WO2023202151A1 - 发光二极管膜层及其成膜方法、发光二极管 - Google Patents

发光二极管膜层及其成膜方法、发光二极管 Download PDF

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WO2023202151A1
WO2023202151A1 PCT/CN2022/143069 CN2022143069W WO2023202151A1 WO 2023202151 A1 WO2023202151 A1 WO 2023202151A1 CN 2022143069 W CN2022143069 W CN 2022143069W WO 2023202151 A1 WO2023202151 A1 WO 2023202151A1
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film
forming
layer
forming solution
megasonic
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French (fr)
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关杰豪
张建新
杨一行
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TCL Technology Group Co Ltd
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TCL Technology Group Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/002—Processes for applying liquids or other fluent materials the substrate being rotated
    • B05D1/005—Spin coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • 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]
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H10K71/15—Deposition of organic active material using liquid deposition, e.g. spin coating characterised by the solvent used

Definitions

  • the present application relates to the field of display technology, and in particular to a light-emitting diode film layer and a film forming method thereof, and a light-emitting diode.
  • the device structure used by most light-emitting diodes includes a substrate, anode, a transparent hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer and a cathode. In some cases, it also includes a barrier layer, etc. In order to improve the light extraction efficiency and working life of the device, the preparation of these functional layers requires controlling the plane roughness and film thickness.
  • the solution method has the advantages of simple process, low cost, and easy realization of large-area film formation. It is an important method for preparing different film layers of display devices. Common solution methods include spin coating, inkjet printing, etc. During film preparation, the film-forming solution is generally placed in a dropping device (see Figure 1). For colloidal solutions, layered solutions, metastable solutions, etc.
  • the solution is prone to changes in solution concentration due to problems such as solute coagulation and precipitation, making it difficult to control the thickness of the prepared film layer; and the solution in the dripping device (such as quantum dot metal oxide ZnO colloidal solution)
  • solute agglomeration occurs, the particles formed will cause bumps in the film layer. This may cause the intrusion of water and oxygen, thus affecting the life of the device. What's more, the device may be damaged due to discharge at the tip of the bumps in the film layer. damage.
  • their properties are very unstable and need to be prepared and used immediately, which puts forward higher process requirements for the application of solution methods.
  • the present application provides a light-emitting diode film layer and a film forming method thereof, a light-emitting diode film layer and a film forming method thereof.
  • Embodiments of the present application provide a method for forming a light-emitting diode film layer, which includes: providing a substrate; and applying an atomized film-forming solution to the substrate and depositing the film-forming solution.
  • the film-forming solution is atomized using megasonic waves, and the frequency of the megasonic waves is 400 to 1000 kHz.
  • the power of the megasonic wave is 20-200W.
  • the steps of applying atomized film-forming solution to the substrate and depositing the film-forming solution are performed in a protective gas environment; wherein, the protective gas The water content in the environment is less than 5 ppm; and/or the protective gas is selected from one or more of nitrogen and argon.
  • the film-forming solution is a film-forming solution dispersed by the megasonic waves.
  • the film-forming solution is atomized to form the atomized film-forming solution after being dispersed by the megasonic wave.
  • the film-forming solution includes a film-forming solute and a film-forming solvent
  • the film-forming solute includes a ligand
  • the ligand is selected from C1 to 8 thiols, One or more of C3-8 phosphine, C1-8 phosphonic acid, C1-8 amine, C1-4 carboxylic acid, C1-4 alcohol.
  • the film-forming solute is synthesized using reactants, and during the synthesis of the film-forming solute, the megasonic waves are used to disperse the reactants.
  • using the reactants to synthesize the film-forming solute includes: providing the reactants and a polar solvent, the reactants including metal salts and precipitants; and The metal salt, the precipitant and the polar solvent are mixed under the dispersion of the megasonic wave.
  • the metal salt is selected from one or more of nitrate, acetate, sulfate, chloride salt, carbonate, and perchlorate; and/or the precipitating agent is selected from one or more of oxalic acid, urea, ammonia, sodium hydroxide, potassium hydroxide, carbonic acid, bicarbonate, thiourea, tetramethylammonium hydroxide, and ethanolamine; and/or Or the polar solvent is selected from one or more types of methanol, ethanol, isopropyl alcohol, and water.
  • the film-forming solute includes ZnO
  • the metal salt is selected from zinc organic salts
  • the precipitant is selected from alkali
  • the mass of the zinc organic salt and the alkali is The ratio is 1 ⁇ 3:1.
  • the megasonic waves when dispersing the film-forming solution or synthesizing the film-forming solute, are used to perform continuous disturbance; or the megasonic waves are used to cause continuous disturbance in a time of 0.5 to 10 minutes. Intermittent disturbances are performed at intervals.
  • the megasonic waves are used to perform intermittent perturbation at intervals of 0.5 to 1 min.
  • the method further includes: using the megasonic wave to atomize the cleaning agent to the surface formed by the film-forming solution; and/or after the deposition, After the film-forming solution is provided, the method further includes: using the megasonic wave to atomize the ligand exchange solution to the surface formed by the film-forming solution.
  • the light-emitting diode film layer is a hole injection layer, a hole transport layer, a hole blocking layer, a light emitting layer, an electron blocking layer, an electron transport layer, or an electron injection layer. of one or more.
  • the material of the hole injection layer is selected from poly(3,4-ethylenedioxythiophene)-polystyrenesulfonic acid, 2,3,5,6- Tetrafluoro-7,7',8,8'-tetracyanodimethylp-benzoquinone, copper phthalocyanine, 1,4,5,8,9,11-hexaazabenzonitrile, NiO x , MoO x , WO x , CrO x , CuO, MoS x , MoS x , WS x , WSe x , one or more of CuS, the value range of x is 1 to 3; and/or the hole transport
  • the material of the layer is selected from poly(9,9-dioctylfluorene-CO-N-(4-butylphenyl)diphenylamine), polyvinylcarbazole, poly(N,N'bis(4-butyl) (phen
  • the luminescent layer is a quantum dot luminescent layer, and the material of the quantum dot luminescent layer is selected from CdSe, CdS, ZnSe, ZnS , CdTe, ZnTe, CdZnS, CdZnSe, CdZnTe, ZnSeS, ZnSeTe, ZnTeS, CdSeS, CdSeTe, CdTeS, CdZnSeS, CdZnSeTe, CdZnSTe, CdSeSTe, ZnSeSTe, CdZnSeSTe, CdSe/ZnS, CdZnSe/ZnS, CdS/C dZnS,InP,InAs , one or more of InAsP, InP/InAsP, PbS, PbSe, PbT
  • the light-emitting diode film layer includes a hole injection layer, a hole transport layer, a light-emitting layer and an electron transport layer; wherein the light-emitting diode film layer is the hole injection layer.
  • megasonic waves are used to atomize the film-forming solution, wherein the film-forming solution includes a film-forming solute and a film-forming solvent, and the film-forming solute is poly(3,4-ethylenedioxythiophene)-polymer Styrene sulfonic acid, the film-forming solvent is toluene;
  • the film-forming solution includes a film-forming solute and a film-forming solvent, the film-forming solute is poly[9,9-dioctyl-fluorene-co-N-(4-butylphenyl)-diphenylamine], and the film-forming solvent is tetrahydrofuran;
  • the light-emitting diode film layer is a light-emitting layer
  • megasonic waves are used to atomize the film-forming solution, wherein the light-emitting diode film layer is a light-emitting layer, megasonic waves are used to atomize the film-forming solution, where
  • the film-forming solution Before using the megasonic wave to atomize the film-forming solution, the film-forming solution is dispersed by megasonic waves and intermittently disturbed by the megasonic waves; the light-emitting diode film layer is for electron transmission. layer, using megasonic waves to atomize the film-forming solution; wherein, the preparation method of the film-forming solution includes: providing reactants and ethanol, the reactants include zinc acetate and sodium hydroxide; and in the megasonic wave The zinc acetate, the sodium hydroxide and the ethanol are mixed under dispersion, and the megasonic waves are used for continuous disturbance to obtain the film-forming solution.
  • the frequency of the megasonic wave in the film-forming solution atomized by megasonic waves is 600 kHz and the power is 50W; the megasonic wave is used for intermittent atomization.
  • Disturbance includes: using the megasonic wave to perform intermittent disturbance at a time interval of 1 minute; the film-forming solution is dispersed by the megasonic wave, the frequency of the megasonic wave is 600kHz, and the power is 100W; The zinc acetate, the sodium hydroxide and the ethanol are mixed under dispersion, and the megasonic wave is used for continuous disturbance.
  • the frequency of the megasonic wave is 600kHz and the power is 100W.
  • embodiments of the present application provide a light-emitting diode film layer, which is produced by the above-mentioned film forming method of a light-emitting diode film layer.
  • embodiments of the present application provide a light-emitting diode, including the above-mentioned light-emitting diode film layer.
  • Figure 1 is a schematic diagram of the film-forming solution standing in a dripping device in the prior art
  • Figure 2 is a schematic flow chart of an embodiment of a method for forming a light-emitting diode film layer provided in this application;
  • Figure 3 is a schematic diagram of using sound waves to atomize the film-forming solution of the hole transport layer in Example 1 of the present application;
  • Figure 4 is a schematic diagram of forming a hole injection layer in Example 1 of the present application.
  • Figure 5 is a schematic diagram of forming a quantum dot light-emitting layer in Example 3 of the present application.
  • Figure 6 is a schematic diagram of the film formation of the electron transport layer in Example 5 of the present application.
  • Figure 7 is a data diagram showing the relationship between current density and voltage of the device
  • Figure 8 is a data graph showing the relationship between device efficiency and brightness of the device.
  • 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. Additionally, whenever a numerical range is indicated herein, it is intended to include any cited number (fractional or whole) within the indicated range.
  • At least one means one or more, and “plurality” means two or more.
  • At least one means one or more, and “plurality” means two or more.
  • At least one means one of the following” or similar expressions thereof refers to any combination of these items, including any combination of a single item (items) or a plurality of items (items).
  • at least one of a, b, or c or “at least one of a, b, and c” can mean: a, b, c, a-b ( That is, a and b), a-c, b-c, or a-b-c, where a, b, and c can be single or multiple respectively.
  • Figure 2 is a schematic flow chart of an embodiment of a method for forming a light-emitting diode film layer provided by the present application.
  • the embodiment of the present application provides a method of forming a light-emitting diode film layer, including:
  • Step S11 providing a substrate
  • Step S12 Apply atomized film-forming solution to the substrate and deposit the film-forming solution.
  • the film-forming solution is atomized into a fine liquid flow, and after the atomized fine liquid flow is applied to the substrate, the atomized fine liquid flow can be evenly dispersed on the substrate to form bubbles with a certain flow rate.
  • the liquid film With less liquid film, the liquid film has the effect of cleaning and wetting the surface, thereby smoothing the film layer and improving the flatness and bonding of the film layer.
  • the above-mentioned substrate may be a substrate including electrodes, or may be a substrate including electrodes and other functional layers.
  • the metal electrodes on the substrate can be ultrasonically cleaned using solvents such as acetone, ethanol, and deionized water. After cleaning and drying the residual solvent on the metal electrode, ultraviolet light can be used to irradiate the metal electrode on the substrate to improve the work function of the metal electrode.
  • the above "applying the atomized film-forming solution to the substrate” can be achieved by spraying the atomized film-forming solution onto the substrate through a nozzle.
  • the “on” of “on the substrate” is used in a broad sense, and the film-forming solution may be applied directly on the substrate, or the film-forming solution may be applied on a film layer formed on the surface of the substrate.
  • the above-mentioned deposition may be carried out by spin coating or inkjet printing. When spin coating, the rotation speed of the substrate can be 500 to 5000 rpm.
  • the deposited film-forming solution can be annealed and dried.
  • the film-forming solution can be dried by heating.
  • the heating temperature can be 80 to 100°C.
  • the specific heating temperature can be based on the film forming solution. It depends on the type and nature of the solvent in the solution.
  • the deposited film-forming solution can also be annealed and dried through vacuum drying or other drying methods, which is not limited here.
  • the atomization method of the film-forming solution is to use megasonic waves to atomize the film-forming solution.
  • the frequency of the megasonic waves is 400 to 1000 kHz. When the frequency of the megasonic waves is within the above range, the megasonic waves can atomize the film-forming solution.
  • Atomized into a fine liquid flow with a certain flow rate it has a certain cleaning effect on the fine dots of the film layer on the surface of the substrate, thereby making the film layer on the surface of the substrate cleaner and smoother, and the surface energy of the cleaned surface will increase, which will also make The film layer on the surface of the substrate has better bonding; at the same time, when the frequency of the megasonic wave is within the above range, it can reduce or even avoid the cavitation effect (effect) in the atomized film-forming solution, thereby protecting the film layer and making it immune to Destroyed by cavitation effect.
  • megasonic waves with a frequency of 400 to 1000 kHz are used to atomize the film-forming solution and deposit the atomized film-forming solution.
  • the above-mentioned megasonic waves can atomize the film-forming solution into a fine liquid flow. After the atomized fine liquid flow is applied to the substrate, the atomized fine liquid flow can be evenly dispersed on the substrate to form a certain flow rate and few bubbles.
  • the liquid film has the effect of cleaning and wetting the surface, thereby smoothing the film layer and improving the flatness and bonding of the film layer.
  • the frequency of megasonic waves is between 400 and 1000kHz, due to its high frequency, it can Reduce or even avoid the cavitation effect of atomized film-forming solution and damage to the film layer, thereby improving device performance.
  • the power of the megasonic wave is 20-200W.
  • the film-forming solution can be effectively atomized. Furthermore, the thickness and uniformity of the prepared film layer can be adjusted by adjusting the power of the megasonic wave.
  • applying the atomized film-forming solution to the substrate and depositing the film-forming solution are performed in a protective gas environment; the water content in the protective gas environment is less than 5 ppm.
  • the above protective gas may be selected from one or more of nitrogen, argon or other inert gases.
  • the water content in the protective gas environment is less than 5 ppm, which means that the volume fraction of water vapor contained in one million parts of the protective gas is less than 5.
  • the preparation of the film layer can be performed in a glove box.
  • the film-forming solution is a megasonically dispersed film-forming solution.
  • Some film-forming solutions are unstable when left standing and easily form agglomerated particles and crystals (such as colloidal film-forming solutions).
  • agglomerated particles or crystals of large particles are formed in the film-forming solution
  • the large particles in the film-forming solution atomized by megasonic waves will impact the film layer with the fine flow of atomization, causing damage to the film layer.
  • the large particles in the film-forming solution will The particles will remain in the film layer after spin coating, causing large bumps on the surface of the film layer, which may eventually pierce the film layer, causing water and oxygen to penetrate into the film layer and affecting device performance. Therefore, for the above film-forming solution, when using It needs to be dispersed before megasonic atomization.
  • Mechanical stirring is a traditional dispersion method. Its dispersion principle is to make the liquid flow as a whole.
  • the application range of mechanical stirring has limitations.
  • traditional mechanical stirring is difficult to prevent the agglomeration of nanoparticles. Therefore, this application uses megasonic waves to disperse the film-forming solution.
  • the high-energy disturbance of megasonic waves can avoid the agglomeration or crystallization of particles including nanoparticles, ensuring the smoothness and uniformity of the formed film layer; on the other hand, in this application,
  • the frequency of megasonic waves used is 400 to 1000 kHz.
  • the frequency of megasonic waves When the frequency of megasonic waves is within the above range, it can effectively reduce or even avoid the cavitation effect of megasonic waves in the film-forming solution during dispersion, thereby retaining the nanoparticles in the film-forming solution.
  • the original surface structure ensures that the photoelectric properties of the film material remain unchanged.
  • the megasonic parameters of the dispersed film-forming solution and the atomized film-forming solution are consistent, it is understood that the megasonic waves of the dispersed film-forming solution and the megasonic waves of the atomized film-forming solution can be generated by different devices.
  • the film-forming solution can be atomized and deposited on the substrate immediately after being dispersed by megasonic waves. This can shorten the time spent in preparing and transferring the film-forming solution, and can reduce the extremely unstable and easily agglomerated components.
  • the application of membrane solution to the solution method broadens the selection range of film-forming solutions in the solution method process.
  • the film-forming solution includes a film-forming solute and a film-forming solvent.
  • the film-forming solute includes a ligand, and the ligand can be selected from C1 to 8 thiols, C3 to 8 phosphines, and C1 to 8 phosphonic acids. , one or more of C1-8 amines, C1-4 carboxylic acids, and C1-4 alcohols.
  • the film-forming solute in the film-forming solution is the material of the film layer formed after depositing the film-forming solution.
  • the above ligand can be regarded as a short carbon chain ligand.
  • the ligand is a short carbon chain ligand, the ligands on the surface of the solute in the film-forming solution are more likely to fall off and cause the solute to agglomerate into particles. Therefore, for solutes with short carbon chain ligands, the above megasonic wave is used Dispersion is more conducive to obtaining a stable film-forming solution without agglomeration of solutes.
  • film-forming solutes including longer carbon chain ligands may also be dispersed.
  • the longer carbon chain ligands may be selected from, but are not limited to, oleic acid (OA), n-trioctylphosphine (TOP), 1-Dodecanethiol (DDT), dodecylamine (DDA).
  • the short carbon chain ligands may include C3-8 thiols, C3-8 phosphine or phosphine Acids, C3 ⁇ 8 amines, etc.; when the solute in the film-forming solution is nanoparticles such as ZnO, the short carbon chain ligands can include C1 ⁇ 4 thiols, C1 ⁇ 4 phosphonic acids, C1 ⁇ 4 amines , C1-4 carboxylic acids, C1-4 alcohols, etc.
  • the solute in the film-forming solution is synthesized using reactants, and megasonic waves are used to disperse the reactants during the synthesis of the solute.
  • Directly using megasonic waves to synthesize film-forming solutes can disperse the film-forming solutes during the synthesis process.
  • the film-forming solution including the synthesized solutes can be directly atomized and deposited using megasonic waves. This can reduce the number of film-forming steps. It is also beneficial to the stability of the film-forming solution.
  • different reactants can be injected into the reactor at a certain volume ratio or mass ratio at a certain flow rate and the above-mentioned acoustic wave disturbance can be used. It can be understood that using megasonic waves to disperse reactants, synthesizing solutes can be a relatively independent operation.
  • the film-forming solution including the above solutes can be further dispersed, or the solute can be synthesized and then the film-forming solution including the solutes can be synthesized and stopped. Dispersion of film-forming solutions of the above solutes.
  • the film-forming solution including the above solute is further dispersed.
  • using reactants to synthesize film-forming solutes includes:
  • reactants and polar solvents include metal salts and precipitants.
  • Metal salts, precipitants and polar solvents are mixed under the dispersion of megasonic waves.
  • the metal salt may be selected from one or more of nitrate, acetate, sulfate, chloride salt, carbonate, and perchlorate.
  • the precipitating agent may be selected from one or more of oxalic acid, urea, ammonia, sodium hydroxide, potassium hydroxide, carbonic acid, bicarbonate, thiourea, tetramethylammonium hydroxide, and ethanolamine.
  • the precipitating agent may also be referred to as a nucleating reagent.
  • the polar solvent may be selected from one or more of methanol, ethanol, isopropyl alcohol, and water.
  • the synthesized solute can be a metal oxide colloid (such as ZnO colloid).
  • the reactant can be an organic salt such as zinc acetate
  • the precipitating agent can be potassium hydroxide.
  • the mass ratio of zinc organic salt and alkali can be 1 to 3:1
  • the reaction temperature can be 40 to 70°C
  • the reaction time can be 30 to 60 minutes.
  • the synthesized solute can also be a quantum dot colloid synthesized in a halide salt system containing Zn, K, and Na.
  • the film-forming solution or synthetic solute is dispersed and continuously perturbed using megasonic waves; or
  • Megasonic waves are used to perform intermittent disturbances at intervals of 0.5 to 10 minutes.
  • megasonic waves are used to intermittently disturb the film-forming solution at intervals of 0.5 to 1 min.
  • the method further includes: using megasonic waves to atomize the cleaning agent to the surface formed by the film-forming solution. That is, the cleaning agent is atomized to the surface formed by the film-forming solution through megasonic waves.
  • the film-forming solution may be dried and solidified, or the film-forming solvent may not be dried and solidified.
  • megasonic waves are used to atomize the cleaning agent to the surface formed by the film-forming solution before the film-forming solution is dried and solidified. In this way, the cleaning time can be shortened, and defects such as bumps and burrs on the surface of the nanoparticle film can be removed, making the film smoother and more uniform.
  • the method further includes: using megasonic waves to atomize the ligand exchange solution to the surface formed by the film-forming solution. That is, the ligand exchange solution is atomized to the surface formed by the film-forming solution through megasonic waves.
  • the film-forming solution may also be dried and solidified, or the film-forming solvent may not be dried and solidified.
  • megasonic waves are used to atomize the ligand exchange solution to the surface formed by the film-forming solution before drying and solidifying the film-forming solution.
  • the film layer is one or more of a hole injection layer, a hole transport layer, a hole blocking layer, a light emitting layer, an electron blocking layer, an electron transport layer, and an electron injection layer.
  • the above-mentioned film forming method can be used to prepare only the hole injection layer, the hole transport layer, the hole blocking layer, the light emitting layer, the electron blocking layer, the electron transport layer, and the electron injection layer during the preparation process of the light emitting diode.
  • One layer, the above film forming method can also be used to laminate the hole injection layer, the hole transport layer, the hole blocking layer, the light emitting layer, the electron blocking layer, the electron transport layer, and the electron injection layer during the preparation process of the light emitting diode. All film layers.
  • the film-forming solvents between adjacent film layers need not be miscible with each other.
  • the above-mentioned light-emitting diode can be a light-emitting diode with an upright structure or an inverted structure.
  • the above-mentioned light-emitting diode can be a top-emitting light-emitting diode, a bottom-emitting light-emitting diode, or a double-sided emitting diode. of light-emitting diodes.
  • the above-mentioned light-emitting diode may include a cathode and an anode.
  • the material of the anode may be selected from but not limited to ITO, FTO, IZO, ITZO, ICO, SnO 2 , In 2 O 3 , Cd:ZnO, F:SnO 2 , In:SnO 2 , One or more of Ga:SnO 2 , AZO, Ni, Pt, Au, Ag, and Ir; the “:” in the above “Cd:ZnO” indicates doping.
  • the material of the cathode may be selected from, but is not limited to, one or more of metal materials, carbon materials, and metal oxides.
  • the metal material can be selected from but not limited to one or more of Al, Ag, Cu, Mo, Au, Ba, Ca, Mg
  • the carbon material can be selected from but not limited to graphite, carbon nanotubes, graphene, One or more types of carbon fiber
  • the metal oxide can be doped or undoped metal oxide, which can be selected from but not limited to ITO, FTO, ATO, AZO, GZO, IZO, MZO, and AMO.
  • the cathode can also have a doped or undoped metal oxide-metal-doped or undoped metal oxide structure (doped or undoped metal oxides are sandwiched between Metal) composite electrode
  • the composite electrode can be selected from but not limited to AZO-Ag-AZO, AZO-Al-AZO, ITO-Ag-ITO, ITO-Al-ITO, ZnO-Ag-ZnO, ZnO-Al-ZnO, One or more of TiO 2 -Ag-TiO 2 , TiO 2 -Al-TiO 2 , ZnS-Ag-ZnS, ZnS-Al-ZnS, TiO 2 -Ag-TiO 2 , TiO 2 -Al-TiO 2 .
  • the material of the hole injection layer is selected from poly(3,4-ethylenedioxythiophene)-polystyrenesulfonic acid (PEDOT: PSS), 2,3,5,6-tetrafluoro-7 ,7',8,8'-tetracyanodimethyl-p-benzoquinone (F4-TCNQ), copper phthalocyanine (CuPc), 1,4,5,8,9,11-hexaazabenzonitrile (HATCN ), one or more of NiO x , MoO x , WO x , CrO x , CuO, MoS x , MoS x , WS x , WSe x , and CuS, and the value range of x is 1 to 3;
  • PEDOT poly(3,4-ethylenedioxythiophene)-polystyrenesulfonic acid
  • F4-TCNQ 2,3,5,6-tetrafluoro-7 ,7',8,8'-te
  • the material of the hole transport layer is selected from poly(9,9-dioctylfluorene-CO-N-(4-butylphenyl)diphenylamine) (TFB), polyvinylcarbazole (PVK), poly( N,N'bis(4-butylphenyl)-N,N'-bis(phenyl)benzidine) (POLY-TPD), 4,4',4"-tris(carbazol-9-yl) Triphenylamine (TCTA), 4,4'-bis(9-carbazole)biphenyl (DCBP), N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1, 1'-biphenyl-4,4'-diamine ( TPD ), N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4' -One or more of diamine (NPB), graphene
  • the material of the hole blocking layer is selected from one or more of ZnO, TiO 2 , SnO, ZrO 2 , and Ta 2 O 3 ;
  • the light-emitting layer is a quantum dot light-emitting layer, and the material of the quantum dot light-emitting layer is selected from the group consisting of CdSe, CdS, ZnSe, ZnS, CdTe, ZnTe, CdZnS, CdZnSe, CdZnTe, ZnSeS, ZnSeTe, ZnTeS, CdSeS, CdSeTe, CdTeS, CdZnSeS , CdZnSeTe, CdZnSTe, CdSeSTe, ZnSeSTe, CdZnSeSTe, CdSe/ZnS, CdZnSe/ZnS, CdS/CdZnS, InP, InAs, InAsP, InP/InAsP, PbS, PbSe, PbTe, PbSeS, PbSeTe, P
  • the material of the electron blocking layer is selected from polyvinylcarbazole (PVK), poly[9,9-dioctyl-fluorene-co-N-(4-butylphenyl)-diphenylamine] (TFB) , 1,1-bis[(di-4-methylphenylamino)phenylcyclohexane (TAPC), N,N'-diphenyl-N,N'-(1-naphthyl)-1,1' -One or more of biphenyl-4,4'-diamine (NPB), NiO, V 2 O 5 , MoO 3 , and WO 3 ;
  • PVK polyvinylcarbazole
  • TFB poly[9,9-dioctyl-fluorene-co-N-(4-butylphenyl)-diphenylamine]
  • TAPC 1,1-bis[(di-4-methylphenylamino)phenylcycl
  • the material of the electron transport layer is selected from one or more of ZnO, TiO 2 , SnO 2 , Ta 2 O 3 , ZrO 2 , NiO, TiLiO, ZnAlO, ZnO, ZnSnO, ZnLiO, and InSnO, which may or may not include ligands. species; the ligand of the material of the electron transport layer is selected from one or more of hydroxyl group, carboxyl group, thiol group, phosphine group, amine group, and cyano group;
  • the material of the electron injection layer is selected from one or more of LiF and CsF.
  • the film-forming solvent of the hole injection layer can be selected from but not limited to chlorobenzene , toluene, dichlorobenzene, one or more of ethyl benzoate;
  • the film-forming solvent of the hole injection layer can be selected from but not limited to one or more polar solvents such as water
  • the film-forming solvent of the hole transport layer can be Selected from but not limited to one or more weakly polar solvent
  • the material of the light-emitting layer can be a direct bandgap compound semiconductor with light-emitting ability, which can be selected from, but is not limited to, II-VI compounds, III-V compounds, II-V compounds, III-VI compounds, IV compounds.
  • -One or more quantum dot materials such as Group VI compounds, Group I-III-VI compounds, Group II-IV-VI compounds or Group IV elements.
  • the above-mentioned quantum dot materials may have longer carbon chain ligands or shorter carbon chain ligands, wherein the longer carbon chain ligands may be selected from, but are not limited to, oleic acid (OA), n-trioctylphosphine (TOP), one or more of 1-dodecanethiol (DDT), dodecylamine (DDA); the shorter carbon chain ligand can be selected from but not limited to C3-8 thiols, C3 ⁇ 8 phosphine or phosphonic acid, one or more of C3 ⁇ 8 amines; the film-forming solvent of the luminescent layer can be selected from but not limited to alkanes (such as heptane, n-hexane), chloroform, toluene and other weak polar One or more solvents.
  • alkanes such as heptane, n-hexane
  • chloroform toluene and other weak polar One or more solvent
  • the film-forming solvent of the above-mentioned electron transport layer may be selected from but not limited to one or more polar solvents such as water, ethanol, methanol, isopropyl alcohol, etc.
  • This embodiment discloses a method for preparing and testing a light-emitting diode with a positive top-emitting structure, including:
  • Step 1 Provide a substrate 101 coated with an ITO film layer (anode), ultrasonically clean the ITO film layer with acetone and ethanol for 15 minutes, then clean the ITO film layer with deionized water, and then dry the above-mentioned substrate on a heating plate at 150°C for 10 minutes. , and then use ultraviolet light (UV) to irradiate the ITO film layer on the substrate 101 for 20 minutes to increase the ITO work function;
  • UV ultraviolet light
  • Step 2 Put the cleaned substrate into the glove box, use the sonic nozzle 102 to atomize the film-forming solution of the hole injection layer, spray the atomized film-forming solution of the hole injection layer onto the ITO film layer, and spin Apply the film-forming solution of the hole injection layer.
  • the sound waves can play a certain cleaning role in the fine point protrusions 20 of the film layer on the surface of the substrate 101, thereby making the film layer on the surface of the substrate 101 cleaner and smoother (see Figure 3 ), in which the film-forming solute in the hole injection layer film-forming solution is PEDOT:PSS (mass fraction 2.8%), the film-forming solvent is toluene, the frequency of the above sound wave is 600kHz, the power is 50W, the spraying time is 5s, and the substrate rotation speed is 2000rpm, the spin coating time is 30s, and then the substrate is heated on a heating plate at 150°C for 10120min (see Figure 4 for a schematic diagram of atomized spin coating of the film-forming solution of the hole injection layer);
  • PEDOT:PSS mass fraction 2.8%
  • the film-forming solvent is toluene
  • the frequency of the above sound wave is 600kHz
  • the power is 50W
  • the spraying time is 5s
  • the substrate rotation speed is 2000rpm
  • Step 3 Spin-coat the hole transport layer on the prepared hole injection layer.
  • the film-forming solute of the hole transport layer is TFB (the concentration in the film-forming solution is 6.5 mg/mL), and the film-forming solvent is tetrahydrofuran.
  • the substrate rotation speed is 3000rpm, the spin coating time is 30s, and then the substrate is heated on a heating plate at 120°C for 10120min;
  • Step 4 Spin-coat the quantum dot light-emitting layer on the prepared hole transport layer.
  • the film-forming solute of the quantum dot light-emitting layer is CdSe (the concentration in the film-forming solution is 10 mg/mL), the film-forming solvent is toluene, and the substrate
  • the rotation speed is 1500 rpm, the spin coating time is 30 s, and then the substrate is heated on a hot plate at 100°C for 101 5 min.
  • Step 5 Spin-coat the electron transport layer on the completed quantum dot luminescent layer.
  • the film-forming solute of the electron transport layer is ZnO (the concentration in the film-forming solution is 30 mg/mL), the film-forming solvent is ethanol, and the substrate rotation speed is 4000rpm, spin coating time is 30s, then heat the substrate on a hot plate at 80°C for 101 10min;
  • Step 6 Through thermal evaporation, evaporate Al as the cathode of the light-emitting diode on the electron transport layer in an environment with a vacuum degree of no higher than 3x10 -4 Pa.
  • the evaporation speed is 1 Angstrom/second and the evaporation time is 200s.
  • the thickness of the evaporated Al film is 20nm, and a top-emitting positive quantum dot light-emitting diode is obtained;
  • Step 7 Test the JVL data of the device to determine the current density of the device (see Figure 7), and the device efficiency (see Figure 8).
  • Step 8 Use 2mA constant current drive to test the working life of the device, as shown in Table 1.
  • This embodiment discloses a method for preparing and testing a light-emitting diode with a positive top-emitting structure, including:
  • Steps 1 to 2 Same as steps 1 to 2 in Example 1;
  • Step 3 Use an acoustic nozzle to atomize the film-forming solution of the hole transport layer, spray the atomized film-forming solution of the hole transport layer onto the hole injection layer, and spin-coat the film-forming solution of the hole transport layer,
  • the film-forming solute in the hole transport layer film-forming solution is TFB (the concentration in the film-forming solution is 10 mg/mL)
  • the film-forming solvent is tetrahydrofuran
  • the frequency of the above-mentioned sound wave is 600kHz
  • the power is 50W
  • the spraying time is 5s.
  • the substrate rotation speed is 2000rpm
  • the spin coating time is 30s, and then the substrate is heated on a heating plate at 120°C for 20min;
  • Step 4 Use an acoustic nozzle to atomize the film-forming solution of the quantum dot luminescent layer, spray the atomized film-forming solution of the quantum dot luminescent layer onto the hole transport layer, and spin-coat the film-forming solution of the quantum dot luminescent layer.
  • the film-forming solute of the quantum dot light-emitting layer is CdSe (the concentration in the film-forming solution is 14mg/mL), the film-forming solvent is toluene, the frequency of the above-mentioned sound wave is 600kHz, the power is 50W, the spraying time is 5s, and the substrate rotation speed is 1000rpm, spin coating time is 30s, then heat the substrate on a hot plate at 100°C for 5min;
  • Step 5 Use an acoustic nozzle to atomize the film-forming solution of the electron transport layer, spray the atomized film-forming solution of the electron transport layer onto the quantum dot light-emitting layer, and spin-coat the film-forming solution of the electron transport layer, where the electron transport layer
  • the film-forming solute of the layer is ZnO (the concentration in the film-forming solution is 30mg/mL)
  • the film-forming solvent is ethanol
  • the frequency of the above-mentioned sound wave is 600kHz
  • the power is 50W
  • the spraying time is 5s
  • the substrate rotation speed is 2500rpm
  • spin coating The time is 30s, and then the substrate is heated on a hot plate at 80°C for 10min;
  • Step 6 Through thermal evaporation, evaporate Al as the cathode of the light-emitting diode on the electron transport layer in an environment with a vacuum degree of no higher than 3x10 -4 Pa.
  • the evaporation speed is 1 Angstrom/second and the evaporation time is 100s.
  • the thickness of the evaporated Al film is 10nm, and a top-emitting positive quantum dot light-emitting diode is obtained;
  • Steps 7-8 Same as steps 1-3 in Example 1.
  • This embodiment discloses a method for preparing and testing a light-emitting diode with a positive top-emitting structure, including:
  • Steps 1 to 3 Same as steps 1 to 3 in Example 1;
  • Step 4 The film-forming solution of the quantum dot luminescent layer is placed in the acoustic wave dispersion container 103.
  • the frequency of the acoustic wave in the acoustic wave dispersion container 103 is set to 600kHz, and the power is set to 100W.
  • the acoustic wave is used to intermittently disturb the film-forming solution of the quantum dot luminescent layer. , the intermittent duration is 1 minute; then use the sonic nozzle 102 to atomize the film-forming solution of the quantum dot luminescent layer, spray the atomized film-forming solution of the quantum dot luminescent layer onto the hole transport layer, and spin-coat the quantum dot luminescent layer.
  • Film-forming solution in which the film-forming solute of the quantum dot light-emitting layer is CdSe (the concentration in the film-forming solution is 14mg/mL), the film-forming solvent is toluene, the frequency of the above-mentioned sound wave is 600kHz, the power is 50W, and the spraying time is 5s , the substrate rotation speed is 1000 rpm, the spin coating time is 30 s, and then the substrate is heated on a heating plate at 100°C for 101 5 min (see Figure 5 for a schematic diagram of the film-forming solution that disperses and atomizes the spin-coated quantum dot luminescent layer);
  • Step 5 The electron transport layer film-forming solution is placed in the acoustic wave dispersion container 103.
  • the acoustic wave frequency in the acoustic wave dispersion container 103 is set to 600kHz, and the power is set to 100W. Use sound waves to intermittently disturb the electron transport layer film-forming solution.
  • the duration is 0.5 minutes; then use the sonic nozzle 102 to atomize the film-forming solution of the electron transport layer, spray the atomized film-forming solution of the electron transport layer onto the quantum dot light-emitting layer, and spin-coat the film-forming solution of the electron transport layer,
  • the film-forming solute of the electron transport layer is ZnO (the concentration in the film-forming solution is 30mg/mL), the film-forming solvent is ethanol, the frequency of the above-mentioned sound wave is 600kHz, the power is 50W, the spraying time is 5s, and the substrate rotation speed is 2500rpm. , the spin coating time is 30s, and then the substrate is heated on a hot plate at 80°C for 101 10min;
  • Steps 6 to 8 Same as steps 6 to 8 in Example 2.
  • This embodiment discloses a method for preparing and testing a light-emitting diode with a positive top-emitting structure, including:
  • Steps 1 to 4 Same as steps 1 to 4 in Example 3;
  • Step 5 Place the ligand exchange solution including the target ligand octanethiol (the solvent of the ligand exchange solution is ethanol) in a sonic dispersion container.
  • the sonic frequency in the container is set to 600kHz and the power is set to 100W.
  • Steps 6 to 9 Same as steps 5 to 8 in Example 3.
  • This embodiment discloses a method for preparing and testing a light-emitting diode with a positive top-emitting structure, including:
  • Steps 1 to 4 Same as steps 1 to 4 in Example 3;
  • Step 5 Prepare a 0.1 mol/L zinc acetate absolute ethanol solution and place it in the first container 104, prepare a 1 mol/L sodium hydroxide ethanol solution and place it in the second container 105, and place 200 ml of the sonic wave dispersion container 103. Absolute ethanol is used as the diluting solvent, and then the anhydrous ethanol solution of zinc acetate and the ethanol solution of sodium hydroxide are injected into the acoustic wave dispersion container 103 at a volume ratio of 2:1 to form a mixed reaction liquid.
  • the acoustic wave frequency in the acoustic wave dispersion container 103 is set is 600kHz, the power is set to 100W, use sound waves to continuously disturb the above-mentioned mixed reaction solution for 2 hours, so that it reacts to generate a 30mg/mL ZnO colloidal solution, which is used as the film-forming solution of the electron transport layer; then use the sonic nozzle 102 to atomize the electron transport layer For the film-forming solution, spray the atomized film-forming solution of the electron transport layer onto the quantum dot light-emitting layer, and spin-coat the film-forming solution of the electron transport layer.
  • the frequency of the above sound wave is 600kHz, the power is 50W, and the spraying time is 5s.
  • the substrate rotation speed is 2500rpm
  • the spin coating time is 30s
  • the substrate is heated 101 on a heating plate at 80°C for 10min (see Figure 6 for a schematic diagram of synthesizing, dispersing and atomizing the film-forming solution of the electron transport layer);
  • Steps 6 to 8 Same as steps 6 to 8 in Example 3.
  • This comparative example discloses a preparation and testing method for a light-emitting diode with a positive top-emitting structure, including:
  • Step 1 Same as step 1 in Example 1.
  • Step 2 Spin-coat the hole injection layer on the ITO film layer.
  • the film-forming solute of the hole injection layer is PEDOT:PSS (mass fraction 2.8%), the film-forming solvent is toluene, the substrate rotation speed is 3000rpm, and the spin coating time is time 30s, then heat the substrate on a heating plate at 150°C for 20min;
  • Steps 3 to 8 Same as steps 3 to 8 in Example 1.
  • L represents the maximum brightness of the device, in cd/m2
  • T95 represents the time it takes for the brightness of the device to decay to 95% under a constant current drive of 2mA, in h
  • T95_1K represents the time required for the brightness to decay to 95% when the brightness of the device is 1000nit. Time, unit is h.
  • the T95 and T95_1K of the devices prepared by the film forming method of the present application have increased, indicating that the devices prepared by the film forming method of the present application have increased.
  • the device life has been improved.
  • the brightness of the device is also improved, indicating that the film layers formed by the film forming method of the present application are smoother and more uniform, thereby improving the device's brightness. performance.
  • the device when sound waves are used to directly synthesize and disperse film-forming solutes and then used for film formation (Example 5), the device has the longest life, indicating that sound waves can more effectively avoid the agglomeration of film-forming solutes and thus can Produce a smoother and more uniform film layer.

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Abstract

本申请公开了发光二极管膜层及其成膜方法、发光二极管。本申请的发光二极管膜层的成膜方法，通过将成膜溶液雾化为细液流，将雾化后的细液流施加在基板上后，雾化后的细液流能够在基板上均匀分散形成具有一定流速、气泡少的液膜，该液膜具有清洗-浸润表面的效果，从而能够平滑膜层，提高膜层平整度以及结合性。

Description

发光二极管膜层及其成膜方法、发光二极管
本申请要求于2022年04月18日在中国专利局提交的、申请号为202210405597.2、申请名称为“发光二极管膜层的成膜方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本申请涉及显示技术领域，尤其涉及一种发光二极管膜层及其成膜方法、发光二极管。
背景技术
近年来，发光二极管已实现产业化应用，其中一些发光二极管，例如量子点发光二极管因为具有高亮度、高色纯度、100％Rec.2020色域、高外量子效率，低功耗，低制造成本等诸多优点而备受关注。目前多数发光二极管采用的器件结构包括基板、阳极、透明空穴注入层、空穴传输层、发光层、电子传输层、电子注入层和阴极，在一些情况下，也会包括阻挡层等。为提高器件的出光效率和工作寿命，这些功能层的制备都需要控制平面粗糙度和膜层厚度。
薄膜的制备方法有很多，其中，溶液法具有工艺简单、成本低廉、易实现大面积成膜等优点，是显示器件不同膜层制备的重要方法。常见的溶液法包括旋转涂布、喷墨打印等，薄膜制备期间，成膜溶液一般静置在滴液装置中(参见图1)，对于胶体溶液、分层溶液、介稳态溶液等而言，静置过程中溶液容易因溶质聚沉、析出等问题而导致溶液浓度发生变化，使得制备的膜层的厚度难以控制；而滴液装置中的溶液(例如量子点金属氧化物ZnO胶体溶液)出现溶质团聚后，形成的颗粒会使成膜的膜层存在凸点，如此，则可能会导致水氧的侵入，从而影响器件寿命，更甚的会由于膜层凸点的尖端放电而造成器件损坏。此外，对于一些液体而言，其性质十分不稳定，需要现配现用，这对于溶液法的应用提出了更高的工艺要求。
有研究披露，使用超声喷雾代替液滴的溶液法，可有效提高膜层的均匀度。然而，对于现有的超声波而言，超声喷雾过程中，液体在超声的作用下容易形成气泡，所形成的气泡在破裂瞬间会在周围形成水流冲击波，导致水流加速度 非常大，破裂的气泡周围的局部的压力可达到上千个大气压，此种现象被称为超声的空化作用。空化作用会使得材料表面状态破坏，进而造成材料光电特性发生变化，影响器件性能，并且空化作用也会在一定程度上破坏膜层。因此，亟待一种技术方案来解决溶液法制备膜层时溶质团聚的问题。
技术解决方案
因此，本申请提供一种发光二极管膜层及其成膜方法、发光二极管
本申请实施例提供一种发光二极管膜层的成膜方法，包括：提供基板；以及往所述基板施加雾化的成膜溶液并沉积所述成膜溶液。
可选的，在本申请的一些实施例中，所述成膜溶液的雾化方式为利用兆声波进行雾化，所述兆声波的频率为400～1000kHz。
可选的，在本申请的一些实施例中，所述兆声波的功率为20～200W。
可选的，在本申请的一些实施例中，所述往所述基板施加雾化的成膜溶液并沉积所述成膜溶液的步骤，在保护气体的环境下进行；其中，所述保护气体的环境中的水含量小于5ppm；和/或所述保护气体选自氮气、氩气中的一种或多种。
可选的，在本申请的一些实施例中，所述成膜溶液为经所述兆声波分散的成膜溶液。
可选的，在本申请的一些实施例中，所述成膜溶液经过所述兆声波分散之后，雾化形成所述雾化的成膜溶液。
可选的，在本申请的一些实施例中，所述成膜溶液包括成膜溶质和成膜溶剂，所述成膜溶质包括配体，所述配体选自于C1～8的硫醇、C3～8的膦、C1～8的膦酸、C1～8的胺、C1～4的羧酸、C1～4的醇中的一种或多种。
可选的，在本申请的一些实施例中，所述成膜溶质利用反应物合成，在合成所述成膜溶质的过程中，利用所述兆声波分散所述反应物。
可选的，在本申请的一些实施例中，利用所述反应物合成所述成膜溶质包括：提供所述反应物以及极性溶剂，所述反应物包括金属盐以及沉淀剂；以及在所述兆声波的分散下将所述金属盐、所述沉淀剂以及所述极性溶剂混合。
可选的，在本申请的一些实施例中，所述金属盐选自于硝酸盐、醋酸盐、 硫酸盐、氯化盐、碳酸盐、高氯酸盐中的一种或多种；和/或所述沉淀剂选自于草酸、尿素、氨水、氢氧化钠、氢氧化钾、碳酸、碳酸氢盐、硫脲、氢氧化四甲铵、乙醇胺中的一种或多种；和/或所述极性溶剂选自于甲醇、乙醇、异丙醇、水中的一种或多种。
可选的，在本申请的一些实施例中，所述成膜溶质包括ZnO，所述金属盐选自锌有机盐，所述沉淀剂选自碱，所述锌有机盐与所述碱的质量比为1～3：1。
可选的，在本申请的一些实施例中，分散所述成膜溶液或合成所述成膜溶质时，利用所述兆声波进行持续性扰动；或者利用所述兆声波以0.5～10min的时间间隔进行间歇式扰动。
可选的，在本申请的一些实施例中，利用所述兆声波以0.5～1min的时间间隔进行间歇式扰动。
可选的，在本申请的一些实施例中，在沉积所述成膜溶液之后，还包括：利用所述兆声波雾化清洗剂至所述成膜溶液形成的表面；和/或在沉积所述成膜溶液之后，还包括：利用所述兆声波雾化配体交换溶液至所述成膜溶液形成的表面。
可选的，在本申请的一些实施例中，所述发光二极管膜层为空穴注入层、空穴传输层、空穴阻挡层、发光层、电子阻挡层、电子传输层、电子注入层中的一种或多种。
可选的，在本申请的一些实施例中，所述空穴注入层的材料选自于聚(3,4-乙烯二氧噻吩)-聚苯乙烯磺酸、2,3,5,6-四氟-7,7',8,8'-四氰二甲基对苯醌、铜酞菁、1,4,5,8,9,11-六氮杂苯甲腈、NiO x、MoO x、WO x、CrO x、CuO、MoS x、MoSe x、WS x、WSe x、CuS中的一种或多种，所述x的取值范围为1～3；和/或所述空穴传输层的材料选自于聚(9,9-二辛基芴-CO-N-(4-丁基苯基)二苯胺)、聚乙烯基咔唑、聚(N,N'双(4-丁基苯基)-N,N'-双(苯基)联苯胺)、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、N,N'-二苯基-N,N'-(1-萘基)-1,1'-联苯-4,4'-二胺、石墨烯、C60、NiO y、MoO y、WO y、CrO y、CuO、MoS y、MoSe y、WS y、WSe y、CuS中的一种或多种，所述y的取值范围为1～3；和/或所述空穴阻挡层的材料选自于ZnO、TiO 2、 SnO、ZrO 2、Ta 2O 3中的一种或多种；和/或所述发光层为量子点发光层，所述量子点发光层的材料选自于CdSe、CdS、ZnSe、ZnS、CdTe、ZnTe、CdZnS、CdZnSe、CdZnTe、ZnSeS、ZnSeTe、ZnTeS、CdSeS、CdSeTe、CdTeS、CdZnSeS、CdZnSeTe、CdZnSTe、CdSeSTe、ZnSeSTe、CdZnSeSTe、CdSe/ZnS、CdZnSe/ZnS、CdS/CdZnS、InP、InAs、InAsP、InP/InAsP、PbS、PbSe、PbTe、PbSeS、PbSeTe、PbSTe、PbSe/PbS中的一种或多种；和/或所述电子阻挡层的材料选自于聚乙烯基咔唑、聚[9,9-二辛基-芴-共-N-(4-丁基苯基)-二苯基胺]、1,1-双[(二-4-甲苯基氨基)苯基环己烷、N,N'-二苯基-N,N'-(1-萘基)-1,1'-联苯-4,4'-二胺、NiO、V 2O 5、MoO 3、WO 3中的一种或多种；和/或所述电子传输层的材料选自于包括或未包括配体的ZnO、TiO 2、SnO 2、Ta 2O 3、ZrO 2、NiO、TiLiO、ZnAlO、ZnO、ZnSnO、ZnLiO、InSnO中的一种或多种；所述配体选自于羟基、羧基、硫醇基、膦基、胺基、氰基中的一种或多种；和/或所述电子注入层的材料选自于LiF、CsF中的一种或多种。
可选的，在本申请的一些实施例中，所述发光二极管膜层包括空穴注入层、空穴传输层、发光层和电子传输层；其中，所述发光二极管膜层为所述空穴注入层时，利用兆声波雾化所述成膜溶液，其中，所述成膜溶液包括成膜溶质和成膜溶剂，所述成膜溶质为聚(3,4-乙烯二氧噻吩)-聚苯乙烯磺酸，所述成膜溶剂为甲苯；所述发光二极管膜层为所述空穴传输层时，利用兆声波雾化所述成膜溶液，其中，所述成膜溶液包括成膜溶质和成膜溶剂，所述成膜溶质为聚[9,9-二辛基-芴-共-N-(4-丁基苯基)-二苯基胺]，所述成膜溶剂为四氢呋喃；所述发光二极管膜层为发光层时，利用兆声波雾化所述成膜溶液，其中，所述成膜溶液包括成膜溶质和成膜溶剂，所述成膜溶质为CdSe，所述成膜溶剂为甲苯，所述利用所述兆声波雾化所述成膜溶液之前，所述成膜溶液经过兆声波分散，并利用所述兆声波进行间歇式扰动；所述发光二极管膜层为电子传输层时，利用兆声波雾化所述成膜溶液；其中，所述成膜溶液的制备方法包括：提供反应物以及乙醇，所述反应物包括醋酸锌以及氢氧化钠；以及在所述兆声波的分散下将所述醋酸锌、所述氢氧化钠以及所述乙醇混合，并利用所述兆声波进行持续扰动，得到所述成膜溶液。
可选的，在本申请的一些实施例中，所述利用兆声波雾化所述成膜溶液中 的所述兆声波的频率为600kHz，功率为50W；所述利用所述兆声波进行间歇式扰动，包括：利用所述兆声波以1min的时间间隔进行间歇式扰动；所述成膜溶液经过兆声波分散中，所述兆声波的频率为600kHz，功率为100W；所述在所述兆声波的分散下将所述醋酸锌、所述氢氧化钠以及所述乙醇混合，并利用所述兆声波进行持续扰动中，所述兆声波的频率为600kHz，功率为100W。
相应的，本申请实施例提供一种发光二极管膜层，由上述的发光二极管膜层的成膜方法制得。
相应的，本申请实施例提供一种发光二极管，包括上述的发光二极管膜层。
附图说明
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。
图1是现有技术中成膜溶液静置在滴液装置中的示意图；
图2是本申请提供的发光二极管膜层的成膜方法一实施例的流程示意图；
图3是本申请实施例1中利用声波雾化空穴传输层的成膜溶液时的示意图；
图4是本申请实施例1中对空穴注入层进行成膜的示意图；
图5是本申请实施例3中对量子点发光层进行成膜的示意图；
图6是本申请实施例5中对电子传输层的成膜的示意图；
图7是器件的电流密度与电压的关系的数据图；
图8是器件的器件效率与亮度的关系的数据图。
其中，附图标记说明：
基板101；兆声波喷头102；兆声波分散容器103；第一容器104；第二容器105；细点凸起20。
本申请的实施方式
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。
此外，应当理解的是，此处所描述的具体实施方式仅用于说明和解释本申请，并不用于限制本申请。在本申请中，在未作相反说明的情况下，使用的方位词如“上”和“下”具体为附图中的图面方向。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形式存在；应当理解，以一范围形式的描述仅仅是因为方便及简洁，不应理解为对本申请范围的硬性限制；因此，应当认为所述的范围描述已经具体公开所有可能的子范围以及该范围内的单一数值。例如，应当认为从1到6的范围描述已经具体公开子范围，例如从1到3，从1到4，从1到5，从2到4，从2到6，从3到6等，以及所述范围内的单一数字，例如1、2、3、4、5及6，此不管范围为何皆适用。另外，每当在本文中指出数值范围，是指包括所指范围内的任何引用的数字(分数或整数)。
在本申请中，“和/或”，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：单独存在A，同时存在A和B，单独存在B的情况。其中A，B可以是单数或者复数。
在本申请中，“至少一个”是指一个或者多个，“多个”是指两个或两个以上。“至少一种”、“以下至少一项(个)”或其类似表达，是指的这些项中的任意组合，包括单项(个)或复数项(个)的任意组合。例如，“a,b,或c中的至少一项(个)”，或，“a,b,和c中的至少一项(个)”，均可以表示：a,b,c,a-b(即a和b),a-c,b-c,或a-b-c，其中a,b,c分别可以是单个，也可以是多个。
参阅图2，图2是本申请提供的发光二极管膜层的成膜方法一实施例的流程示意图，本申请实施例提供发光二极管膜层的成膜方法，包括：
步骤S11：提供基板；以及
步骤S12：往基板上施加雾化的成膜溶液并沉积成膜溶液。
本实施例中，通过将成膜溶液雾化为细液流，将雾化后的细液流施加在基板上后，雾化后的细液流能够在基板上均匀分散形成具有一定流速、气泡少的液膜，该液膜具有清洗-浸润表面的效果，从而能够平滑膜层，提高膜层平整度以及结合性。
上述基板可以为包括电极的基板，也可以为包括电极和其他功能层的基板。当上述基板为包括电极的基板时，在往基板上施加雾化的成膜溶液之前，可以利用丙酮、乙醇、去离子水等溶剂对基板上的金属电极进行超声清洗。清洗完毕将金属电极上残余的溶剂干燥之后，可以利用紫外光照射基板上的金属电极，以提高金属电极的功函数。
上述“往基板上施加雾化的成膜溶液”可以通过喷头往基板上喷涂上述雾化的成膜溶液实现。上述“基板上”的“上”为广义的上，既可以是直接将成膜溶液施加在基板上，也可以是将成膜溶液施加在形成于基板表面的膜层之上。进一步地，上述沉积可以采用旋涂的方法，也可以采用喷墨打印的方法。当旋涂时，基板的转速可以为500～5000rpm。
进一步地，沉积成膜溶液后，可以对沉积的成膜溶液进行退火干燥，例如可以通过加热的方式对成膜溶液进行干燥，加热的温度可以为80～100℃，具体加热温度可以根据成膜溶液中溶剂的种类和性质决定，当然也可以通过真空干燥或其他干燥方式对沉积的成膜溶液进行退火干燥，在此不做限定。
在一实施例中，成膜溶液的雾化方式为利用兆声波雾化成膜溶液，兆声波的频率为400～1000kHz，当兆声波的频率在上述范围内时，兆声波可以将成膜溶液雾化成具有一定流速的细液流，对基板表面的膜层的细点凸起起到一定的清洗作用，从而使得基板表面的膜层更加清洁平整，清洁表面的表面能会增高，这也会使得基板表面的膜层具有更好的结合性；同时兆声波的频率在上述范围内时，能够减少甚至避免雾化的成膜溶液中的空化效应(作用)，从而保护膜层，使其免遭空化效应的破坏。
本实施例中，利用频率为400～1000kHz的兆声波雾化成膜溶液并沉积上述雾化的成膜溶液。通过上述兆声波能够将成膜溶液雾化为细液流，将雾化后的细液流施加在基板上后，雾化后的细液流能够在基板上均匀分散形成具有一定流速、气泡少的液膜，该液膜具有清洗-浸润表面的效果，从而能够平滑膜层，提高膜层平整度以及结合性，同时由于兆声波的频率在400～1000kHz之间，由于频率较高，其能够减少甚至避免雾化的成膜溶液产生空化效应而对膜层造成破坏，进而提高器件性能。
在一些实施例中，兆声波的功率为20～200W。
当兆声波的功率在上述范围内时，能够有效雾化成膜溶液。进一步地，可以通过调整兆声波的功率能够调整制备膜层的厚度以及均匀性。
在一些实施例中，往基板上施加雾化的成膜溶液并沉积成膜溶液是在保护气体的环境下进行；保护气体的环境中的水含量小于5ppm。
上述保护气体可以选自于氮气、氩气或其他惰性气体中的一种或多种。保护气体的环境中的水含量小于5ppm是指，在一百万份数的体积保护气体中所含水蒸汽的体积份数小于5。进一步的，为了实现上述保护气体环境，膜层的制备可以在手套箱中进行。
在一些实施例中，成膜溶液为经兆声波分散的成膜溶液。
一些成膜溶液静置时不稳定，容易形成团聚颗粒、结晶(例如胶体成膜溶液)。当成膜溶液中形成大颗粒的团聚颗粒或结晶时，通过兆声波雾化的成膜溶液中的大颗粒会随着雾化的细微流冲击膜层造成膜层损伤，同时成膜溶液中的大颗粒在经过旋涂后会留在膜层中，使得膜层表面存在大凸点，最终可能刺破膜层，使得水氧渗透进膜层而影响器件性能，因此对于上述成膜溶液，在利用兆声波雾化其之前需要对其进行分散处理。机械搅拌作为一种传统的分散方法，其分散原理是使液体整体流动，但机械搅拌的应用范围具有局限性，例如传统的机械搅拌很难阻止纳米颗粒的团聚。因此本申请通过兆声波分散成膜溶液，一方面兆声波的高能扰动能够避免包括纳米颗粒在内的颗粒发生团聚或结晶，保证了所成膜层的平整、均匀；另一方面，本申请中使用的兆声波的频率为400～1000kHz，当兆声波频率在上述范围内时，能够有效减少甚至避免分散时兆声波在成膜溶液中产生空化效应，从而能够保留成膜溶液中纳米颗粒的原始表面结构，进而保证膜层材料的光电性能不发生改变。
虽然分散成膜溶液的兆声波与雾化成膜溶液的声波参数一致，但可以理解的是分散成膜溶液的兆声波与雾化成膜溶液的兆声波可以通过不同的设备产生。
进一步地，可以将成膜溶液经兆声波分散后立刻雾化并沉积至基板之上，如此能够缩短成膜溶液制备、转移所花费的时间，并且能够将极不稳定、极易产生团聚的成膜溶液应用至溶液法中，拓宽了溶液法工艺对成膜溶液的选择范围。
在一些实施例中，成膜溶液包括成膜溶质和成膜溶剂，成膜溶质包括配体，配体可以选自于C1～8的硫醇、C3～8的膦、C1～8的膦酸、C1～8的胺、C1～4的羧酸、C1～4的醇中的一种或多种。
可以理解的是，上述成膜溶液中的成膜溶质就是沉积成膜溶液后形成的膜层的材料。基于上述配体碳链中碳原子数未超过8，上述配体可以被视为短碳链配体。当配体为短碳链配体时，成膜溶液中的溶质表面的配体更容易脱落而使溶质团聚成颗粒，因此，对于带有短碳链配体的溶质而言，利用上述兆声波进行分散更有利于得到稳定的、溶质未团聚的成膜溶液。在一些实施例中，也可以对包括较长碳链配体的成膜溶质进行分散，上述较长碳链配体可以选自但不限于油酸(OA)、正三辛基膦(TOP)、1-十二硫醇(DDT)、十二烷胺(DDA)。
进一步地，当成膜溶液中的溶质为CdS基量子点、ZnSe基量子点、InP基量子点等量子点时，短碳链配体可以包括C3～8的硫醇，C3～8的膦或膦酸，C3～8的胺类等；当成膜溶液中的溶质为ZnO等纳米颗粒时，短碳链配体可以包括C1～4的硫醇，C1～4的膦酸，C1～4的胺类，C1～4的羧酸，C1～4的醇类等。
在一些实施例中，成膜溶液中的溶质利用反应物合成，在合成溶质的过程中，利用兆声波分散所述反应物。
直接利用兆声波合成成膜溶质，能够在合成的过程中对成膜溶质进行分散，将包括合成得到的溶质的成膜溶液直接利用兆声波雾化并沉积，如此既能够减少成膜的步骤，也有利于成膜溶液的性质稳定。合成溶质时，根据所需合成的需要，可以是以一定的体积比或质量比将不同的反应物以一定流速注入反应器中并利用上述声波扰动。可以理解的是，利用兆声波分散反应物，合成溶质可以是相对独立的操作，换言之，合成得到溶质后，可以进一步对包括上述溶质的成膜溶液继续分散，也可以合成得到溶质后停止对包括上述溶质的成膜溶液的分散。优选地，合成得到溶质后，进一步对包括上述溶质的成膜溶液继续分散。
在一些实施例中，利用反应物合成成膜溶质包括：
提供反应物以及极性溶剂，反应物包括金属盐以及沉淀剂；以及
在兆声波的分散下将金属盐、沉淀剂以及极性溶剂混合。在一些实施例中，金属盐可以选自于硝酸盐、醋酸盐、硫酸盐、氯化盐、碳酸盐、高氯酸盐中的一种或多种。
在一些实施例中，沉淀剂可以选自于草酸、尿素、氨水、氢氧化钠、氢氧化钾、碳酸、碳酸氢盐、硫脲、氢氧化四甲铵、乙醇胺中的一种或多种。在一些实施例中，沉淀剂也可以被称为成核反应剂。
在一些实施例中，极性溶剂可以选自于甲醇、乙醇、异丙醇、水中的一种或多种。
在一些实施例中，合成的溶质可以为金属氧化物胶体(例如ZnO胶体)，进一步地，当合成的溶质为ZnO胶体时，反应物可以是醋酸锌等有机盐，沉淀剂可以是氢氧化钾，其中锌有机盐和碱的质量比可以是1～3：1，反应温度可以是40～70℃，反应时长可以为30～60min。
进一步地，合成的溶质还可以为在含有Zn、K、Na的卤盐体系中合成的量子点胶体。
在一些实施例中，分散成膜溶液或合成溶质，利用兆声波进行持续性扰动；或者
利用兆声波以0.5～10min的时间间隔进行间歇式扰动。
优选地，利用兆声波以0.5～1min的时间间隔间歇式扰动成膜溶液。
在一些实施例中，在沉积成膜溶液之后，还包括：利用兆声波雾化清洗剂至成膜溶液形成的表面。即通过兆声波将清洗剂雾化至成膜溶液形成的表面。
需要说明的是，此处“在沉积成膜溶液之后”，可以对成膜溶液进行干燥固化，也可以不对成膜溶剂进行干燥固化。优选地，在成膜溶液干燥固化之前利用兆声波雾化清洗剂至成膜溶液形成的表面。如此，既能够缩短清洗时间，又能够清除纳米颗粒膜层表面的凸起、毛刺等缺陷，使膜层更加平整均匀。
在一些实施例中，在沉积成膜溶液之后，还包括：利用兆声波雾化配体交换溶液至成膜溶液形成的表面。即通过兆声波将配体交换溶液雾化至成膜溶液形成的表面。
此处“在沉积成膜溶液之后”，同样既可以对成膜溶液进行干燥固化，也可以不对成膜溶剂进行干燥固化。优选地，在成膜溶液干燥固化之前利用兆声波 雾化配体交换溶液至成膜溶液形成的表面。
在一些实施例中，膜层为空穴注入层、空穴传输层、空穴阻挡层、发光层、电子阻挡层、电子传输层、电子注入层中的一种或多种。
进一步地，可以利用上述的成膜方法在发光二极管的制备过程中仅制备空穴注入层、空穴传输层、空穴阻挡层、发光层、电子阻挡层、电子传输层、电子注入层中的一层，也可以利用上述成膜方法在发光二极管的制备过程中层叠制备空穴注入层、空穴传输层、空穴阻挡层、发光层、电子阻挡层、电子传输层、电子注入层中的所有膜层。当层叠制备上述膜层时，相邻设置的膜层间的成膜溶剂可以不互溶，如此能够避免在已成膜的膜层上制备新膜层时，新膜层的成膜溶剂破坏已制备的膜层。进一步地，上述发光二极管可以为正置结构的发光二极管，也可以为倒置结构的发光二极管；上述发光二极管可以为顶发射的发光二极管，也可以为底发射的发光二极管，还可以为双面发射的发光二极管。
上述发光二极管可以包括阴极和阳极，阳极的材料可以选自但不限于ITO、FTO、IZO、ITZO、ICO、SnO 2、In 2O 3、Cd:ZnO、F:SnO 2、In:SnO 2、Ga:SnO 2、AZO、Ni、Pt、Au、Ag、Ir中的一种或多种；上述“Cd:ZnO”中的“：”表示掺杂。
阴极的材料可以选自但不限于金属材料、碳材料、金属氧化物中的一种或多种。其中，金属材料可以选自但不限于Al、Ag、Cu、Mo、Au、Ba、Ca、Mg中的一种或多种；碳材料可以选自但不限于石墨、碳纳米管、石墨烯、碳纤维中的一种或多种；金属氧化物可以是掺杂或未掺杂金属氧化物，具体可以选自但不限于ITO、FTO、ATO、AZO、GZO、IZO、MZO、AMO中的一种或多种；进一步地，阴极还可以为具有掺杂或未掺杂的金属氧化物-金属-掺杂或未掺杂的金属氧化物结构(掺杂或未掺杂金属氧化物之间夹着金属)的复合电极，复合电极可以选自但不限于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、TiO 2-Al-TiO 2中的一种或多种。
在一些实施例中，空穴注入层的材料选自于聚(3,4-乙烯二氧噻吩)-聚苯乙烯磺酸(PEDOT：PSS)、2,3,5,6-四氟-7,7',8,8'-四氰二甲基对苯醌(F4-TCNQ)、 铜酞菁(CuPc)、1,4,5,8,9,11-六氮杂苯甲腈(HATCN)、NiO x、MoO x、WO x、CrO x、CuO、MoS x、MoSe x、WS x、WSe x、CuS中的一种或多种，所述x的取值范围为1～3；
空穴传输层的材料选自于聚(9,9-二辛基芴-CO-N-(4-丁基苯基)二苯胺)(TFB)、聚乙烯基咔唑(PVK)、聚(N,N'双(4-丁基苯基)-N,N'-双(苯基)联苯胺)(POLY-TPD)、4,4',4”-三(咔唑-9-基)三苯胺(TCTA)、4,4'-二(9-咔唑)联苯(DCBP)、N,N'-二苯基-N,N'-二(3-甲基苯基)-1,1'-联苯-4,4'-二胺( TPD)、N,N'-二苯基-N,N'-(1-萘基)-1,1'-联苯-4,4'-二胺(NPB)、石墨烯、C60、NiO x、MoO x、WO x、CrO x、CuO、MoS y、MoSe y、WS y、WSe y、CuS中的一种或多种，所述y的取值范围为1～3；
空穴阻挡层的材料选自于ZnO、TiO 2、SnO、ZrO 2、Ta 2O 3中的一种或多种；
发光层为量子点发光层，所述量子点发光层的材料选自于CdSe、CdS、ZnSe、ZnS、CdTe、ZnTe、CdZnS、CdZnSe、CdZnTe、ZnSeS、ZnSeTe、ZnTeS、CdSeS、CdSeTe、CdTeS、CdZnSeS、CdZnSeTe、CdZnSTe、CdSeSTe、ZnSeSTe、CdZnSeSTe、CdSe/ZnS、CdZnSe/ZnS、CdS/CdZnS、InP、InAs、InAsP、InP/InAsP、PbS、PbSe、PbTe、PbSeS、PbSeTe、PbSTe、PbSe/PbS中的一种或多种；
电子阻挡层的材料选自于聚乙烯基咔唑(PVK)、聚[9,9-二辛基-芴-共-N-(4-丁基苯基)-二苯基胺](TFB)、1,1-双[(二-4-甲苯基氨基)苯基环己烷(TAPC)、N,N'-二苯基-N,N'-(1-萘基)-1,1'-联苯-4,4'-二胺(NPB)、NiO、V 2O 5、MoO 3、WO 3中的一种或多种；
电子传输层的材料选自于包括或未包括配体的ZnO、TiO 2、SnO 2、Ta 2O 3、ZrO 2、NiO、TiLiO、ZnAlO、ZnO、ZnSnO、ZnLiO、InSnO中的一种或多种；所述电子传输层的材料的配体选自于羟基、羧基、硫醇基、膦基、胺基、氰基中的一种或多种；
电子注入层的材料选自于LiF、CsF中的一种或多种。
进一步地，当空穴注入层的材料为聚(3,4-乙烯二氧噻吩)-聚苯乙烯磺酸、2,3,5,6-四氟-7,7',8,8'-四氰二甲基对苯醌、铜酞菁、1,4,5,8,9,11-六氮杂苯甲腈等有机物时，空穴注入层的成膜溶剂可以选自但不限于氯苯、甲苯、二氯苯、苯 甲酸乙酯中的一种或多种；当空穴注入层的材料为NiO x、MoO x、WO x、CrO x、CuO、MoS x、MoSe x、WS x、WSe x、CuS等无机物时，空穴注入层的成膜溶剂可以选自但不限于水、乙醇、甲醇、异丙醇等极性溶剂中的一种或多种。
进一步地，当空穴传输层的材料为聚(9,9-二辛基芴-CO-N-(4-丁基苯基)二苯胺)、聚乙烯基咔唑、聚(N,N'双(4-丁基苯基)-N,N'-双(苯基)联苯胺)、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、N,N'-二苯基-N,N'-(1-萘基)-1,1'-联苯-4,4'-二胺、石墨烯、C60时，空穴传输层的成膜溶剂可以选自但不限于二氯苯、苯、氯苯、甲苯、二甲苯、四氢呋喃、氯仿、1，2-二氯乙烷或三氯乙烯等弱极性溶剂中的一种或多种；当空穴传输层的材料为NiO x、MoO x、WO x、CrO x、CuO、MoS x、MoSe x、WS x、WSe x、CuS，空穴传输层的成膜溶剂可以选自但不限于水、乙醇、甲醇、异丙醇等极性溶剂中的一种或多种。
进一步地，发光层的材料可以为具备发光能力的直接带隙化合物半导体，具体可以选自但不限于II-VI族化合物、III-V族化合物、II-V族化合物、III-VI化合物、IV-VI族化合物、I-III-VI族化合物、II-IV-VI族化合物或IV族单质等量子点材料中的一种或多种。进一步地，上述量子点材料可以具有较长碳链的配体或较短碳链的配体，其中，较长碳链的配体可以选自但不限于油酸(OA)、正三辛基膦(TOP)、1-十二硫醇(DDT)、十二烷胺(DDA)中的一种或多种；较短碳链的配体可以选自但不限于C3～8的硫醇，C3～8的膦或膦酸，C3～8的胺类中的一种或多种；发光层的成膜溶剂可以选自但不限于烷烃(如庚烷、正己烷)、氯仿、甲苯等弱极性溶剂中的一种或多种。
进一步地，上述电子传输层的成膜溶剂可以选自但不限于水、乙醇、甲醇、异丙醇等极性溶剂中的一种或多种。
实施例1
本实施例公开一种正置顶发射结构的发光二极管的制备及测试方法，包括：
步骤1：提供镀有ITO膜层(阳极)的基板101，利用丙酮和乙醇对ITO膜层进行超声清洗15min然后用去离子水清洗ITO膜层，然后在150℃的加热板上 干燥上述基板10min，之后利用紫外光照射(UV)基板101上的ITO膜层20min，以增加ITO功函数；
步骤2：将清洗干净的基板放入手套箱，利用声波喷头102雾化空穴注入层的成膜溶液，将雾化后的空穴注入层的成膜溶液喷涂至ITO膜层上，并旋涂空穴注入层的成膜溶液，喷涂过程中，声波可以对基板101表面的膜层的细点凸起20起到一定的清洗作用，从而使得基板101表面的膜层更加清洁平整(参见图3)，其中空穴注入层成膜溶液中的成膜溶质为PEDOT：PSS(质量分数2.8％)，成膜溶剂为甲苯，上述声波的频率为600kHz，功率为50W，喷涂时间为5s，基板转速为2000rpm，旋涂时间为30s，随后在150℃的加热板上加热基板10120min(雾化旋涂空穴注入层的成膜溶液的示意图参见图4)；
步骤3：在制备完成的空穴注入层上旋涂空穴传输层，空穴传输层的成膜溶质为TFB(在成膜溶液中的浓度为6.5mg/mL)，成膜溶剂为四氢呋喃，基板转速为3000rpm，旋涂时间为时间30s，随后在120℃的加热板上加热基板10120min；
步骤4：在制备完成的空穴传输层上旋涂量子点发光层，量子点发光层的成膜溶质为CdSe(在成膜溶液中的浓度为10mg/mL)，成膜溶剂为甲苯，基板转速为1500rpm，旋涂时间为30s，随后于100℃的加热板上加热基板101 5min。
步骤5：在植被完成的量子点发光层上旋涂电子传输层，电子传输层的成膜溶质为ZnO(在成膜溶液中的浓度为30mg/mL)，成膜溶剂为乙醇，基板转速为4000rpm，旋涂时间为30s，随后于80℃的加热板上加热基板101 10min；
步骤6：通过热蒸发，在真空度不高于3x10 -4Pa的环境下在电子传输层上，蒸镀Al作为发光二极管的阴极，蒸镀速度为1埃/秒，蒸镀时间为200s，蒸镀的Al膜层厚度为20nm，得到顶发射的正置型量子点发光二极管；
步骤7：测试器件的JVL数据，确定器件的电流密度(参见图7)，以及器件效率(参见图8)。
步骤8：使用2mA的恒流驱动，测试器件的工作寿命，如表1所示。
实施例2
本实施例公开一种正置顶发射结构的发光二极管的制备及测试方法，包括：
步骤1～2：与实施例1中步骤1～2相同；
步骤3：利用声波喷头雾化空穴传输层的成膜溶液，将雾化后的空穴传输层的成膜溶液喷涂至空穴注入层上，并旋涂空穴传输层的成膜溶液，其中空穴传输层成膜溶液中的成膜溶质为TFB(在成膜溶液中的浓度为10mg/mL)，成膜溶剂为四氢呋喃，上述声波的频率为600kHz，功率为50W，喷涂时间为5s，基板转速为2000rpm，旋涂时间为30s，随后在120℃的加热板上加热基板20min；
步骤4：利用声波喷头雾化量子点发光层的成膜溶液，将雾化后的量子点发光层的成膜溶液喷涂至空穴传输层上，并旋涂量子点发光层的成膜溶液，其中量子点发光层的成膜溶质为CdSe(在成膜溶液中的浓度为14mg/mL)，成膜溶剂为甲苯，上述声波的频率为600kHz，功率为50W，喷涂时间为5s，基板转速为1000rpm，旋涂时间为30s，随后在100℃的加热板上加热基板5min；
步骤5：利用声波喷头雾化电子传输层的成膜溶液，将雾化后的电子传输层的成膜溶液喷涂至量子点发光层上，并旋涂电子传输层的成膜溶液，其中电子传输层的成膜溶质为ZnO(在成膜溶液中的浓度为30mg/mL)，成膜溶剂为乙醇，上述声波的频率为600kHz，功率为50W，喷涂时间为5s，基板转速为2500rpm，旋涂时间为30s，随后在80℃的加热板上加热基板10min；
步骤6：通过热蒸发，在真空度不高于3x10 -4Pa的环境下在电子传输层上，蒸镀Al作为发光二极管的阴极，蒸镀速度为1埃/秒，蒸镀时间为100s，蒸镀的Al膜层厚度为10nm，得到顶发射的正置型量子点发光二极管；
步骤7～8：与实施例1中步骤1～3相同。
实施例3
本实施例公开一种正置顶发射结构的发光二极管的制备及测试方法，包括：
步骤1～3：与实施例1中步骤1～3相同；
步骤4：量子点发光层的成膜溶液置于声波分散容器103中，声波分散容器103中的声波频率设置为600kHz，功率设置为100W，利用声波间歇式扰动上述量子点发光层的成膜溶液，间歇时长1min；然后利用声波喷头102雾化量子点发光层的成膜溶液，将雾化后的量子点发光层的成膜溶液喷涂至空穴传输层上，并旋涂量子点发光层的成膜溶液，其中量子点发光层的成膜溶质为CdSe (在成膜溶液中的浓度为14mg/mL)，成膜溶剂为甲苯，上述声波的频率为600kHz，功率为50W，喷涂时间为5s，基板转速为1000rpm，旋涂时间为30s，随后在100℃的加热板上加热基板101 5min(分散并雾化旋涂量子点发光层的成膜溶液的示意图参见图5)；
步骤5：电子传输层成膜的溶液置于声波分散容器103中，声波分散容器103中的声波频率设置为600kHz，功率设置为100W，利用声波间歇式扰动上述电子传输层的成膜溶液，间歇时长0.5min；然后利用声波喷头102雾化电子传输层的成膜溶液，将雾化后的电子传输层的成膜溶液喷涂至量子点发光层上，并旋涂电子传输层的成膜溶液，其中电子传输层的成膜溶质为ZnO(在成膜溶液中的浓度为30mg/mL)，成膜溶剂为乙醇，上述声波的频率为600kHz，功率为50W，喷涂时间为5s，基板转速为2500rpm，旋涂时间为30s，随后在80℃的加热板上加热基板101 10min；
步骤6～8：与实施例2中步骤6～8相同。
实施例4
本实施例公开一种正置顶发射结构的发光二极管的制备及测试方法，包括：
步骤1～4：与实施例3中步骤1～4相同；
步骤5：将包括目标配体辛硫醇的配体交换溶液(配体交换溶液的溶剂为乙醇)置于声波分散容器中，容器中的声波频率设置为600kHz，功率设置为100W，利用声波间歇式扰动上述电子传输层的成膜溶液，间歇时长1min；然后利用声波喷头雾化配体交换溶液，将雾化后的配体交换溶液喷涂至量子点发光层上，并旋涂配体交换溶液，随后在80℃的加热板上加热基板10min；
步骤6～9：与实施例3中的步骤5～8相同。
实施例5
本实施例公开一种正置顶发射结构的发光二极管的制备及测试方法，包括：
步骤1～4：与实施例3中步骤1～4相同；
步骤5：配制0.1mol/L的醋酸锌的无水乙醇溶液置于第一容器104中，配制1mol/L的氢氧化钠乙醇溶液置于第二容器105，在声波分散容器103中放置 200ml的无水乙醇作为稀释溶剂，然后将醋酸锌的无水乙醇溶液与氢氧化钠乙醇溶液以体积比2:1注入到声波分散容器103中形成混合反应液，在声波分散容器103中的声波频率设置为600kHz，功率设置为100W，利用声波持续扰动上述混合反应液2h，使其反应生成30mg/mL的ZnO胶体溶液，作为电子传输层的成膜溶液；然后利用声波喷头102雾化电子传输层的成膜溶液，将雾化后的电子传输层的成膜溶液喷涂至量子点发光层上，并旋涂电子传输层的成膜溶液，上述声波的频率为600kHz，功率为50W，喷涂时间为5s，基板转速为2500rpm，旋涂时间为30s，随后在80℃的加热板上加热基板101 10min(合成、分散并雾化电子传输层的成膜溶液的示意图参见图6)；
步骤6～8：与实施例3中步骤6～8相同。
对比例(常规制备方法)：
本对比例公开一种正置顶发射结构的发光二极管的制备及测试方法，包括：
步骤1：与实施例1中的步骤1相同。
步骤2：在ITO膜层上旋涂空穴注入层，空穴注入层的成膜溶质为PEDOT：PSS(质量分数2.8％)，成膜溶剂为甲苯，基板转速为3000rpm，旋涂时间为时间30s，随后在150℃的加热板上加热基板20min；
步骤3～8：与实施例1中的步骤3～8相同。
使用2mA的恒流驱动各实施例和对比例制备的器件，测试器件的工作寿命等数据，参见表1。其中L表示器件的最高亮度，单位为cd/m2；T95表示器件在2mA的恒流驱动下亮度衰减至95％所用时间单位为h；T95_1K表示器件亮度为1000nit时，亮度衰减至95％所需时间,单位为h。
表1器件工作寿命测试数据
Figure PCTCN2022143069-appb-000001
Figure PCTCN2022143069-appb-000002
从表1中可以看出：相对于对比例，利用本申请的成膜方法成膜(实施例1～5)制备的器件T95与T95_1K均有所上升，说明利用本申请的成膜方法所制备的器件寿命有所提升。当发光二极管器件的所有膜层均按照本申请中的成膜方法制备时，器件的亮度也有所提升，说明利用本申请的成膜方法所成膜层更为平整、均匀，从而提升了器件的性能。另外，当利用声波直接合成并分散成膜溶质后用于成膜时(实施例5)，器件的寿命最长，说明声波合成并分散成膜溶质能够更有效地避免成膜溶质团聚，从而能够制得更为平整、均匀的膜层。
另外从图7中可以看出，实施例1～5与对比例的器件的电流密度变化不大，但从图8可以看出，相对对比例，利用本申请中的成膜方法制备的器件的器件效率明显提升，进一步佐证本申请中技术方案所成膜层的平整度和膜层均匀性较佳。
以上对本申请实施例所提供的发光二极管膜层及其成膜方法、发光二极管进行了详细介绍，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。

Claims (20)

  1. 一种发光二极管膜层的成膜方法，其中，包括：
    提供基板；以及
    往所述基板施加雾化的成膜溶液并沉积所述成膜溶液。
  2. 根据权利要求1所述的成膜方法，其中，所述成膜溶液的雾化方式为利用兆声波进行雾化，所述兆声波的频率为400～1000kHz。
  3. 根据权利要求2所述的成膜方法，其中，所述兆声波的功率为20～200W。
  4. 根据权利要求1-3任一项所述的成膜方法，其中，所述往所述基板施加雾化的成膜溶液并沉积所述成膜溶液的步骤，在保护气体的环境下进行；
    其中，所述保护气体的环境中的水含量小于5ppm；和/或
    所述保护气体选自氮气、氩气中的一种或多种。
  5. 根据权利要求1-4任一项所述的成膜方法，其中，所述成膜溶液为经所述兆声波分散的成膜溶液。
  6. 根据权利要求5所述的成膜方法，其中，所述成膜溶液经过所述兆声波分散之后，雾化形成所述雾化的成膜溶液。
  7. 根据权利要求2-6任一项所述的成膜方法，其中，所述成膜溶液包括成膜溶质和成膜溶剂，所述成膜溶质包括配体，所述配体选自于C1～8的硫醇、C3～8的膦、C1～8的膦酸、C1～8的胺、C1～4的羧酸、C1～4的醇中的一种或多种。
  8. 根据权利要求7所述的成膜方法，其中，所述成膜溶质利用反应物合成，在合成所述成膜溶质的过程中，利用所述兆声波分散所述反应物。
  9. 根据权利要求8所述的成膜方法，其中，利用所述反应物合成所述成膜溶质包括：
    提供所述反应物以及极性溶剂，所述反应物包括金属盐以及沉淀剂；以及
    在所述兆声波的分散下将所述金属盐、所述沉淀剂以及所述极性溶剂混合。
  10. 根据权利要求9所述的成膜方法，其中，所述金属盐选自于硝酸盐、醋酸盐、硫酸盐、氯化盐、碳酸盐、高氯酸盐中的一种或多种；和/或
    所述沉淀剂选自于草酸、尿素、氨水、氢氧化钠、氢氧化钾、碳酸、碳酸氢盐、硫脲、氢氧化四甲铵、乙醇胺中的一种或多种；和/或
    所述极性溶剂选自于甲醇、乙醇、异丙醇、水中的一种或多种。
  11. 根据权利要求9所述的成膜方法，其中，所述成膜溶质包括ZnO，所述金属盐选自锌有机盐，所述沉淀剂选自碱，所述锌有机盐与所述碱的质量比为1～3：1。
  12. 根据权利要求7-11任一项所述的成膜方法，其中，分散所述成膜溶液或合成所述成膜溶质时，利用所述兆声波进行持续性扰动；或者
    利用所述兆声波进行间歇式扰动。
  13. 根据权利要求12所述的成膜方法，其中，利用所述兆声波以0.5～1min的时间间隔进行间歇式扰动。
  14. 根据权利要求1-13任一项所述的成膜方法，其中，在沉积所述成膜溶液之后，还包括：利用所述兆声波雾化清洗剂至所述成膜溶液形成的表面；和/或
    在沉积所述成膜溶液之后，还包括：利用所述兆声波雾化配体交换溶液至所述成膜溶液形成的表面。
  15. 根据权利要求1-14任一项所述的成膜方法，其中，所述发光二极管膜层为空穴注入层、空穴传输层、空穴阻挡层、发光层、电子阻挡层、电子传输层、电子注入层中的一种或多种。
  16. 根据权利要求15所述的成膜方法，其中，所述空穴注入层的材料选自于聚(3,4-乙烯二氧噻吩)-聚苯乙烯磺酸、2,3,5,6-四氟-7,7',8,8'-四氰二甲基对苯醌、铜酞菁、1,4,5,8,9,11-六氮杂苯甲腈、NiO x、MoO x、WO x、CrO x、CuO、MoS x、MoSe x、WS x、WSe x、CuS中的一种或多种，所述x的取值范围为1～3；和/或
    所述空穴传输层的材料选自于聚(9,9-二辛基芴-CO-N-(4-丁基苯基)二苯胺)、聚乙烯基咔唑、聚(N,N'双(4-丁基苯基)-N,N'-双(苯基)联苯胺)、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、N,N'-二苯基-N,N'-(1-萘基)-1,1'-联苯-4,4'-二胺、石墨烯、C60、NiO y、MoO y、WO y、CrO y、CuO、MoS y、MoSe y、WS y、WSe y、CuS中的一 种或多种，所述y的取值范围为1～3；和/或
    所述空穴阻挡层的材料选自于ZnO、TiO 2、SnO、ZrO 2、Ta 2O 3中的一种或多种；和/或
    所述发光层为量子点发光层，所述量子点发光层的材料选自于CdSe、CdS、ZnSe、ZnS、CdTe、ZnTe、CdZnS、CdZnSe、CdZnTe、ZnSeS、ZnSeTe、ZnTeS、CdSeS、CdSeTe、CdTeS、CdZnSeS、CdZnSeTe、CdZnSTe、CdSeSTe、ZnSeSTe、CdZnSeSTe、CdSe/ZnS、CdZnSe/ZnS、CdS/CdZnS、InP、InAs、InAsP、InP/InAsP、PbS、PbSe、PbTe、PbSeS、PbSeTe、PbSTe、PbSe/PbS中的一种或多种；和/或
    所述电子阻挡层的材料选自于聚乙烯基咔唑、聚[9,9-二辛基-芴-共-N-(4-丁基苯基)-二苯基胺]、1,1-双[(二-4-甲苯基氨基)苯基环己烷、N,N'-二苯基-N,N'-(1-萘基)-1,1'-联苯-4,4'-二胺、NiO、V 2O 5、MoO 3、WO 3中的一种或多种；和/或
    所述电子传输层的材料选自于包括或未包括配体的ZnO、TiO 2、SnO 2、Ta 2O 3、ZrO 2、NiO、TiLiO、ZnAlO、ZnO、ZnSnO、ZnLiO、InSnO中的一种或多种；所述配体选自于羟基、羧基、硫醇基、膦基、胺基、氰基中的一种或多种；和/或
    所述电子注入层的材料选自于LiF、CsF中的一种或多种。
  17. 根据权利要求1所述的成膜方法，其中，所述发光二极管膜层包括空穴注入层、空穴传输层、发光层和电子传输层；
    其中，所述发光二极管膜层为所述空穴注入层时，利用兆声波雾化所述成膜溶液，其中，所述成膜溶液包括成膜溶质和成膜溶剂，所述成膜溶质为聚(3,4-乙烯二氧噻吩)-聚苯乙烯磺酸，所述成膜溶剂为甲苯；
    所述发光二极管膜层为所述空穴传输层时，利用兆声波雾化所述成膜溶液，其中，所述成膜溶液包括成膜溶质和成膜溶剂，所述成膜溶质为聚[9,9-二辛基-芴-共-N-(4-丁基苯基)-二苯基胺]，所述成膜溶剂为四氢呋喃；
    所述发光二极管膜层为发光层时，利用兆声波雾化所述成膜溶液，其中，所述成膜溶液包括成膜溶质和成膜溶剂，所述成膜溶质为CdSe，所述成膜溶剂为甲苯，所述利用所述兆声波雾化所述成膜溶液之前，所述成膜溶液经过兆 声波分散，并利用所述兆声波进行间歇式扰动；
    所述发光二极管膜层为电子传输层时，利用兆声波雾化所述成膜溶液；其中，所述成膜溶液的制备方法包括：提供反应物以及乙醇，所述反应物包括醋酸锌以及氢氧化钠；以及在所述兆声波的分散下将所述醋酸锌、所述氢氧化钠以及所述乙醇混合，并利用所述兆声波进行持续扰动，得到所述成膜溶液。
  18. 根据权利要求17所述的成膜方法，其中，
    所述利用兆声波雾化所述成膜溶液中的所述兆声波的频率为600kHz，功率为50W；
    所述利用所述兆声波进行间歇式扰动，包括：利用所述兆声波以1min的时间间隔进行间歇式扰动；
    所述成膜溶液经过兆声波分散中，所述兆声波的频率为600kHz，功率为100W；
    所述在所述兆声波的分散下将所述醋酸锌、所述氢氧化钠以及所述乙醇混合，并利用所述兆声波进行持续扰动中，所述兆声波的频率为600kHz，功率为100W。
  19. 一种发光二极管膜层，其中，由权利要求1-18任一项所述的发光二极管膜层的成膜方法制得。
  20. 一种发光二极管，其中，包括权利要求19所述的发光二极管膜层。
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002233796A (ja) * 2001-02-07 2002-08-20 Auto Network Gijutsu Kenkyusho:Kk 薄膜形成装置及び薄膜形成方法
JP2009199757A (ja) * 2008-02-19 2009-09-03 Konica Minolta Holdings Inc 有機エレクトロルミネッセンスパネルの製造方法
CN108778527A (zh) * 2016-03-11 2018-11-09 株式会社尼康 雾气产生装置、成膜装置、雾气产生方法、成膜方法、及元件制造方法
JP2018181658A (ja) * 2017-04-17 2018-11-15 独立行政法人国立高等専門学校機構 有機発光素子の製造方法
CN109599508A (zh) * 2018-12-17 2019-04-09 嘉兴纳鼎光电科技有限公司 电致发光器件及其制备方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002233796A (ja) * 2001-02-07 2002-08-20 Auto Network Gijutsu Kenkyusho:Kk 薄膜形成装置及び薄膜形成方法
JP2009199757A (ja) * 2008-02-19 2009-09-03 Konica Minolta Holdings Inc 有機エレクトロルミネッセンスパネルの製造方法
CN108778527A (zh) * 2016-03-11 2018-11-09 株式会社尼康 雾气产生装置、成膜装置、雾气产生方法、成膜方法、及元件制造方法
JP2018181658A (ja) * 2017-04-17 2018-11-15 独立行政法人国立高等専門学校機構 有機発光素子の製造方法
CN109599508A (zh) * 2018-12-17 2019-04-09 嘉兴纳鼎光电科技有限公司 电致发光器件及其制备方法

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