frequency of the AC voltage is 10Hz to 200Hz, the effective voltage value is 10V to 30V, and the frequency of the AC voltage is, for example, 10Hz to 30Hz, 30Hz to 50Hz, 50Hz. to 80Hz, 80Hz to 100Hz, 100Hz to 120Hz, 120Hz to 150Hz, 150Hz to 180Hz, or 180Hz to 200Hz, the effective voltage value is, for example, 10V to 15V, 15V to 20V, 20V to 25V, or 25V to 30V.
在本申请的一些实施例中，电子传输前驱层为湿膜，所述制备方法还包括步骤：对电子传输前驱层进行退火处理。“退火处理”包括所有能使湿膜状态的电子传输前驱层获得更高能量而至少去除部分溶剂的工序，包括但不限于是恒温式热处理工序或非恒温式热处理(例如温度呈梯度式变化)工序，在本申请的一些实施例中，“退火处理”是指在80℃至250℃下恒温热处理5min至120min，退火处理的温度例如可以是80℃至100℃、100℃至120℃、120℃至140℃、140℃至160℃、160℃至180℃、180℃至200℃、200℃至220℃、220℃至240℃、或者240℃至250℃，退火处理的时间例如可以是5min至10min、10min至20min、20min至30min、30min至40min、40min至50min、50min至60min、60min至70min、70min至80min、80min至90min、90min至100min、100min至110min、或者110min至120min。In some embodiments of the present application, the electron transport precursor layer is a wet film, and the preparation method further includes the step of: annealing the electron transport precursor layer. "Annealing treatment" includes all processes that can enable the electron transport precursor layer in the wet film state to obtain higher energy and remove at least part of the solvent, including but not limited to isothermal heat treatment processes or non-isothermal heat treatments (such as temperature gradient changes) Process, in some embodiments of the present application, "annealing treatment" refers to constant temperature heat treatment at 80°C to 250°C for 5 minutes to 120 minutes. The temperature of the annealing treatment can be, for example, 80°C to 100°C, 100°C to 120°C, 120°C ℃ to 140 ℃, 140 ℃ to 160 ℃, 160 ℃ to 180 ℃, 180 ℃ to 200 ℃, 200 ℃ to 220 ℃, 220 ℃ to 240 ℃, or 240 ℃ to 250 ℃, the annealing treatment time can be, for example, 5 minutes to 10min, 10min to 20min, 20min to 30min, 30min to 40min, 40min to 50min, 50min to 60min, 60min to 70min, 70min to 80min, 80min to 90min, 90min to 100min, 100min to 110min, or 110min to 120min.
在本申请的至少一个实施例中，退火处理为连续式的，且带电处理为连续式的，退火处理与带电处理的重叠时间为5min至120min，退火处理与带电处理的重叠时间例如为5min至10min、10min至20min、20min至30min、30min至40min、40min至50min、50min至60min、60min至70min、70min至80min、80min至90min、90min至100min、100min至110min、或者110min至120min。退火处理的时间例如为5min至120min，退火处理的温度例如为80℃至250℃，带电处理的时间例如为5min至120min。In at least one embodiment of the present application, the annealing treatment is continuous, and the charging treatment is continuous. The overlap time of the annealing treatment and the charging treatment is 5 min to 120 min. The overlap time of the annealing treatment and the charging treatment is, for example, 5 min to 120 min. 10min, 10min to 20min, 20min to 30min, 30min to 40min, 40min to 50min, 50min to 60min, 60min to 70min, 70min to 80min, 80min to 90min, 90min to 100min, 100min to 110min, or 110min to 120min. The time of the annealing treatment is, for example, 5 min to 120 min, the temperature of the annealing treatment is, for example, 80°C to 250°C, and the time of the charging treatment is, for example, 5 min to 120 min.
在本申请的至少一个实施例中，退火处理为连续式的，且带电处理为间断式的，退火处理与带电处理的重叠时间为5min至115min，退火处理与带电处 理的重叠时间例如为5min至10min、10min至20min、20min至30min、30min至40min、40min至50min、50min至60min、60min至70min、70min至80min、80min至90min、90min至100min、100min至115min。退火处理的时间例如为5min至120min，退火处理的温度例如为80℃至250℃，带电处理的时间例如为5min至120min，单次带电处理的时间例如为5min至20min，相邻带电处理的间隔时间例如为5min至20min。In at least one embodiment of the present application, the annealing treatment is continuous, and the charging treatment is intermittent. The overlap time of the annealing treatment and the charging treatment is 5 min to 115 min. The overlap time of the annealing treatment and the charging treatment is, for example, 5 min to 115 min. 10min, 10min to 20min, 20min to 30min, 30min to 40min, 40min to 50min, 50min to 60min, 60min to 70min, 70min to 80min, 80min to 90min, 90min to 100min, 100min to 115min. The time of the annealing treatment is, for example, 5min to 120min, the temperature of the annealing treatment is, for example, 80°C to 250°C, the time of the charging treatment is, for example, 5min to 120min, the time of a single charging treatment is, for example, 5min to 20min, and the interval between adjacent charging treatments The time is, for example, 5 min to 20 min.
在本申请的至少一个实施例中，退火处理为间断式的，且带电处理为连续式的，相邻退火处理的间隔时间为5min至10min，单次退火处理的时间为10min至30min，退火处理与带电处理的重叠时间为5min至115min，退火处理的温度例如为80℃至250℃。退火处理的间隔时间例如为5min至6min、6min至7min、7min至8min、8min至9min、或9min至10min，单次退火处理的时间例如为10min至15min、15min至20min、20min至25min、或者25min至30min，退火处理与带电处理的重叠时间例如为5min至10min、10min至20min、20min至30min、30min至40min、40min至50min、50min至60min、60min至70min、70min至80min、80min至90min、90min至100min、100min至115min。带电处理的时间例如为5min至120min。In at least one embodiment of the present application, the annealing treatment is intermittent, and the charging treatment is continuous. The interval between adjacent annealing treatments is 5 min to 10 min, and the time of a single annealing treatment is 10 min to 30 min. The overlap time with the charging treatment is 5 min to 115 min, and the temperature of the annealing treatment is, for example, 80°C to 250°C. The interval time of the annealing treatment is, for example, 5min to 6min, 6min to 7min, 7min to 8min, 8min to 9min, or 9min to 10min. The time of a single annealing treatment is, for example, 10min to 15min, 15min to 20min, 20min to 25min, or 25min. to 30min, the overlap time of annealing treatment and charging treatment is, for example, 5min to 10min, 10min to 20min, 20min to 30min, 30min to 40min, 40min to 50min, 50min to 60min, 60min to 70min, 70min to 80min, 80min to 90min, 90min to 100min, 100min to 115min. The charging treatment time is, for example, 5 min to 120 min.
在本申请的至少一个实施例中，退火处理为间断式的，且带电处理为间断式的，相邻退火处理的间隔时间为5min至10min，单次退火处理的时间为10min至30min，退火处理与带电处理的重叠时间为5min至115min，退火处理的温度例如为80℃至250℃。带电处理的时间例如为5min至120min，单次带电处理的时间例如为5min至20min，相邻带电处理的间隔时间例如为5min至20min。In at least one embodiment of the present application, the annealing treatment is intermittent, and the charging treatment is intermittent. The interval between adjacent annealing treatments is 5 min to 10 min, and the time of a single annealing treatment is 10 min to 30 min. The overlap time with the charging treatment is 5 min to 115 min, and the temperature of the annealing treatment is, for example, 80°C to 250°C. The time of the charging treatment is, for example, 5 min to 120 min, the time of a single charging treatment is, for example, 5 min to 20 min, and the interval time between adjacent charging treatments is, for example, 5 min to 20 min.
在本申请的另一些实施例中，退火处理的时间段与带电处理的时间段不发生重叠。例如：退火处理与带电处理交替进行，退火处理和带电处理均为间断式的，带电处理的时间例如为5min至120min，单次带电处理的时间例如为5min至20min，退火处理的时间例如为5min至120min，单次退火处理的时间例如为5min至20min。又如：对电子传输前驱层完成所述带电处理之后，再进行所述退火处理，带电处理可以是连续式的或间断式的，同理，退火处理也可以是连续式的或间断式的，带电处理的时间例如为5min至120min，退火处 理的时间例如为5min至120min。In other embodiments of the present application, the time period of the annealing process does not overlap with the time period of the charging process. For example: annealing treatment and charging treatment are performed alternately. Both annealing treatment and charging treatment are intermittent. The time of charging treatment is, for example, 5min to 120min. The time of single charging treatment is, for example, 5min to 20min. The time of annealing treatment is, for example, 5min. to 120 min, and the time of a single annealing treatment is, for example, 5 min to 20 min. Another example: after completing the charging treatment on the electron transmission precursor layer, the annealing treatment is then performed. The charging treatment can be continuous or intermittent. In the same way, the annealing treatment can also be continuous or intermittent. The charging treatment time is, for example, 5 min to 120 min, and the annealing treatment time is, for example, 5 min to 120 min.
需要说明的是，退火处理和带电处理是在惰性气体氛围下进行，“惰性气体”是指化学性质不活泼，且不会与电子传输前驱层和其他功能层发生反应，且具有隔绝氧气和水特性的一类气体，惰性气体例如选自氮气、氦气、氖气、氩气、氪气或氙气中的至少一种。It should be noted that the annealing treatment and charging treatment are carried out in an inert gas atmosphere. "Inert gas" means that it is chemically inactive, does not react with the electron transport precursor layer and other functional layers, and has the ability to isolate oxygen and water. A type of gas with special characteristics, the inert gas is, for example, at least one selected from nitrogen, helium, neon, argon, krypton or xenon.
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形成顶电极，顶电极为阴极。可以理解的是，当发光器件为正置型结构时，预制器件可以是包含阳极、空穴功能层和发光层的叠层结构，因此，所述制备方法还包括步骤：提供阳极，在阳极的一侧依次制备形成空穴功能层和发光层，其中，空穴功能层包括空穴传输层和/或空穴注入层，当空穴功能层包括空穴传输层和空穴注入层时，空穴注入层靠近阳极，空穴传输层靠近发光层。In some embodiments of the present application, when the light-emitting device has a positive structure, the preparation method further includes the step of forming a top electrode on the side of the electron transport layer away from the light-emitting layer, and the top electrode is a cathode. It can be understood that when the light-emitting device has a positive structure, the prefabricated device can be a stacked structure including an anode, a hole functional layer and a light-emitting layer. Therefore, the preparation method further includes the step of: providing an anode, one side of the anode. The hole functional layer and the light-emitting layer are sequentially prepared on the side, wherein the hole functional layer includes a hole transport layer and/or a hole injection layer. When the hole functional layer includes a hole transport layer and a hole injection layer, the hole injection layer The layer is close to the anode, and the hole transport layer is close to the light-emitting layer.
在本申请的至少一个实施例中，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 at least one embodiment of the present application, when the light-emitting device has an upright structure, the preparation method includes the following steps:
S101、提供衬底，在衬底的一侧制备形成阳极；S101. Provide a substrate, and prepare and form an anode on one side of the substrate;
S102、在阳极远离衬底的一侧制备形成空穴注入层；S102. Prepare and form a hole injection layer on the side of the anode away from the substrate;
S103、在空穴注入层远离阳极的一侧制备形成空穴传输层；S103. Prepare and form a hole transport layer on the side of the hole injection layer away from the anode;
S104、在空穴传输层远离空穴注入层的一侧制备形成发光层；S104. Prepare and form a light-emitting layer on the side of the hole transport layer away from the hole injection layer;
S105、在发光层远离空穴传输层的一侧施加包含纳米金属氧化物的溶液，获得湿膜状态的电子传输前驱层，然后在预设的时间范围内，对电子传输前驱层进行退火处理和带电处理，以使电子传输前驱层携带正电荷或负电荷，或使电子传输前驱层交替变换地携带正电荷和负电荷，获得电子传输层；S105. Apply a solution containing nanometal oxide on the side of the light-emitting layer away from the hole transport layer to obtain an electron transport precursor layer in a wet film state, and then anneal the electron transport precursor layer within a preset time range. Charging treatment to make the electron transport precursor layer carry positive charge or negative charge, or to make the electron transport precursor layer carry positive charge and negative charge alternately to obtain the electron transport layer;
S106、在电子传输层远离发光层的一侧制备形成阴极。S106. 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:
在预制器件的一侧形成电子传输层之后，在电子传输层远离底电极的一侧形成发光层；以及After the electron transport layer is formed on one side of the prefabricated device, a light-emitting layer is formed on a side of the electron transport layer away from the bottom electrode; and
在发光层远离电子传输层的一侧制备形成顶电极，顶电极为阳极。A top electrode is prepared on the side of the light-emitting layer away from the electron transport layer, and the top electrode is the anode.
进一步地，当发光器件为倒置型结构时，所述制备方法还包括步骤：在阳 极与发光层之间形成空穴功能层，空穴功能层包括空穴注入层和/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，空穴传输层靠近所述发光层，且所述空穴注入层靠近所述阳极。可以理解的是，“在阳极与发光层之间形成空穴功能层”是在发光层远离电子传输层的一侧先制备形成空穴功能层，然后在空穴功能层远离发光层的一侧制备形成阳极；此外，当空穴功能层包括空穴注入层和空穴传输层时，在发光层远离电子传输层的一侧依次制备形成空穴传输层、空穴注入层和发光层。Further, when the light-emitting device has an inverted structure, the preparation method further includes the steps of: forming a hole function layer between the anode and the light-emitting layer, the hole function layer including 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 is close to the anode. It can be understood that "forming the hole functional layer between the anode and the light-emitting layer" means first preparing and forming the hole functional layer on the side of the light-emitting layer away from the electron transport layer, and then forming the hole functional layer on the side far from the light-emitting layer. An anode is prepared and formed; in addition, when the hole functional layer includes a hole injection layer and a hole transport layer, a hole transport layer, a hole injection layer and a light-emitting layer are sequentially prepared on the side of the light-emitting layer away from the electron transport layer.
在本申请的至少一个实施例中，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 at least one embodiment of the present application, when the light-emitting device has an inverted structure, the preparation method includes the following steps:
S101’、提供衬底，在衬底的一侧制备形成阴极；S101', provide a substrate, prepare and form a cathode on one side of the substrate;
S102’、在阴极远离衬底的一侧施加包含纳米金属氧化物的溶液，获得湿膜状态的电子传输前驱层，然后在预设的时间范围内，对电子传输前驱层进行退火处理和带电处理，以使电子传输前驱层携带正电荷或负电荷，或使电子传输前驱层交替变换地携带正电荷和负电荷，获得电子传输层；S102', apply a solution containing nanometal oxides on the side of the cathode away from the substrate to obtain an electron transport precursor layer in a wet film state, and then perform annealing and charging treatments on the electron transport precursor layer within a preset time range , so that the electron transport precursor layer carries positive charge or negative charge, or the electron transport precursor layer alternately carries positive charge and negative charge to obtain the electron transport layer;
S103’、在电子传输层远离阴极的一侧制备形成发光层；S103', prepare and form a light-emitting layer on the side of the electron transport layer away from the cathode;
S104’、在发光层远离电子传输层的一侧制备形成空穴传输层；S104', prepare and form a hole transport layer on the side of the light-emitting layer away from the electron transport layer;
S105’、在空穴传输层远离发光层的一侧制备形成空穴注入层；S105', prepare and form a hole injection layer on the side of the hole transport layer away from the light-emitting layer;
S106’、在空穴注入层远离空穴传输层的一侧制备形成阳极。S106', prepare and form an anode on the side of the hole injection layer away from the hole transport layer.
对上述任意一种制备方法需要说明的是，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，需增设退火处理工序，以使湿膜转变为干膜。It should be noted that for any of the above preparation methods, 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, scraping, dipping, soaking, spraying, roller coating 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, electrolytic deposition method or co-precipitation method. Physical methods include but are 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 pulsed laser deposition method. When the solution method is used to prepare the film layer, an annealing process is required 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发光器件，所述发光器件采用上述任意一种所 述的制备方法制得，如图4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。可以理解的是，发光器件包括但不限于是OLED或QLED，并且发光器件可以是正置型结构，发光器件还可以是倒置型结构。相较于现有的发光器件(电子传输层的材料为纳米金属氧化物)，本申请实施例中发光器件的电子传输层致密性更高，即相邻纳米颗粒之间的间隙更小，使得电子传输层的导电性和稳定性更高，从而本申请实施例中发光器件的综合性能更佳。The embodiment of the present application also provides a light-emitting device. The light-emitting device is produced by any one of the above preparation methods. As shown in Figure 4, the light-emitting device 1 includes an anode 11, a cathode 12, a light-emitting layer 13 and an electron Transport layer 14, in which the anode 11 and the cathode 12 are arranged oppositely, the luminescent layer 13 is arranged between the anode 11 and the cathode 12, and the electron transport layer 14 is arranged between the cathode 12 and the luminescent layer 13. It can be understood that the light-emitting device includes but is not limited to OLED or QLED, and the light-emitting device may have an upright structure, or the light-emitting device may also have an inverted structure. Compared with existing light-emitting devices (the material of the electron transport layer is nanometal oxide), the electron transport layer of the light-emitting device in the embodiment of the present application is denser, that is, the gap between adjacent nanoparticles is smaller, so that The electron transport layer has higher conductivity and stability, so that the overall performance of the light-emitting device in the embodiment of the present application is better.
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的材料选自有机发光材料或量子点。发光层13的厚度例如可以是20nm至60nm。有机发光材料包括但不限于是二芳香基蒽衍生物、二苯乙烯芳香族衍生物、芘衍生物、芴衍生物、TBPe荧光材料、TTPA荧光材料、TBRb荧光材料或DBP荧光材料中的至少一种。The material of the light-emitting layer 13 is selected from organic light-emitting materials or quantum dots. The thickness of the light-emitting layer 13 may be, for example, 20 nm to 60 nm. Organic light-emitting materials include, but are not limited to, at least one of diarylanthracene derivatives, stilbene aromatic derivatives, pyrene derivatives, fluorene derivatives, TBPe fluorescent materials, TTPA fluorescent materials, TBRb fluorescent materials or DBP fluorescent materials. kind.
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。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、核壳结构量子点的核的材料以及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 material of the single-component quantum dot, the material of the core of the core-shell structure quantum dot, and the material of the shell of the core-shell structure quantum dot are independently selected from each other. At least one of Group II-VI compounds, Group III-V compounds, Group IV-VI compounds or Group I-III-VI compounds, wherein the Group II-VI compounds are selected from the group consisting of 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, At least one of 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, GaInNAs, GaInNSb, At least one of GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs or InAlPSb, the IV-VI compound is selected from SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, At least one of 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5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100nm。In order to obtain better photoelectric performance and service life, in some embodiments of the present application, as shown in FIG. 5 , the light-emitting device 1 further includes a hole function layer 15 , and the hole function layer 15 is disposed between 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 100 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。 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.
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。 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.
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制备方法制得的发光器件，或者本申请实施例中任意一种所述的发光器件，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. The display device includes a light-emitting device produced by any one of the preparation methods described in the embodiments of this application, or a light-emitting device described in any one of the embodiments of this application. , 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, televisions machine or e-book reader, wherein 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 are described in detail below through specific embodiments. The following embodiments 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的制备方法及制得的发光器件，所述制备方法包括如下步骤：This embodiment provides a method for preparing a light-emitting device and the prepared light-emitting device. The preparation method includes the following steps:
S1.1、在常温常压的大气环境下，提供0.5mm的玻璃衬底，在玻璃衬底的一侧溅射ITO以获得厚度为40nm的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，获得包括阳极的玻璃衬底；S1.1. Under an atmospheric environment of normal temperature and pressure, provide a 0.5mm glass substrate, sputter ITO on one side of the glass substrate to obtain an ITO layer with a thickness of 40nm, and wipe the ITO layer with a cotton swab dipped in a small amount of soapy water. surface to remove visible impurities on the surface, and then the substrate including ITO is ultrasonically cleaned with deionized water for 15 minutes, acetone for 15 minutes, ethanol for 15 minutes, and isopropyl alcohol for 15 minutes. After drying, use UV-ozone to clean the surface. Process for 15 minutes to obtain a glass substrate including an anode;
S1.2、在常温常压的大气环境下，在步骤S1.1的阳极远离玻璃衬底的一侧旋涂PEDOT：PSS水溶液，然后置于150℃下恒温热处理15min，获得厚度为20nm的空穴注入层；S1.2. In an atmospheric environment at normal temperature and pressure, spin-coat the PEDOT:PSS aqueous solution on the side of the anode away from the glass substrate in step S1.1, and then place it for constant temperature heat treatment at 150°C for 15 minutes to obtain an air layer with a thickness of 20nm. 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30min，获得厚度为30nm的空穴传输层；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 for constant temperature heat treatment at 150°C for 30 minutes to obtain a thickness of 30nm. 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10mg/mL的CdZnSe/CdZnS/ZnS量子点-正辛烷溶液，然后置于100℃下恒温热处理5min，获得厚度为20nm的发光层；S1.4. In a nitrogen environment at normal temperature and pressure, spin-coat CdZnSe/CdZnS/ZnS quantum dots-n-octane with a concentration of 10 mg/mL on the side of the hole transport layer away from the hole injection layer in step S1.3. The solution is then placed in a constant temperature heat treatment at 100°C for 5 minutes to obtain a luminescent layer with a thickness of 20nm;
S1.5、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30mg/mL的纳米ZnO(粒径为5nm)-乙醇溶液以获得湿膜，采用夹具固定包含湿膜的预制器件，将外接电源的阳极与湿膜的第一侧(左侧)连接，并将外接电源的阴极与湿膜的第二侧(右侧)连接，且第一侧与第二侧相对设置，然后置于150℃的恒定温度下连续地退火处理60min，并在退火处理的过程中，采用外接电源对湿膜进行连续地恒流式通电处理60min，通电处理过程中湿膜的电流密度为200mA/cm 2，获得厚度为50nm的电子传输层； S1.5. In a nitrogen environment at normal temperature and pressure, spin-coat a nano-ZnO (particle size: 5 nm)-ethanol solution with a concentration of 30 mg/mL on the side of the light-emitting layer away from the hole transport layer in step S1.4 to obtain Wet film, use a clamp to fix the prefabricated device containing the wet film, connect the anode of the external power supply to the first side (left side) of the wet film, and connect the cathode of the external power supply to the second side (right side) of the wet film, The first side and the second side are set opposite each other, and then placed at a constant temperature of 150°C for continuous annealing treatment for 60 minutes. During the annealing treatment, an external power supply is used to continuously energize the wet film with constant current for 60 minutes. During the electrification process, the current density of the wet film is 200mA/cm 2 , and an electron transport layer with a thickness of 50nm is obtained;
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，获得厚度为100nm的阴极，然后采用环氧树脂和玻璃板封装，获得如图4所示结构的发光器件。 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 with a thickness of 100nm, and then use epoxy resin and Glass plate packaging is used to obtain a light-emitting device with the structure shown in Figure 4.
请参阅图6，在由下至上的方向上，发光器件1包括依次层叠设置的玻璃衬底10、阳极11、空穴功能层15、发光层13、电子传输层14以及阴极12组成，其中，空穴功能层15由层叠设置的空穴注入层151和空穴传输层152组成，且空穴注入层151靠近阳极11，空穴传输层152靠近发光层13。Please refer to Figure 6. In the direction from bottom to top, the light-emitting device 1 includes a glass substrate 10, an anode 11, a hole functional layer 15, a light-emitting layer 13, an electron transport layer 14 and a cathode 12 which are stacked in sequence, wherein, The hole functional layer 15 is composed of a stacked hole injection layer 151 and a hole transport layer 152 . The hole injection layer 151 is close to the anode 11 and the hole transport layer 152 is close to the light-emitting layer 13 .
实施例2Example 2
本实施例提供了一种发光器件的制备方法及制得的发光器件，相较于实施例1提供的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点在于：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30mg/mL的纳米ZnO(粒径为5nm)-乙醇溶液以获得湿膜，采用夹具固定包含湿膜的预制器件，将外接电源的阳极与湿膜的第 一侧(左侧)连接，并将外接电源的阴极与湿膜的第二侧(右侧)连接，且第一侧与第二侧相对设置，然后置于150℃的恒定温度下连续地恒温热处理60min，并在退火处理的过程中，采用外接电源对湿膜进行连续地频率为50Hz的200mA/cm 2矩形交流电处理60min，获得厚度为50nm的电子传输层”。 This embodiment provides a method for preparing a light-emitting device and the prepared light-emitting device. Compared with the method for preparing a light-emitting device provided in Embodiment 1, the difference between the method for preparing a light-emitting device in this embodiment is that step S1 is .5 is replaced with "In a nitrogen environment at normal temperature and pressure, spin-coat a nano-ZnO (particle size: 5 nm)-ethanol solution with a concentration of 30 mg/mL on the side of the light-emitting layer away from the hole transport layer in step S1.4. Obtain the wet film, use a clamp to fix the prefabricated device containing the wet film, connect the anode of the external power supply to the first side (left side) of the wet film, and connect the cathode of the external power supply to the second side (right side) of the wet film , and the first side and the second side are set opposite each other, and then placed at a constant temperature of 150°C for continuous constant temperature heat treatment for 60 minutes, and during the annealing process, an external power supply is used to continuously conduct 200mA/200mA/ cm 2 rectangle was treated with alternating current for 60 minutes to obtain an electron transport layer with a thickness of 50nm."
实施例3Example 3
本实施例提供了一种发光器件的制备方法及制得的发光器件，相较于实施例1提供的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点在于：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30mg/mL的纳米ZnO(粒径为5nm)-乙醇溶液以获得湿膜，采用夹具固定包含湿膜的预制器件，将外接电源的阳极与湿膜的第一侧(左侧)连接，并将外接电源的阴极与湿膜的第二侧(右侧)连接，且第一侧与第二侧相对设置，然后置于150℃恒定温度下连续地退火处理60min，并在退火处理过程中，采用外接电源对湿膜进行间断地恒流式通电处理60min，通电处理过程中湿膜的电流密度为200mA/cm 2，相邻通电处理的间隔时间为10min，单次电处理的时间为10min，获得厚度为50nm的电子传输层”。 This embodiment provides a method for preparing a light-emitting device and the prepared light-emitting device. Compared with the method for preparing a light-emitting device provided in Embodiment 1, the difference between the method for preparing a light-emitting device in this embodiment is that step S1 is .5 is replaced with "In a nitrogen environment at normal temperature and pressure, spin-coat a nano-ZnO (particle size: 5 nm)-ethanol solution with a concentration of 30 mg/mL on the side of the light-emitting layer away from the hole transport layer in step S1.4. Obtain the wet film, use a clamp to fix the prefabricated device containing the wet film, connect the anode of the external power supply to the first side (left side) of the wet film, and connect the cathode of the external power supply to the second side (right side) of the wet film , and the first side and the second side are set opposite each other, and then placed at a constant temperature of 150°C for continuous annealing treatment for 60 minutes. During the annealing treatment process, an external power supply is used to intermittently energize the wet film with constant current for 60 minutes. During the treatment process, the current density of the wet film is 200mA/cm 2 , the interval between adjacent current treatments is 10 minutes, and the time for a single electrical treatment is 10 minutes, to obtain an electron transport layer with a thickness of 50nm."
实施例4Example 4
本实施例提供了一种发光器件的制备方法及制得的发光器件，相较于实施例1提供的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点在于：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30mg/mL的纳米ZnO(粒径为5nm)-乙醇溶液以获得湿膜，采用夹具固定包含湿膜的预制器件，将外接电源的阳极与湿膜的第一侧(左侧)连接，并将外接电源的阴极与湿膜的第二侧(右侧)连接，且第一侧与第二侧相对设置，然后置于150℃恒定温度下连续地退火处理60min，并在退火处理过程中，采用外接电源对电子传输前驱层进行间断地频率为50Hz的200mA/cm 2矩形交流电处理60min，相邻通电处理的间隔时间为10min，单次电处理的时间为10min，获得厚度为50nm的电子传输层”。 This embodiment provides a method for preparing a light-emitting device and the prepared light-emitting device. Compared with the method for preparing a light-emitting device provided in Embodiment 1, the difference between the method for preparing a light-emitting device in this embodiment is that step S1 is .5 is replaced with "In a nitrogen environment at normal temperature and pressure, spin-coat a nano-ZnO (particle size: 5 nm)-ethanol solution with a concentration of 30 mg/mL on the side of the light-emitting layer away from the hole transport layer in step S1.4. Obtain the wet film, use a clamp to fix the prefabricated device containing the wet film, connect the anode of the external power supply to the first side (left side) of the wet film, and connect the cathode of the external power supply to the second side (right side) of the wet film , and the first side and the second side are set opposite each other, and then placed at a constant temperature of 150°C for continuous annealing treatment for 60 minutes, and during the annealing treatment process, an external power supply is used to conduct intermittently 200mA / 50Hz frequency on the electron transmission precursor layer. cm 2 rectangle was treated with alternating current for 60 minutes, the interval between adjacent current treatments was 10 minutes, and the time for a single electrical treatment was 10 minutes to obtain an electron transport layer with a thickness of 50nm."
实施例5Example 5
本实施例提供了一种发光器件的制备方法及制得的发光器件，相较于实施例1提供的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点在 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30mg/mL的纳米ZnO(粒径为5nm)-乙醇溶液以获得湿膜，采用夹具固定包含湿膜的预制器件，将外接电源的阳极与湿膜的第一侧(左侧)连接，并将外接电源的阴极与湿膜的第二侧(右侧)连接，且第一侧与第二侧相对设置，采用外接电源对湿膜进行连续地恒流式通电处理60min，通电处理过程中电子传输前驱层的电流密度为200mA/cm 2，并在通电处理的过程中，对湿膜进行间断式退火处理60min，退火处理的温度为150℃，相邻退火处理的间隔时间为5min，单次退火处理的时间为15min，获得厚度为50nm的电子传输层”。 This embodiment provides a method for preparing a light-emitting device and the prepared light-emitting device. Compared with the method for preparing a light-emitting device provided in Embodiment 1, the difference between the method for preparing a light-emitting device in this embodiment is that step S1 is .5 is replaced with "In a nitrogen environment at normal temperature and pressure, spin-coat a nano-ZnO (particle size: 5 nm)-ethanol solution with a concentration of 30 mg/mL on the side of the light-emitting layer away from the hole transport layer in step S1.4. Obtain the wet film, use a clamp to fix the prefabricated device containing the wet film, connect the anode of the external power supply to the first side (left side) of the wet film, and connect the cathode of the external power supply to the second side (right side) of the wet film , and the first side and the second side are set opposite each other, and the wet film is continuously energized with constant current for 60 minutes using an external power supply. During the energization process, the current density of the electron transmission precursor layer is 200mA/cm 2 , and during the energization treatment During the process, the wet film was subjected to intermittent annealing for 60 minutes, the annealing temperature was 150°C, the interval between adjacent annealing treatments was 5 minutes, and the single annealing treatment time was 15 minutes to obtain an electron transport layer with a thickness of 50nm."
实施例6Example 6
本实施例提供了一种发光器件的制备方法及制得的发光器件，相较于实施例1提供的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点在于：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30mg/mL的纳米ZnO(粒径为5nm)-乙醇溶液以获得湿膜，采用夹具固定包含湿膜的预制器件，将外接电源的阳极与湿膜的第一侧(左侧)连接，并将外接电源的阴极与湿膜的第二侧(右侧)连接，且第一侧与第二侧相对设置，采用外接电源对湿膜进行连续地频率为50Hz的200mA/cm 2矩形交流电处理60min，并在通电处理的过程中，对湿膜进行间断式退火处理60min，退火处理的温度为150℃，相邻退火处理的间隔时间为5min，单次退火处理的时间为15min，获得厚度为50nm的电子传输层”。 This embodiment provides a method for preparing a light-emitting device and the prepared light-emitting device. Compared with the method for preparing a light-emitting device provided in Embodiment 1, the difference between the method for preparing a light-emitting device in this embodiment is that step S1 is .5 is replaced with "In a nitrogen environment at normal temperature and pressure, spin-coat a nano-ZnO (particle size: 5 nm)-ethanol solution with a concentration of 30 mg/mL on the side of the light-emitting layer away from the hole transport layer in step S1.4. Obtain the wet film, use a clamp to fix the prefabricated device containing the wet film, connect the anode of the external power supply to the first side (left side) of the wet film, and connect the cathode of the external power supply to the second side (right side) of the wet film , and the first side and the second side are set opposite each other, use an external power supply to continuously treat the wet film with a rectangular alternating current of 200mA/ cm2 with a frequency of 50Hz for 60 minutes, and perform intermittent annealing treatment on the wet film during the power-on treatment process. 60 minutes, the annealing temperature is 150°C, the interval between adjacent annealing treatments is 5 minutes, the time of a single annealing treatment is 15 minutes, and an electron transport layer with a thickness of 50nm is obtained."
实施例7Example 7
本实施例提供了一种发光器件的制备方法及制得的发光器件，相较于实施例1提供的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点在于：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30mg/mL的纳米ZnO(粒径为5nm)-乙醇溶液以获得湿膜，采用夹具固定包含湿膜的预制器件，将外接电源的阳极与湿膜的第一侧(左侧)连接，并将外接电源的阴极与湿膜的第二侧(右侧)连接，且第一侧与第二侧相对设置，采用外接电源对湿膜进行间断地恒流式通电处理60min，通电处理过程中湿膜的电流密度为200mA/cm 2，并对湿膜进行间断式退火处理 60min，退火处理的温度为150℃，并且通电处理与退火处理交替进行，相邻通电处理的间隔时间为15min，单次通电处理的时间为5min，相邻退火处理的间隔时间为5min，单次退火处理的时间为15min，获得厚度为50nm的电子传输层”。 This embodiment provides a method for preparing a light-emitting device and the prepared light-emitting device. Compared with the method for preparing a light-emitting device provided in Embodiment 1, the difference between the method for preparing a light-emitting device in this embodiment is that step S1 is .5 is replaced with "In a nitrogen environment at normal temperature and pressure, spin-coat a nano-ZnO (particle size: 5 nm)-ethanol solution with a concentration of 30 mg/mL on the side of the light-emitting layer away from the hole transport layer in step S1.4. Obtain the wet film, use a clamp to fix the prefabricated device containing the wet film, connect the anode of the external power supply to the first side (left side) of the wet film, and connect the cathode of the external power supply to the second side (right side) of the wet film , and the first side and the second side are set opposite each other. The wet film is intermittently energized with constant current for 60 minutes using an external power supply. During the energization process, the current density of the wet film is 200mA/cm 2 and the wet film is intermittently energized. The annealing treatment is 60 minutes, the temperature of the annealing treatment is 150°C, and the energization treatment and the annealing treatment are performed alternately. The interval between adjacent energization treatments is 15 minutes, the time of a single energization treatment is 5 minutes, and the interval between adjacent annealing treatments is 5 minutes. The time of a single annealing treatment is 15 minutes, and an electron transport layer with a thickness of 50nm is obtained."
实施例8Example 8
本实施例提供了一种发光器件的制备方法及制得的发光器件，相较于实施例1提供的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点在于：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30mg/mL的纳米ZnO(粒径为5nm)-乙醇溶液以获得湿膜，采用夹具固定包含湿膜的预制器件，将外接电源的阳极与湿膜的第一侧(左侧)连接，并将外接电源的阴极与湿膜的第二侧(右侧)连接，且第一侧与第二侧相对设置，采用外接电源对湿膜进行间断地频率为50Hz的200mA/cm 2矩形交流电处理60min，并对湿膜进行间断式退火处理60min，退火处理的温度为150℃，并且退火处理与通电处理交替进行，相邻通电处理的间隔时间为15min，单次通电处理的时间为5min，相邻退火处理的间隔时间为5min，单次退火处理的时间为15min，获得厚度为50nm的电子传输层”。 This embodiment provides a method for preparing a light-emitting device and the prepared light-emitting device. Compared with the method for preparing a light-emitting device provided in Embodiment 1, the difference between the method for preparing a light-emitting device in this embodiment is that step S1 is .5 is replaced with "In a nitrogen environment at normal temperature and pressure, spin-coat a nano-ZnO (particle size: 5 nm)-ethanol solution with a concentration of 30 mg/mL on the side of the light-emitting layer away from the hole transport layer in step S1.4. Obtain the wet film, use a clamp to fix the prefabricated device containing the wet film, connect the anode of the external power supply to the first side (left side) of the wet film, and connect the cathode of the external power supply to the second side (right side) of the wet film , and the first side and the second side are set opposite each other, use an external power supply to intermittently treat the wet film with a rectangular alternating current of 200 mA/ cm2 with a frequency of 50 Hz for 60 minutes, and perform intermittent annealing treatment on the wet film for 60 minutes. The temperature of the annealing treatment is 150℃, and the annealing treatment and the energizing treatment are carried out alternately. The interval between adjacent energizing treatments is 15 minutes, and the time of a single energizing treatment is 5 minutes. The interval between adjacent annealing treatments is 5 minutes, and the time of a single annealing treatment is 15 minutes. Obtain an electron transport layer with a thickness of 50nm."
实施例9Example 9
本实施例提供了一种发光器件的制备方法及制得的发光器件，相较于实施例1提供的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点在于：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30mg/mL的纳米ZnO(粒径为5nm)-乙醇溶液以获得湿膜，采用夹具固定包含湿膜的预制器件，将外接电源的阳极与湿膜的第一侧(左侧)连接，并将外接电源的阴极与湿膜的第二侧(右侧)连接，且第一侧与第二侧相对设置，然后置于150℃的恒定温度下连续地退火处理60min，并在退火处理的过程中，采用外接电源对湿膜进行连续地恒流式通电处理60min，通电处理过程中电子传输前驱层的电流密度为400mA/cm 2，获得厚度为50nm的电子传输层”。 This embodiment provides a method for preparing a light-emitting device and the prepared light-emitting device. Compared with the method for preparing a light-emitting device provided in Embodiment 1, the difference between the method for preparing a light-emitting device in this embodiment is that step S1 is .5 is replaced with "In a nitrogen environment at normal temperature and pressure, spin-coat a nano-ZnO (particle size: 5 nm)-ethanol solution with a concentration of 30 mg/mL on the side of the light-emitting layer away from the hole transport layer in step S1.4. Obtain the wet film, use a clamp to fix the prefabricated device containing the wet film, connect the anode of the external power supply to the first side (left side) of the wet film, and connect the cathode of the external power supply to the second side (right side) of the wet film , and the first side and the second side are set opposite each other, and then placed at a constant temperature of 150°C for continuous annealing treatment for 60 minutes. During the annealing treatment, an external power supply is used to continuously energize the wet film with constant current for 60 minutes. , the current density of the electron transport precursor layer during the electrification process is 400mA/cm 2 , and an electron transport layer with a thickness of 50nm is obtained.”
实施例10Example 10
本实施例提供了一种发光器件的制备方法及制得的发光器件，相较于实施 例1提供的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点在于：将步骤S1.5替换为“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30mg/mL的纳米ZnO(粒径为5nm)-乙醇溶液以获得湿膜，采用夹具固定包含湿膜的预制器件，将外接电源的阳极与湿膜的第一侧(左侧)连接，并将外接电源的阴极与湿膜的第二侧(右侧)连接，且第一侧与第二侧相对设置，然后置于150℃的恒定温度下连续地退火处理60min，并在退火处理的过程中，采用外接电源对湿膜进行连续地频率为50Hz的400mA/cm 2矩形交流电处理60min，获得厚度为50nm的电子传输层”。 This embodiment provides a method for preparing a light-emitting device and the prepared light-emitting device. Compared with the method for preparing a light-emitting device provided in Embodiment 1, the difference between the method for preparing a light-emitting device in this embodiment is that step S1 is .5 is replaced with "Under normal temperature and normal pressure in a nitrogen environment, spin-coat a nano-ZnO (particle size: 5 nm)-ethanol solution with a concentration of 30 mg/mL on the side of the light-emitting layer away from the hole transport layer in step S1.4 to obtain Wet film, use a clamp to fix the prefabricated device containing the wet film, connect the anode of the external power supply to the first side (left side) of the wet film, and connect the cathode of the external power supply to the second side (right side) of the wet film, The first side and the second side are set opposite each other, and then placed at a constant temperature of 150°C for continuous annealing treatment for 60 minutes. During the annealing treatment, an external power supply is used to continuously conduct 400mA/cm with a frequency of 50Hz on the wet film. 2. Treat the rectangle with alternating current for 60 minutes to obtain an electron transport layer with a thickness of 50nm."
实施例11Example 11
本实施例提供了一种发光器件的制备方法及制得的发光器件，所述制备方法包括如下步骤：This embodiment provides a method for preparing a light-emitting device and the prepared light-emitting device. The preparation method includes the following steps:
S11.1、在常温常压的大气环境下，提供0.5mm的玻璃衬底，在玻璃衬底的一侧溅射ITO以获得厚度为40nm的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，获得包括阳极的玻璃衬底；S11.1. Under an atmospheric environment of normal temperature and pressure, provide a 0.5mm glass substrate, sputter ITO on one side of the glass substrate to obtain an ITO layer with a thickness of 40nm, and wipe the ITO layer with a cotton swab dipped in a small amount of soapy water. surface to remove visible impurities on the surface, and then the substrate including ITO is ultrasonically cleaned with deionized water for 15 minutes, acetone for 15 minutes, ethanol for 15 minutes, and isopropyl alcohol for 15 minutes. After drying, use UV-ozone to clean the surface. Process for 15 minutes to obtain a glass substrate including an anode;
S11.2、在常温常压的大气环境下，在步骤S11.1的阳极远离玻璃衬底的一侧旋涂PEDOT：PSS水溶液，然后置于150℃下恒温热处理15min，获得厚度为20nm的空穴注入层；S11.2. In an atmospheric environment at normal temperature and pressure, spin-coat the PEDOT:PSS aqueous solution on the side of the anode away from the glass substrate in step S11.1, and then place it for constant temperature heat treatment at 150°C for 15 minutes to obtain an air layer with a thickness of 20 nm. hole injection layer;
S11.3、在常温常压的氮气环境下，在步骤S11.2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30min，获得厚度为30nm的空穴传输层；S11.3. 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 S11.2, and then place it for constant temperature heat treatment at 150°C for 30 minutes to obtain a thickness of 30nm. hole transport layer;
S11.4、在常温常压的氮气环境下，在步骤S11.3的空穴传输层远离空穴注入层的一侧旋涂浓度为10mg/mL的CdZnSe/CdZnS/ZnS量子点-正辛烷溶液，然后置于100℃下恒温热处理5min，获得厚度为20nm的发光层；S11.4. In a nitrogen environment at normal temperature and pressure, spin-coat CdZnSe/CdZnS/ZnS quantum dots-n-octane with a concentration of 10 mg/mL on the side of the hole transport layer away from the hole injection layer in step S11.3. The solution is then placed in a constant temperature heat treatment at 100°C for 5 minutes to obtain a luminescent layer with a thickness of 20nm;
S11.5、在常温常压的氮气环境下，在步骤S11.4的发光层远离空穴传输层的一侧旋涂浓度为30mg/mL的纳米ZnO(粒径为5nm)-乙醇溶液，获得包含电子传输前驱层(湿膜)的叠层结构；S11.5. Under a nitrogen environment at normal temperature and pressure, spin-coat a nano-ZnO (particle size: 5 nm)-ethanol solution with a concentration of 30 mg/mL on the side of the light-emitting layer away from the hole transport layer in step S11.4 to obtain A stacked structure including an electron transport precursor layer (wet film);
S11.6、在常温常压的氮气环境下，采用夹具固定包含电子传输前驱层的叠层结构，提供外接电源，并将外接电源的第一端与阳极相连，外接电源的第二端接地，然后置于150℃的恒定温度下连续地退火处理60min，并在退火处理过程中，外接电源向电子传输前驱层施加电压为正25V的恒压以进行连续地带电处理60min，使得包含电子传输前驱层的预制器件整体在退火处理工序中携带正电荷，获得厚度为50nm的电子传输层；S11.6. In a nitrogen environment at normal temperature and pressure, use a clamp to fix the laminated structure containing the electron transmission precursor layer, provide an external power supply, connect the first end of the external power supply to the anode, and the second end of the external power supply to ground. Then it is placed at a constant temperature of 150°C and continuously annealed for 60 minutes. During the annealing process, an external power supply applies a constant voltage of positive 25V to the electron transport precursor layer for continuous charging process for 60 minutes, so that the electron transport precursor layer contains The entire prefabricated device of the layer carries positive charges during the annealing process to obtain an electron transport layer with a thickness of 50nm;
S11.7、在气压为4×10 -6mbar的真空环境下，在步骤S11.6的电子传输层远离发光层的一侧蒸镀Ag，获得厚度为100nm的阴极，然后采用环氧树脂和玻璃板封装，获得如图6所示结构的发光器件。 S11.7. 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 S11.6 to obtain a cathode with a thickness of 100nm, and then use epoxy resin and Glass plate packaging is used to obtain a light-emitting device with a structure as shown in Figure 6.
实施例12Example 12
本实施例提供了一种发光器件的制备方法及制得的发光器件，相较于实施例11提供的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点在于：将步骤S11.6替换为“在常温常压的氮气环境下，采用夹具固定包含电子传输前驱层的叠层结构，提供外接电源，并将外接电源的第一端与阳极相连，外接电源的第二端接地，然后置于150℃的恒定温度下连续地退火处理60min，并在退火处理过程中，外接电源向电子传输前驱层施加电压为-25V的恒压以进行连续地带电处理60min，使得包含电子传输前驱层的预制器件整体在以进行加热退火工序中携带负电荷，获得厚度为50nm的电子传输层”。This embodiment provides a method for preparing a light-emitting device and the prepared light-emitting device. Compared with the method for preparing a light-emitting device provided in Embodiment 11, the difference between the method for preparing a light-emitting device in this embodiment is that step S11 is .6 is replaced with "In a nitrogen environment at normal temperature and pressure, use a clamp to fix the laminated structure containing the electron transmission precursor layer, provide an external power supply, connect the first end of the external power supply to the anode, and the second end of the external power supply to the ground , and then placed at a constant temperature of 150°C for continuous annealing for 60 minutes. During the annealing process, an external power supply applied a constant voltage of -25V to the electron transport precursor layer for continuous charging for 60 minutes, so that the electron transport precursor layer contained The entire prefabricated device of the precursor layer carries negative charges during the heating and annealing process to obtain an electron transport layer with a thickness of 50nm."
实施例13Example 13
本实施例提供了一种发光器件的制备方法及制得的发光器件，相较于实施例11提供的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点在于：将步骤S11.6替换为“在常温常压的氮气环境下，采用夹具固定包含电子传输前驱层的叠层结构，提供外接电源，并将外接电源的第一端与阳极相连，外接电源的第二端接地，然后置于150℃的恒定温度下连续地退火处理60min，并在退火处理过程中，外接电源向电子传输前驱层施加电压为8V的恒压以进行连续地带电处理60min，使得包含电子传输前驱层的预制器件整体携带正电荷，获得厚度为50nm的电子传输层”。This embodiment provides a method for preparing a light-emitting device and the prepared light-emitting device. Compared with the method for preparing a light-emitting device provided in Embodiment 11, the difference between the method for preparing a light-emitting device in this embodiment is that step S11 is .6 is replaced with "In a nitrogen environment at normal temperature and pressure, use a clamp to fix the laminated structure containing the electron transmission precursor layer, provide an external power supply, connect the first end of the external power supply to the anode, and the second end of the external power supply to the ground , and then placed at a constant temperature of 150°C for continuous annealing for 60 minutes. During the annealing process, an external power supply applied a constant voltage of 8V to the electron transport precursor layer for continuous charging for 60 minutes, so that the electron transport precursor layer contained The entire prefabricated device of the layer carries a positive charge, obtaining an electron transport layer with a thickness of 50nm."
实施例14Example 14
本实施例提供了一种发光器件的制备方法及制得的发光器件，相较于实施 例11提供的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点在于：将步骤S11.6替换为“在常温常压的氮气环境下，采用夹具固定包含电子传输前驱层的叠层结构，提供外接电源，并将外接电源的第一端与阳极相连，外接电源的第二端接地，然后置于150℃的恒定温度下连续地退火处理60min，并在退火处理过程中，外接电源向电子传输前驱层施加电压为40V的恒压以进行连续地带电处理60min，使得包含电子传输前驱层的预制器件整体携带正电荷，获得厚度为50nm的电子传输层”。This embodiment provides a method for preparing a light-emitting device and the prepared light-emitting device. Compared with the method for preparing a light-emitting device provided in Embodiment 11, the difference between the method for preparing a light-emitting device in this embodiment is that step S11 is .6 is replaced with "In a nitrogen environment at normal temperature and pressure, use a clamp to fix the laminated structure containing the electron transmission precursor layer, provide an external power supply, connect the first end of the external power supply to the anode, and the second end of the external power supply to the ground , and then placed at a constant temperature of 150°C for continuous annealing for 60 minutes. During the annealing process, an external power supply applied a constant voltage of 40V to the electron transport precursor layer for continuous charging for 60 minutes, so that the electron transport precursor layer contained The entire prefabricated device of the layer carries a positive charge, obtaining an electron transport layer with a thickness of 50nm."
实施例15Example 15
本实施例提供了一种发光器件的制备方法及制得的发光器件，相较于实施例11提供的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点在于：将步骤S11.6替换为“在常温常压的氮气环境下，采用夹具固定包含电子传输前驱层的叠层结构，提供外接电源，并将外接电源的第一端与阳极相连，外接电源的第二端接地，然后置于150℃的恒定温度下连续地退火处理60min，并在退火处理过程中，外接电源向电子传输前驱层施加电压为负25V至正25V的矩形交流电压(频率为50Hz)以进行连续地带电处理60min，使得包含电子传输前驱层的预制器件交替变换地携带正电荷和负电荷，获得厚度为50nm的电子传输层”。This embodiment provides a method for preparing a light-emitting device and the prepared light-emitting device. Compared with the method for preparing a light-emitting device provided in Embodiment 11, the difference between the method for preparing a light-emitting device in this embodiment is that step S11 is .6 is replaced with "In a nitrogen environment at normal temperature and pressure, use a clamp to fix the laminated structure containing the electron transmission precursor layer, provide an external power supply, connect the first end of the external power supply to the anode, and the second end of the external power supply to the ground , and then placed at a constant temperature of 150°C for continuous annealing for 60 minutes, and during the annealing process, an external power supply applied a rectangular AC voltage (frequency 50Hz) from negative 25V to positive 25V to the electron transport precursor layer for continuous The charge treatment was performed for 60 minutes, so that the prefabricated device containing the electron transport precursor layer alternately carries positive and negative charges, and an electron transport layer with a thickness of 50nm was obtained."
实施例16Example 16
本实施例提供了一种发光器件的制备方法及制得的发光器件，相较于实施例11提供的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点在于：将步骤S11.6替换为“在常温常压的氮气环境下，采用夹具固定包含电子传输前驱层的叠层结构，提供外接电源，并将外接电源的第一端与阳极相连，外接电源的第二端接地，然后置于150℃的恒定温度下连续地退火处理60min，并在退火处理过程中，开启外接电源以对电子传输前驱层进行间断地恒压(电压为正25V)带电处理60min，带电处理过程中包含电子传输前驱层的预制器件整体携带正电荷，相邻带电处理的间隔时间为10min，单次带电处理的时间为10min，获得厚度为50nm的电子传输层”。This embodiment provides a method for preparing a light-emitting device and the prepared light-emitting device. Compared with the method for preparing a light-emitting device provided in Embodiment 11, the difference between the method for preparing a light-emitting device in this embodiment is that step S11 is .6 is replaced with "In a nitrogen environment at normal temperature and pressure, use a clamp to fix the laminated structure containing the electron transmission precursor layer, provide an external power supply, connect the first end of the external power supply to the anode, and the second end of the external power supply to the ground , and then placed at a constant temperature of 150°C for continuous annealing treatment for 60 minutes, and during the annealing treatment process, turn on the external power supply to perform intermittently constant voltage (voltage is positive 25V) charging treatment on the electron transmission precursor layer for 60 minutes, the charging treatment process The prefabricated device containing the electron transport precursor layer carries a positive charge as a whole, the interval between adjacent charging treatments is 10 minutes, and the time for a single charging treatment is 10 minutes, to obtain an electron transport layer with a thickness of 50nm."
实施例17Example 17
本实施例提供了一种发光器件的制备方法及制得的发光器件，相较于实施 例11提供的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点在于：将步骤S11.6替换为“在常温常压的氮气环境下，采用夹具固定包含电子传输前驱层的叠层结构，提供外接电源，并将外接电源的第一端与阳极相连，外接电源的第二端接地，然然后置于150℃的恒定温度下连续地退火处理60min，并在退火处理过程中，开启外接电源，对电子传输前驱层施加矩形交流电压(频率为50Hz，电压为负25V至正25V)以进行间断地带电处理60min，带电处理过程中包含电子传输前驱层的预制器件整体交替变换地携带正电荷和负电荷，相邻带电处理的间隔时间为10min，单次带电处理的时间为10min，获得厚度为50nm的电子传输层”。This embodiment provides a method for preparing a light-emitting device and the prepared light-emitting device. Compared with the method for preparing a light-emitting device provided in Embodiment 11, the difference between the method for preparing a light-emitting device in this embodiment is that step S11 is .6 is replaced with "In a nitrogen environment at normal temperature and pressure, use a clamp to fix the laminated structure containing the electron transmission precursor layer, provide an external power supply, connect the first end of the external power supply to the anode, and the second end of the external power supply to the ground , and then placed at a constant temperature of 150°C for continuous annealing for 60 minutes. During the annealing process, turn on the external power supply and apply a rectangular AC voltage to the electron transport precursor layer (frequency is 50Hz, voltage is negative 25V to positive 25V) Perform intermittently charging treatment for 60 minutes. During the charging process, the entire prefabricated device including the electron transport precursor layer alternately carries positive and negative charges. The interval between adjacent charging treatments is 10 minutes, and the time for a single charging treatment is 10 minutes. Obtain an electron transport layer with a thickness of 50nm."
实施例18Example 18
本实施例提供了一种发光器件的制备方法及制得的发光器件，相较于实施例11提供的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点在于：将步骤S11.6替换为“在常温常压的氮气环境下，采用夹具固定包含电子传输前驱层的叠层结构，提供外接电源，并将外接电源的第一端与阳极相连，外接电源的第二端接地，开启外接电源，向电子传输前驱层施加电压为正25V的恒压以进行连续地带电处理60min，使得包含电子传输前驱层的预制器件整体携带正电荷，并在带电处理的过程中，对电子传输前驱层进行间断式恒温(150℃)退火处理60min以进行加热退火工序，相邻退火处理的间隔时间为5min，单次退火处理的时间为15min，获得厚度为50nm的电子传输层”。This embodiment provides a method for preparing a light-emitting device and the prepared light-emitting device. Compared with the method for preparing a light-emitting device provided in Embodiment 11, the difference between the method for preparing a light-emitting device in this embodiment is that step S11 is .6 is replaced with "In a nitrogen environment at normal temperature and pressure, use a clamp to fix the laminated structure containing the electron transmission precursor layer, provide an external power supply, connect the first end of the external power supply to the anode, and the second end of the external power supply to the ground , turn on the external power supply, apply a constant voltage of positive 25V to the electron transport precursor layer for continuous charging treatment for 60 minutes, so that the entire prefabricated device containing the electron transport precursor layer carries a positive charge, and during the charging process, the electrons The transmission precursor layer is subjected to intermittent constant temperature (150°C) annealing for 60 minutes to perform the heating annealing process. The interval between adjacent annealing treatments is 5 minutes, and the time for a single annealing treatment is 15 minutes to obtain an electron transport layer with a thickness of 50nm."
实施例19Example 19
本实施例提供了一种发光器件的制备方法及制得的发光器件，相较于实施例1提供的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点在于：将步骤S11.6替换为“在常温常压的氮气环境下，采用夹具固定包含电子传输前驱层的叠层结构，提供外接电源，并将外接电源的第一端与阳极相连，外接电源的第二端接地，开启外接电源，向电子传输前驱层施加矩形交流电压(频率为50Hz，电压为负25V至正25V)以进行连续地带电处理60min，使得包含电子传输前驱层的预制器件整体交替变换地携带正电荷和负电荷，并在带电处理的过程中，对电子传输前驱层进行间断式恒温(150℃)退火处理60min以进行加热退火工序，使得包含电子传输前驱层的预制器件整体交替变换地携带 正电荷和负电荷，相邻恒温热处理的间隔时间为5min，单次恒温热处理的时间为15min，获得厚度为50nm的电子传输层”。This embodiment provides a method for preparing a light-emitting device and the prepared light-emitting device. Compared with the method for preparing a light-emitting device provided in Embodiment 1, the difference between the method for preparing a light-emitting device in this embodiment is that step S11 is .6 is replaced with "In a nitrogen environment at normal temperature and pressure, use a clamp to fix the laminated structure containing the electron transmission precursor layer, provide an external power supply, connect the first end of the external power supply to the anode, and the second end of the external power supply to the ground , turn on the external power supply, apply a rectangular AC voltage (frequency is 50Hz, voltage is negative 25V to positive 25V) to the electron transmission precursor layer for continuous charging treatment for 60 minutes, so that the entire prefabricated device including the electron transmission precursor layer alternately carries positive energy and negative charges, and during the charging process, the electron transport precursor layer is subjected to intermittent constant temperature (150°C) annealing treatment for 60 minutes to perform the heating annealing process, so that the entire prefabricated device containing the electron transport precursor layer alternately carries positive Charges and negative charges, the interval time between adjacent constant temperature heat treatments is 5 minutes, the time of a single constant temperature heat treatment is 15 minutes, and an electron transport layer with a thickness of 50nm is obtained."
实施例20Example 20
本实施例提供了一种发光器件的制备方法及制得的发光器件，相较于实施例11提供的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点在于：将步骤S11.6替换为“在常温常压的氮气环境下，采用夹具固定包含电子传输前驱层的叠层结构，提供外接电源，并将外接电源的第一端与阳极相连，外接电源的第二端接地，开启外接电源，向电子传输前驱层施加电压为正25V的恒压以进行间断地带电处理60min，带电处理过程中包含电子传输前驱层的预制器件整体携带正电荷，并对电子传输前驱层进行间断式恒温(150℃)退火处理60min，带电处理与退火处理交替进行，单次带电处理的时间为5min，单次退火处理的时间为15min，获得厚度为50nm的电子传输层”。This embodiment provides a method for preparing a light-emitting device and the prepared light-emitting device. Compared with the method for preparing a light-emitting device provided in Embodiment 11, the difference between the method for preparing a light-emitting device in this embodiment is that step S11 is .6 is replaced with "In a nitrogen environment at normal temperature and pressure, use a clamp to fix the laminated structure containing the electron transmission precursor layer, provide an external power supply, connect the first end of the external power supply to the anode, and the second end of the external power supply to the ground , turn on the external power supply, apply a constant voltage of positive 25V to the electron transport precursor layer for intermittently charging treatment for 60 minutes. During the charging process, the entire prefabricated device containing the electron transport precursor layer carries a positive charge, and the electron transport precursor layer is charged. Intermittent constant temperature (150°C) annealing treatment for 60 minutes, charging treatment and annealing treatment are performed alternately, the time of a single charging treatment is 5 minutes, the time of a single annealing treatment is 15 minutes, and an electron transport layer with a thickness of 50nm is obtained."
实施例21Example 21
本实施例提供了一种发光器件的制备方法及制得的发光器件，相较于实施例11提供的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点在于：将步骤S11.6替换为“在常温常压的氮气环境下，采用夹具固定包含电子传输前驱层的叠层结构，提供外接电源，并将外接电源的第一端与阳极相连，外接电源的第二端接地，开启外接电源，向电子传输前驱层施加矩形交流电压(频率为50Hz，电压为负25V至正25V)以进行间断地带电处理60min，带电处理过程中包含电子传输前驱层的预制器件整体交替变换地携带正电荷和负电荷，并对电子传输前驱层进行间断式恒温(150℃)退火处理60min，带电处理与退火处理交替进行，单次带电处理的时间为5min，单次退火处理的时间为15min，获得厚度为50nm的电子传输层”。This embodiment provides a method for preparing a light-emitting device and the prepared light-emitting device. Compared with the method for preparing a light-emitting device provided in Embodiment 11, the difference between the method for preparing a light-emitting device in this embodiment is that step S11 is .6 is replaced with "In a nitrogen environment at normal temperature and pressure, use a clamp to fix the laminated structure containing the electron transmission precursor layer, provide an external power supply, connect the first end of the external power supply to the anode, and the second end of the external power supply to the ground , turn on the external power supply, apply a rectangular AC voltage (frequency is 50Hz, voltage is negative 25V to positive 25V) to the electron transmission precursor layer for intermittently charging treatment for 60 minutes. During the charging process, the entire prefabricated device including the electron transmission precursor layer is alternately transformed The ground carries positive and negative charges, and the electron transport precursor layer is subjected to intermittent constant temperature (150°C) annealing treatment for 60 minutes. The charging treatment and annealing treatment are performed alternately. The time of a single charging treatment is 5 minutes, and the time of a single annealing treatment is In 15 minutes, an electron transport layer with a thickness of 50nm was obtained."
实施例22Example 22
本实施例提供了一种发光器件的制备方法及制得的发光器件，相较于实施例11提供的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点在于：将步骤S11.6替换为“在常温常压的氮气环境下，对电子传输前驱层进行连续地恒温(150℃)退火处理60min以形成干膜，然后采用夹具固定包含干膜的叠层结构，提供外接电源，并将外接电源的第一端与阳极相连，外接电源 的第二端接地，开启外接电源，向干膜施加矩形交流电压(频率为50Hz，电压为负25V至正25V)以进行连续地带电处理60min，带电处理过程中包含干膜的预制器件整体交替变换地携带正电荷和负电荷，获得厚度为50nm的电子传输层”。This embodiment provides a method for preparing a light-emitting device and the prepared light-emitting device. Compared with the method for preparing a light-emitting device provided in Embodiment 11, the difference between the method for preparing a light-emitting device in this embodiment is that step S11 is .6 is replaced by "Under a nitrogen environment at normal temperature and pressure, the electron transport precursor layer is continuously annealed at a constant temperature (150°C) for 60 minutes to form a dry film, and then a clamp is used to fix the stacked structure containing the dry film, and an external power supply is provided , connect the first end of the external power supply to the anode, and connect the second end of the external power supply to ground. Turn on the external power supply and apply a rectangular AC voltage (frequency 50Hz, voltage negative 25V to positive 25V) to the dry film for continuous charging. After 60 minutes of treatment, the entire prefabricated device containing the dry film alternately carries positive and negative charges during the charging process, obtaining an electron transport layer with a thickness of 50nm."
实施例23Example 23
本实施例提供了一种发光器件的制备方法及制得的发光器件，相较于实施例11提供的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点在于：将步骤S11.6替换为“在常温常压的氮气环境下，采用夹具固定包含电子传输前驱层(湿膜)的叠层结构，提供外接电源，并将外接电源的第一端与阳极相连，外接电源的第二端接地，开启外接电源，向电子传输前驱层施加矩形交流电压(频率为50Hz，电压为负25V至正25V)以进行连续地带电处理60min，带电处理过程中包含电子传输前驱层的预制器件整体交替变换地携带正电荷和负电荷，带电处理结束后，对预制器件进行连续地恒温(150℃)退火处理60min以形成厚度为50nm的电子传输层”。This embodiment provides a method for preparing a light-emitting device and the prepared light-emitting device. Compared with the method for preparing a light-emitting device provided in Embodiment 11, the difference between the method for preparing a light-emitting device in this embodiment is that step S11 is .6 is replaced by "In a nitrogen environment at normal temperature and pressure, use a clamp to fix the laminated structure containing the electron transmission precursor layer (wet film), provide an external power supply, and connect the first end of the external power supply to the anode. The second end is grounded, the external power supply is turned on, and a rectangular AC voltage (frequency is 50Hz, voltage is negative 25V to positive 25V) is applied to the electron transmission precursor layer for continuous charging treatment for 60 minutes. The charging process includes the prefabrication of the electron transmission precursor layer The entire device alternately carries positive and negative charges. After the charging process, the prefabricated device is continuously annealed at a constant temperature (150°C) for 60 minutes to form an electron transport layer with a thickness of 50nm."
对比例1Comparative example 1
本对比例提供了一种发光器件的制备方法及制得的发光器件，相较于实施例1提供的发光器件的制备方法，本对比例中发光器件的制备方法的区别点在于：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30mg/mL的纳米ZnO(粒径为5nm)-乙醇溶液以获得湿膜，然后置于150℃的恒定温度下连续地退火处理60min，获得厚度为50nm的电子传输层”。This comparative example provides a method for preparing a light-emitting device and the prepared light-emitting device. Compared with the method for preparing a light-emitting device provided in Embodiment 1, the difference between the method for preparing a light-emitting device in this comparative example is that step S1 is .5 is replaced with "In a nitrogen environment at normal temperature and pressure, spin-coat a nano-ZnO (particle size: 5 nm)-ethanol solution with a concentration of 30 mg/mL on the side of the light-emitting layer away from the hole transport layer in step S1.4. A wet film was obtained and then continuously annealed at a constant temperature of 150°C for 60 minutes to obtain an electron transport layer with a thickness of 50nm."
对比例2Comparative example 2
本对比例提供了一种发光器件的制备方法及制得的发光器件，相较于实施例11提供的发光器件的制备方法，本对比例中发光器件的制备方法的区别点在于：将步骤S11.6替换为“在常温常压的氮气环境下，对电子传输前驱层进行连续地恒温(150℃)退火处理60min，获得厚度为50nm的电子传输层”。This comparative example provides a method for preparing a light-emitting device and the prepared light-emitting device. Compared with the method for preparing a light-emitting device provided in Embodiment 11, the difference between the method for preparing a light-emitting device in this comparative example is that step S11 is .6 is replaced by "Under a nitrogen environment at normal temperature and pressure, the electron transport precursor layer is continuously annealed at a constant temperature (150°C) for 60 minutes to obtain an electron transport layer with a thickness of 50nm."
实验例1Experimental example 1
对实施例1至实施例10以及对比例1的发光器件进行性能检测，比较各个发光器件封装完成当天的最大外量子效率(EQE max,％)和亮度由100％衰减至 95％所需的时间(LT95@1000nit,h)，以及比较各个发光器件封装后放置30天的EQE max和LT95@1000nit。 Conduct performance testing on the light-emitting devices of Examples 1 to 10 and Comparative Example 1, and compare the maximum external quantum efficiency (EQE max , %) and the time required for the brightness to decay from 100% to 95% on the day the packaging of each light-emitting device is completed. (LT95@1000nit,h), and compare the EQE max and LT95@1000nit of each light-emitting device after being packaged for 30 days.
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、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。Use FPD optical characteristic measurement equipment (efficiency test system built by LabView to control QE-PRO spectrometer, Keithley 2400 and Keithley 6485) to detect the voltage, current, brightness, luminescence spectrum and other parameters of each light-emitting device, and then calculate and obtain the external parameters. Quantum efficiency, power efficiency and other key parameters, and use life testing equipment to test the service life of each of the above-mentioned light-emitting devices.
具体的，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的LT95@1000nit，实验结果详见下表1：Specifically, the life test uses the constant current method. Driven by a constant current (2mA current), a silicon photonic system is used to test the brightness changes of each light-emitting device, and the time required for the brightness to decay from 100% to 95% is recorded (T95, h ), and calculate the LT95@1000nit of each light-emitting device. The experimental results are detailed in Table 1 below:
表1 实施例1至实施例10以及对比例1的发光器件的性能检测结果Table 1 Performance test results of the light-emitting devices of Examples 1 to 10 and Comparative Example 1
Figure PCTCN2022140059-appb-000001
Figure PCTCN2022140059-appb-000001
由表1可知，实施例1至实施例10中发光器件的综合性能明显优于对比例1中发光器件，以实施例2为例，在封装当天，实施例2中发光器件的EQE max是对比例1中发光器件的EQE max的2.2倍，且实施例5中发光器件的LT95@1000nit是对比例1中发光器件的LT95@1000nit的3.7倍；封装放置30天后，实施例5中发光器件的EQE max是对比例1中发光器件的EQE max的3.7倍，且实施例5中发光器件的LT95@1000nit是对比例1中发光器件的 LT95@1000nit的15.2倍。比较封装当天和封装放置30天的性能检测数据可知，在封装放置的30天内，实施例1至实施例10中发光器件的发光性能和工作寿命变化幅度较小，稳定性理想，而对比例1中发光器件的EQE max下降了51％，且对比例1中发光器件的LT95@1000nit下降了75％，充分说明：在制备电子传输层的过程中，在预设时间范围内，对湿膜进行退火处理和通电处理，能够提高电子传输层的结晶度和稳定性，从而提升发光器件的发光性能和工作寿命。 As can be seen from Table 1, the comprehensive performance of the light-emitting devices in Examples 1 to 10 is significantly better than that of the light-emitting devices in Comparative Example 1. Taking Example 2 as an example, on the day of packaging, the EQE max of the light-emitting devices in Example 2 is The EQE max of the light-emitting device in Example 1 is 2.2 times, and the LT95@1000nit of the light-emitting device in Example 5 is 3.7 times the LT95@1000nit of the light-emitting device in Comparative Example 1; after the package is placed for 30 days, the EQE max of the light-emitting device in Example 5 The EQE max is 3.7 times that of the light-emitting device in Comparative Example 1, and the LT95@1000nit of the light-emitting device in Example 5 is 15.2 times that of the light - emitting device in Comparative Example 1. Comparing the performance testing data on the day of packaging and the 30 days after the packaging was placed, it can be seen that within the 30 days after the packaging was placed, the luminous performance and working life of the light-emitting devices in Example 1 to Example 10 changed slightly, and the stability was ideal, while Comparative Example 1 The EQE max of the medium-light-emitting device dropped by 51%, and the LT95@1000nit of the medium-light-emitting device in Comparative Example 1 dropped by 75%, which fully demonstrates that during the preparation of the electron transport layer, the wet film was processed within the preset time range. Annealing treatment and electrification treatment can improve the crystallinity and stability of the electron transport layer, thereby improving the luminous performance and working life of the light-emitting device.
实验例2Experimental example 2
对实施例11至实施例23以及对比例2的发光器件进行性能检测，比较各个发光器件封装完成当天的最大外量子效率(EQE max,％)和亮度由100％衰减至95％所需的时间(LT95@1000nit,h)，以及比较各个发光器件封装后放置30天的EQE max和LT95@1000nit。各个发光器件的性能检测方法参照实验例1，实验结果详见下表2： Conduct performance testing on the light-emitting devices of Examples 11 to 23 and Comparative Example 2, and compare the maximum external quantum efficiency (EQE max , %) and the time required for the brightness to decay from 100% to 95% on the day the packaging of each light-emitting device is completed. (LT95@1000nit,h), and compare the EQE max and LT95@1000nit of each light-emitting device after being packaged for 30 days. The performance testing method of each light-emitting device refers to Experimental Example 1. The experimental results are detailed in Table 2 below:
表2 实施例11至实施例23以及对比例2的发光器件的性能检测结果Table 2 Performance test results of the light-emitting devices of Examples 11 to 23 and Comparative Example 2
Figure PCTCN2022140059-appb-000002
Figure PCTCN2022140059-appb-000002
Figure PCTCN2022140059-appb-000003
Figure PCTCN2022140059-appb-000003
由表2可知，实施例11至实施例23中发光器件的综合性能明显优于对比例中发光器件，以实施例15为例，在封装当天，实施例15中发光器件的EQE max是对比例2中发光器件的EQE max的2.2倍，且实施例15中发光器件的LT95@1000nit是对比例2中发光器件的LT95@1000nit的3.4倍；封装放置30天后，实施例15中发光器件的EQE max是对比例2中发光器件的EQE max的3.7倍，且实施例15中发光器件的LT95@1000nit是对比例2中发光器件的LT95@1000nit的14.7倍。比较封装当天和封装放置30天的性能检测数据可知，在封装放置的30天内，实施例11至实施例23中发光器件的发光性能和工作寿命变化幅度较小，稳定性理想，而对比例2中发光器件的EQE max下降了51％，且对比例2中发光器件的LT95@1000nit下降了75％，充分说明：在制备电子传输层的过程中，在预设时间范围内，对电子传输前驱层进行退火处理和带电处理，能够提高电子传输层的结晶度和稳定性，从而提升发光器件的发光性能和工作寿命。 It can be seen from Table 2 that the comprehensive performance of the light-emitting devices in Examples 11 to 23 is significantly better than that of the light-emitting devices in the Comparative Example. Taking Example 15 as an example, on the day of packaging, the EQE max of the light-emitting device in Example 15 is the same as that of the Comparative Example. 2.2 times the EQE max of the light-emitting device in Example 2, and the LT95@1000nit of the light-emitting device in Example 15 is 3.4 times the LT95@1000nit of the light-emitting device in Comparative Example 2; after the package is placed for 30 days, the EQE of the light-emitting device in Example 15 max is 3.7 times that of the EQE max of the light-emitting device in Comparative Example 2, and the LT95@1000nit of the light-emitting device in Example 15 is 14.7 times that of the light-emitting device in Comparative Example 2. Comparing the performance testing data on the day of packaging and the 30 days of packaging placement, it can be seen that within the 30 days of packaging placement, the luminous performance and working life of the light-emitting devices in Example 11 to Example 23 changed slightly, and the stability was ideal, while Comparative Example 2 The EQE max of the medium light-emitting device dropped by 51%, and the LT95@1000nit of the medium light-emitting device in Comparative Example 2 dropped by 75%, which fully demonstrates that during the preparation of the electron transport layer, within the preset time range, the electron transport precursor The layer is annealed and charged to improve the crystallinity and stability of the electron transport layer, thereby improving the luminous performance and working life 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的制备方法、发光器件与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 the preparation method of a light-emitting device, the light-emitting device and the 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:
    提供预制器件，在所述预制器件的一侧施加包含纳米金属氧化物的溶液；以及providing a prefabricated device, applying a solution containing nanometal oxides to one side of the prefabricated device; and
    在预设的时间范围内，对位于所述预制器件的一侧的所述溶液进行退火处理和电处理，以用于形成电子传输层；Within a preset time range, perform annealing treatment and electrical treatment on the solution located on one side of the prefabricated device to form an electron transport layer;
    其中，当所述发光器件为正置型结构时，所述预制器件包括层叠设置的底电极和发光层，所述溶液施加于所述发光层远离所述底电极的一侧，所述底电极为阳极；Wherein, when the light-emitting device has a positive structure, the prefabricated device includes a bottom electrode and a light-emitting layer arranged in a stack, and the solution is applied to the side of the light-emitting layer away from the bottom electrode, and the bottom electrode is anode;
    当所述发光器件为倒置型结构时，所述预制器件包括底电极，所述溶液施加于所述底电极的一侧，所述底电极为阴极。When the light-emitting device has an inverted structure, the prefabricated device includes a bottom electrode, the solution is applied to one side of the bottom electrode, and the bottom electrode is a cathode.
  2. 根据权利要求1所述的制备方法，其中，所述退火处理的时间段与所述电处理的时间段至少部分重叠，所述退火处理的方式和所述电处理的方式为下列任意一种情况：The preparation method according to claim 1, wherein the time period of the annealing treatment and the time period of the electrical treatment at least partially overlap, and the method of the annealing treatment and the method of the electrical treatment is any one of the following situations :
    (a1)所述退火处理为连续式的，且所述电处理为连续式的；(a1) The annealing treatment is continuous, and the electrical treatment is continuous;
    (a2)所述退火处理为连续式的，且所述电处理为间断式的；(a2) The annealing treatment is continuous, and the electrical treatment is intermittent;
    (a3)所述退火处理为间断式的，且所述电处理为连续式的；(a3) The annealing treatment is intermittent, and the electrical treatment is continuous;
    (a4)所述退火处理为间断式的，且所述电处理为间断式的。(a4) The annealing treatment is intermittent, and the electrical treatment is intermittent.
  3. 根据权利要求1所述的制备方法，其中，所述退火处理的时间段与所述电处理的时间段不发生重叠，所述退火处理的方式和所述电处理的方式为下列任意一种情况：The preparation method according to claim 1, wherein the time period of the annealing treatment and the time period of the electrical treatment do not overlap, and the method of the annealing treatment and the method of the electrical treatment are any one of the following situations :
    (b1)所述退火处理与所述电处理交替进行；(b1) The annealing treatment and the electrical treatment are performed alternately;
    (b2)对位于所述预制器件的一侧的所述溶液完成所述电处理之后，再进行所述退火处理。(b2) After completing the electrical treatment on the solution located on one side of the prefabricated device, perform the annealing treatment.
  4. 根据权利要求1至3任一项中所述的制备方法，其中，所述退火处理的温度为80℃至250℃；The preparation method according to any one of claims 1 to 3, wherein the temperature of the annealing treatment is 80°C to 250°C;
    所述退火处理的时间为5min至120min。The time of the annealing treatment is 5 min to 120 min.
  5. 根据权利要求1至4任一项中所述的制备方法，其中，所述电处理为 带电处理，所述带电处理是使所述电子传输前驱层携带正电荷或负电荷，或使所述电子传输前驱层交替变换地携带正电荷和负电荷。The preparation method according to any one of claims 1 to 4, wherein the electrical treatment is a charging treatment, and the charging treatment is to make the electron transport precursor layer carry positive or negative charges, or to make the electrons The transport precursor layer alternately carries positive and negative charges.
  6. 根据权利要求5所述的制备方法，其中，所述带电处理包括步骤：提供外接电源，所述外接电源的第一端与所述底电极相连，且所述外接电源的第二端接地；开启所述外接电源，以使所述第一端与所述第二端之间具有电位差。The preparation method according to claim 5, wherein the charging treatment includes the steps of: providing an external power supply, the first end of the external power supply is connected to the bottom electrode, and the second end of the external power supply is grounded; turning on The external power supply is connected so that there is a potential difference between the first end and the second end.
  7. 根据权利要求5或6所述的制备方法，其中，在所述带电处理的过程中，所述外接电源向所述电子传输前驱层施加恒压或交流电压；The preparation method according to claim 5 or 6, wherein during the charging process, the external power supply applies a constant voltage or an AC voltage to the electron transport precursor layer;
    其中，所述恒压的电压数值为10V至30V；Wherein, the voltage value of the constant voltage is 10V to 30V;
    所述交流电压的频率为10Hz至200Hz，有效电压的数值为10V至30V。The frequency of the AC voltage is 10Hz to 200Hz, and the effective voltage is 10V to 30V.
  8. 根据权利要求5至7任一项中所述的制备方法，其中，所述带电处理的时间为5min至120min；The preparation method according to any one of claims 5 to 7, wherein the charging treatment time is 5 min to 120 min;
    所述带电处理为连续式的；或者，所述带电处理为间断式的，单次所述带电处理的时间为5min至20min，相邻所述带电处理的间隔时间为5min至20min。The charging treatment is continuous; or, the charging treatment is intermittent, the time of a single charging treatment is 5 min to 20 min, and the interval between adjacent charging treatments is 5 min to 20 min.
  9. 根据权利要求5至8任一项中所述的制备方法，其中，所述退火处理与所述带电处理的重叠时间为下列任意一种情况：The preparation method according to any one of claims 5 to 8, wherein the overlap time of the annealing treatment and the charging treatment is any of the following situations:
    (a11)当所述退火处理为连续式的，且所述带电处理为连续式的时，所述退火处理与所述带电处理的重叠时间为5min至120min；(a11) When the annealing treatment is continuous and the charging treatment is continuous, the overlap time of the annealing treatment and the charging treatment is 5 min to 120 min;
    (a12)所述退火处理为连续式的，且所述带电处理为间断式的时，所述退火处理与所述带电处理的重叠时间为5min至115min；(a12) When the annealing treatment is continuous and the charging treatment is intermittent, the overlap time of the annealing treatment and the charging treatment is 5 min to 115 min;
    (a13)当所述退火处理为间断式的，且所述带电处理为连续式的时，相邻所述退火处理的间隔时间为5min至10min，单次所述退火处理的时间为10min至30min，所述退火处理与所述带电处理的重叠时间为5min至115min；(a13) When the annealing treatment is intermittent and the charging treatment is continuous, the interval between adjacent annealing treatments is 5 min to 10 min, and the time for a single annealing treatment is 10 min to 30 min. , the overlap time of the annealing treatment and the charging treatment is 5min to 115min;
    (a14)当所述退火处理为间断式的，且所述带电处理为间断式的时，相邻所述退火处理的间隔时间为5min至10min，单次所述退火处理的时间为10min至30min，所述退火处理与所述带电处理的重叠时间为5min至115min。(a14) When the annealing treatment is intermittent and the charging treatment is intermittent, the interval between adjacent annealing treatments is 5 min to 10 min, and the time for a single annealing treatment is 10 min to 30 min. , the overlap time of the annealing treatment and the charging treatment is 5min to 115min.
  10. 根据权利要求1至4任一项中所述的制备方法，其中，所述电处理为通电处理，所述通电处理是将所述溶液接入外接电源的阴极与阳极之间以形成闭合回路。The preparation method according to any one of claims 1 to 4, wherein the electrical treatment is electrification treatment, and the electrification treatment is to connect the solution between the cathode and the anode of an external power supply to form a closed loop.
  11. 根据权要求10所述的制备方法，其中，所述通电处理包括步骤：将包含所述溶液的所述预制器件固定于夹具上，然后将外接电源的阳极和阴极分别与所述溶液所形成的湿膜中相对设置的两侧相连。The preparation method according to claim 10, wherein the electrification treatment includes the step of: fixing the prefabricated device containing the solution on a fixture, and then connecting the anode and cathode of the external power supply to the electrode formed by the solution respectively. The opposite sides of the wet film are connected.
  12. 根据权利要求10或11所述的制备方法，其中，所述通电处理为恒流式通电处理、恒压式通电处理或交变式通电处理；The preparation method according to claim 10 or 11, wherein the energization treatment is a constant current energization treatment, a constant voltage energization treatment or an alternating current energization treatment;
    在所述通电处理的过程中，位于所述预制器件的一侧的所述溶液的电流密度为100mA/cm 2至300mA/cm 2。 During the electrification treatment, the current density of the solution located on one side of the prefabricated device is 100 mA/cm 2 to 300 mA/cm 2 .
  13. 根据权利要求10至12任一项中所述的制备方法，其中，所述退火处理的时间段与所述通电处理的时间段至少部分交叠，所述退火处理与所述带电处理的处理时间为下述任意一种情况：The preparation method according to any one of claims 10 to 12, wherein the time period of the annealing treatment and the time period of the electrification treatment at least partially overlap, and the processing time of the annealing treatment and the electrification treatment For any of the following situations:
    (a111)当所述退火处理为连续式的，且所述通电处理为间断式的时，相邻所述通电处理的间隔时间为5min至10min，单次所述通电处理的时间为10min至15min；(a111) When the annealing treatment is continuous and the energization treatment is intermittent, the interval time between adjacent energization treatments is 5 min to 10 min, and the time of a single energization treatment is 10 min to 15 min. ;
    (a112)当所述退火处理为间断式的，且所述通电处理为连续式的时，相邻所述退火处理的间隔时间为5min至10min，单次所述退火处理的时间为10min至30min；(a112) When the annealing treatment is intermittent and the energization treatment is continuous, the interval between adjacent annealing treatments is 5 min to 10 min, and the time of a single annealing treatment is 10 min to 30 min. ;
    (a113)所述退火处理为间断式的，且所述通电处理为间断式的时，相邻所述退火处理的间隔时间为5min至20min，单次所述退火处理的时间为5min至20min；相邻所述通电处理的间隔时间为5min至20min，单次所述通电处理的时间为5min至20min；(a113) The annealing treatment is intermittent, and when the energization treatment is intermittent, the interval between adjacent annealing treatments is 5 min to 20 min, and the time for a single annealing treatment is 5 min to 20 min; The interval time between adjacent energization treatments is 5min to 20min, and the time of a single energization treatment is 5min to 20min;
    其中，所述通电处理的总时间为5min至120min，所述退火处理与所述通电处理的交叠总时间为5min至120min。Wherein, the total time of the energization treatment is 5 min to 120 min, and the total overlap time of the annealing treatment and the energization treatment is 5 min to 120 min.
  14. 根据权利要求10至12任一项中所述的制备方法，其中，所述退火处理与所述通电处理交替进行；The preparation method according to any one of claims 10 to 12, wherein the annealing treatment and the electrification treatment are performed alternately;
    所述退火处理的总时间为5min至60min，所述通电处理的总时间为5min至60min；单次所述通电处理的时间为5min至20min，单次所述退火处理的时间为5min至20min。The total time of the annealing treatment is 5min to 60min, and the total time of the energization treatment is 5min to 60min; the time of a single energization treatment is 5min to 20min, and the time of a single annealing treatment is 5min to 20min.
  15. 根据权利要求1至14任一项中所述的制备方法，其中，当所述发光器件为正置型结构时，所述制备方法还包括步骤：在所述预制器件的所述一侧 形成电子传输层之后，在所述电子传输层远离所述发光层的一侧形成阴极；The preparation method according to any one of claims 1 to 14, wherein when the light-emitting device is an upright structure, the preparation method further includes the step of: forming an electron transmission layer on one side of the prefabricated device. After the layer is formed, a cathode is formed on the side of the electron transport layer away from the light-emitting layer;
    当所述发光器件为倒置型结构时，所述制备方法还包括如下步骤：When the light-emitting device has an inverted structure, the preparation method further includes the following steps:
    在所述预制器件的所述一侧形成电子传输层之后，在所述电子传输层远离所述阴极的一侧形成发光层；以及After forming an electron transport layer on the side of the prefabricated device, forming a light-emitting layer on a side of the electron transport layer away from the cathode; and
    在所述发光层远离所述电子传输层的一侧形成阳极。An anode is formed on a side of the light-emitting layer away from the electron transport layer.
  16. 根据权利要求1至15任一项中所述的制备方法，其中，所述制备方法还包括步骤：在所述阳极与所述发光层之间形成空穴功能层，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 preparation method according to any one of claims 1 to 15, wherein the preparation method further includes the step of: forming a hole functional layer between the anode and the light-emitting layer, the hole functional layer comprising One or more of a hole injection layer and a hole transport layer. When the hole functional 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 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'-二胺中的一种或多种； 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' -diamine and one or more of 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，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 transition metal oxides and transition metal chalcogenide compounds, the transition metal oxide is selected from one or more NiO x , MoO x , WO x and CrO x , the transition metal sulfur The system compound is selected from one or more of MoS x , MoS x , WS x , WSe x and CuS.
  17. 一种发光器件，其中，所述发光器件的制备方法包括如下步骤：A light-emitting device, wherein the preparation method of the light-emitting device includes the following steps:
    提供预制器件，在所述预制器件的一侧施加包含纳米金属氧化物的溶液；以及providing a prefabricated device, applying a solution containing nanometal oxides to one side of the prefabricated device; and
    在预设的时间范围内，对位于所述预制器件的一侧的所述溶液进行退火处理和电处理，以用于形成电子传输层；Within a preset time range, perform annealing treatment and electrical treatment on the solution located on one side of the prefabricated device to form an electron transport layer;
    其中，当所述发光器件为正置型结构时，所述预制器件包括层叠设置的底电极和发光层，所述溶液施加于所述发光层远离所述底电极的一侧，所述底电 极为阳极；Wherein, when the light-emitting device has a positive structure, the prefabricated device includes a bottom electrode and a light-emitting layer arranged in a stack, and the solution is applied to the side of the light-emitting layer away from the bottom electrode, and the bottom electrode is anode;
    当所述发光器件为倒置型结构时，所述预制器件包括底电极，所述溶液施加于所述底电极的一侧，所述底电极为阴极。When the light-emitting device has an inverted structure, the prefabricated device includes a bottom electrode, the solution is applied to one side of the bottom electrode, and the bottom electrode is a cathode.
  18. 根据权利要求17所述的发光器件，其中，所述发光层的材料为有机发光材料或量子点；The light-emitting device according to claim 17, wherein the material of the light-emitting layer is an organic light-emitting material or quantum dots;
    所述有机发光材料选自二芳香基蒽衍生物、二苯乙烯芳香族衍生物、芘衍生物、芴衍生物、TBPe荧光材料、TTPA荧光材料、TBRb荧光材料以及DBP荧光材料中的一种或多种；The organic light-emitting material is selected from one of diarylanthracene derivatives, stilbene aromatic derivatives, pyrene derivatives, fluorene derivatives, TBPe fluorescent materials, TTPA fluorescent materials, TBRb fluorescent materials and DBP fluorescent materials, or variety;
    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中的一种或多种；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族化合物以及I-III-VI族化合物中的一种或多种，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以及HgZnSTe中的一种或多种，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以及InAlPSb中的一种或多种，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以及SnPbSTe中的一种或多种，所述I-III-VI族化合物选自CuInS、CuInSe以及AgInS中的一种或多种；The quantum dots are selected from one or more of single component quantum dots, core-shell structure quantum dots, inorganic perovskite quantum dots, and organic-inorganic hybrid perovskite quantum dots; when the quantum dots are selected from In the case of single-component quantum dots or core-shell structure quantum dots, the material of the single-component quantum dot, the material of the core of the core-shell structure quantum dot, and the material of the shell of the core-shell structure quantum dot are selected independently of each other. One or more of Group II-VI compounds, Group III-V compounds, Group IV-VI compounds and Group I-III-VI compounds, wherein the Group 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, HgZnSe ,HgZnTe , one or more of CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe and 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 , one or more of GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs and InAlPSb, the IV-VI compound is selected from SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, SnSeTe , one or more of SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, SnPbSeTe and SnPbSTe, the I-III-VI compound is selected from one or more of CuInS, CuInSe and AgInS kind;
    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.
  19. 一种显示装置，其中，所述显示装置包括发光器件，所述发光器件的制备方法包括如下步骤：A display device, wherein the display device includes a light-emitting device, and the preparation method of the light-emitting device includes the following steps:
    提供预制器件，在所述预制器件的一侧施加包含纳米金属氧化物的溶液；以及providing a prefabricated device, applying a solution containing nanometal oxides to one side of the prefabricated device; and
    在预设的时间范围内，对位于所述预制器件的一侧的所述溶液进行退火处理和电处理，以用于形成电子传输层；Within a preset time range, perform annealing treatment and electrical treatment on the solution located on one side of the prefabricated device to form an electron transport layer;
    其中，当所述发光器件为正置型结构时，所述预制器件包括层叠设置的底电极和发光层，所述溶液施加于所述发光层远离所述底电极的一侧，所述底电极为阳极；Wherein, when the light-emitting device has a positive structure, the prefabricated device includes a bottom electrode and a light-emitting layer arranged in a stack, and the solution is applied to the side of the light-emitting layer away from the bottom electrode, and the bottom electrode is anode;
    当所述发光器件为倒置型结构时，所述预制器件包括底电极，所述溶液施加于所述底电极的一侧，所述底电极为阴极。When the light-emitting device has an inverted structure, the prefabricated device includes a bottom electrode, the solution is applied to one side of the bottom electrode, and the bottom electrode is a cathode.
  20. 根据权利要求19所述的显示装置，其中，所述电处理为下述任意一种情况：The display device according to claim 19, wherein the electrical processing is any one of the following conditions:
    (C1)所述电处理为带电处理，所述带电处理是使所述电子传输前驱层携带正电荷或负电荷，或使所述电子传输前驱层交替变换地携带正电荷和负电荷；(C1) The electrical treatment is a charging treatment, which causes the electron transport precursor layer to carry positive charges or negative charges, or causes the electron transport precursor layer to alternately carry positive charges and negative charges;
    (C2)所述电处理为通电处理，所述通电处理是将所述溶液接入外接电源的阴极与阳极之间以形成闭合回路。(C2) The electrical treatment is an electrification treatment, in which the solution is connected between the cathode and the anode of an external power supply to form a closed loop.
PCT/CN2022/140059 2022-04-14 2022-12-19 Manufacturing method for light emitting device, light emitting device, and display apparatus WO2023197659A1 (en)

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US20140147951A1 (en) * 2012-11-27 2014-05-29 Massachusetts Institute Of Technology Deposition of semiconductor nanocrystals for light emitting devices
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CN108987597A (en) * 2018-07-17 2018-12-11 嘉兴纳鼎光电科技有限公司 The composition of ambient stable storage and the preparation method of light emitting diode with quantum dots device
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