WO2022134892A1 - 电荷传输层的制备方法和发光二极管 - Google Patents

电荷传输层的制备方法和发光二极管 Download PDF

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WO2022134892A1
WO2022134892A1 PCT/CN2021/129007 CN2021129007W WO2022134892A1 WO 2022134892 A1 WO2022134892 A1 WO 2022134892A1 CN 2021129007 W CN2021129007 W CN 2021129007W WO 2022134892 A1 WO2022134892 A1 WO 2022134892A1
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layer
film layer
preparation
solution
transport layer
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PCT/CN2021/129007
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French (fr)
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陈开敏
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Tcl科技集团股份有限公司
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Publication of WO2022134892A1 publication Critical patent/WO2022134892A1/zh
Priority to US17/935,781 priority Critical patent/US20230105743A1/en

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    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • 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
    • H10K50/15—Hole transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting layers
    • 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
    • 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
    • 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
    • H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
    • 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
    • H10K71/811—Controlling the atmosphere during processing
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the application belongs to the field of optoelectronic technology, and in particular relates to a preparation method of a charge transport layer and a light emitting diode.
  • CTLs Charge transport layers
  • ETL electron transport layers
  • HTL hole transport layers
  • colloidal metal oxide nanocrystals have attracted great interest as CTLs.
  • ETL based on colloidal ZnO nanocrystals, which has been used in several prototype devices with good performance.
  • colloidal oxide nanocrystals are fully compatible with large-scale industrial production, thus showing a bright prospect for high-performance, low-cost, and large-area devices.
  • the current research on the application of colloidal metal oxide nanocrystals in optoelectronic devices mainly focuses on the synthesis chemistry of colloidal oxide nanocrystals, ligand chemistry that may be applicable to colloidal oxide nanocrystals, and chemistry related to post-deposition processing.
  • the current ink scheme uses an orthogonal solvent system to deposit adjacent functional layers.
  • the viscosity and surface tension of the ink the continuous, pinhole-free and overall thickness control of the CTL film can be basically achieved.
  • the existing deposited CTL films still have certain deficiencies.
  • the defects caused by the local agglomeration of colloidal metal oxide nanocrystals in the film not only reduce the exciton mobility of CTL, but also the formed excitons may also Dissociation occurs at defects resulting in reduced device efficiency.
  • the main cause of the local defects is the uncontrolled deposition process, and the research on the local defects of the CTL films is rarely reported.
  • the present application provides a method for preparing a charge transport layer and a light emitting diode to solve the technical problem of low exciton mobility or dissociation due to local defects in the charge transport layer formed by existing colloidal metal oxide nanocrystals.
  • the present application provides a method for preparing a charge transport layer.
  • the preparation method of the charge transport layer includes the following steps:
  • the first film layer is formed using the first solution containing the functional material
  • the second film layer is formed using the second solution containing the charge transport material
  • the first film layer and the second film layer are adjacent to each other, or the first solution and the second film layer are formed
  • the mixed solution of the solution forms a mixed film layer
  • the functional material is an organic substance containing an electron-donating group
  • the surface of the charge transport material has a metal cation dangling bond
  • the electron-donating group can be combined with the metal cation dangling bond.
  • the method of contacting the first film layer and the second film layer with each other comprises the steps of:
  • the first solution is formed on the surface of the second film layer to form a first film layer.
  • the method of contacting the first film layer and the second film layer with each other comprises the steps of:
  • the second solution is formed on the surface of the first film layer to form a second film layer.
  • the method for forming the mixed film layer from the mixed solution of the first solution and the second solution includes the following steps:
  • the mixed solution of the first solution and the second solution is formed on the substrate to form a mixed film layer.
  • the molar ratio of the functional material to the charge transport material is 1.5-3:1.
  • the functional material includes triethylamine.
  • the volume ratio of the functional material to the solvent is 1:(1 ⁇ 50).
  • the solvent of the first solution includes at least one of acetone, n-butanol, tetrahydrofuran, and methyl formate.
  • the solvents of the first solution and the second solution are mutually soluble or have similar polarities.
  • the method for removing functional materials comprises the steps of:
  • heat treatment is performed on the first film layer and the second film layer or the mixed film layer, so that the functional material is volatilized and removed.
  • the temperature of the heat treatment is 90°C to 150°C.
  • the heat treatment time is 5 min ⁇ 24 h.
  • the charge transport material is a hole transport material or an electron transport material.
  • the hole transport material includes at least one of MoO 3 , NiO, V 2 O 5 and WO 3 , or includes at least one metal doped with Li, Al, Mg, Cs, In, Ga, and Zr. At least one of mixed MoO 3 , NiO, V 2 O 5 and WO 3 .
  • the electron transport material includes at least one of ZnO, SnO, TiO 2 and ZrO 2 , or includes ZnO doped with at least one metal of Li, Al, Mg, Cs, In, Ga, Zr, At least one of SnO, TiO 2 and ZrO 2 .
  • a light emitting diode in yet another aspect of the present application, includes an electron transport layer, and the electron transport layer is prepared and formed according to the preparation method of the charge transport layer of the present application, wherein the charge transport material is an electron transport material.
  • the light-emitting diode includes a hole transport layer, and the hole transport layer is prepared according to the preparation method of the charge transport layer of the present application, wherein the charge transport material is a hole transport material.
  • the light-emitting diode includes an electron transport layer and a hole transport layer
  • the electron transport layer is prepared according to the preparation method of the charge transport layer of the present application, wherein the charge transport material is an electron transport material;
  • the preparation method is prepared and formed, wherein the charge transport material is a hole transport material.
  • the light emitting diode is QLED or OLED.
  • the second solution and the first solution are respectively formed into a film layer or a mixture is formed first and then the film is formed, so that the functional material will be combined with the metal cation dangling bonds on the surface of the metal oxide nanomaterial. , to achieve the effect of end capping.
  • the solvent in the charge transport wet film layer is volatilized, the metal oxide nanomaterials with functional materials on the surface will first form a stable state similar to "oligomers", and will During the deposition process, these "oligomers” will undergo an ordered arrangement similar to polymer polymerization, so that the metal oxide nanomaterials become ordered during the deposition process and reduce the chance of defects in the film formation process.
  • the prepared charge The metal oxide nanomaterials in the transport layer can be arranged in an orderly manner, and the charge transport layer has few or no defects, so that the charge transport layer has a high transfer rate for excitons and can avoid the phenomenon of excitons dissociating.
  • the formation conditions of the layer structure in the preparation method of the charge transport layer are controllable, which effectively ensures the stability of the preparation performance of the charge transport layer, and the efficiency is high.
  • the light-emitting diode of the present application contains the charge transport layer prepared by the above-mentioned preparation method of the charge transport layer of the present application, the electron transport layer and/or the hole transport layer prepared according to the above-mentioned preparation method of the charge transport layer of the present application, in this way, the light-emitting diode contains The metal oxide nanomaterials contained in the electron transport layer and/or hole transport layer can be arranged in an orderly manner, and the charge transport layer has little or no defects, thereby endowing the charge transport layer with the characteristics of high exciton migration rate, thereby The light-emitting diode of the present application is endowed with high luminous efficiency.
  • FIG. 1 is a schematic diagram of a process flow of a method for preparing a charge transport layer in an embodiment of the present application; wherein, Figure a is a first method for preparing a charge transport layer in an embodiment of the present application, and Figure b is a second method for preparing a charge transport layer in an embodiment of the present application.
  • a preparation method, Figure c is the third preparation method of the charge transport layer in the embodiment of the present application;
  • FIG. 2 is a schematic structural diagram of a positive configuration light-emitting diode provided by an embodiment of the present application
  • FIG. 3 is a schematic structural diagram of a light-emitting diode with an inversion configuration provided by an embodiment of the present application
  • FIG. 4 is the EL topography diagram of the positive light emitting diodes provided in Examples 1 to 2 and Comparative Example 3 of the present application; wherein, FIG. 4( a ) is the EL topography diagram of the positive light emitting diode provided in Example 1 FIG. 4(b) is the EL topography of the positive light-emitting diode provided by Example 2; FIG. 4(c) is the EL topography of the positive light-emitting diode provided by Comparative Example 3.
  • a method for preparing a charge transport layer includes forming a first film layer using a first solution containing a functional material and forming a second film layer using a second solution containing a charge transport material, and making the first film layer and the second film layer adjacent to each other , and then removing the functional material to obtain a charge transport layer; or using a mixed solution of the first solution and the second solution to form a mixed film layer, and then removing the functional material to obtain a charge transport layer. Therefore, in the embodiment, the preparation method of the charge transport layer includes at least the following three preparation methods of the charge transport layer:
  • the first preparation method of the charge transport layer is the first preparation method of the charge transport layer
  • the second film layer 2 will be formed on the substrate 1 by using the second solution containing the charge transport material;
  • S02 will use the first solution containing the functional material to form the first film layer 3 on the surface of the second film layer 2;
  • the functional material contained in the first solution in steps S02, S04 and S07 of the above-mentioned preparation method of the charge transport layer is an organic substance containing an electron donating group
  • the functional material contained in the second solution is an electron-donating group.
  • the surface of the contained charge transport material has metal cation dangling bonds, and the electron-donating group contained in the functional material can be combined with the metal cation dangling bonds on the surface of the charge transport material.
  • the two solvents will fuse.
  • the functional material will be in direct contact with the charge transport material in the composite wet film layer, so that the electron-donating group contained in the functional material can interact with the metal cation dangling bonds on the surface of the charge transport material. combine.
  • the mixed solution of step S07 the functional material and the charge transport material are in direct contact in the mixed film layer 4 .
  • the electron-donating group contained in the functional material is combined with the metal cation dangling bond on the surface of the charge transport material to achieve the effect of end capping.
  • the surface is bound with the charge transport of the functional material.
  • the material will first form a stable state similar to "oligomers”, and these "oligomers” will undergo an ordered arrangement similar to polymer polymerization during the deposition process, so that the charge transport material becomes order, reducing the chance of defects in the film formation process.
  • the charge transport materials in the prepared charge transport layer can be arranged in an orderly manner, and the charge transport layer has few or no defects, so that the charge transport layer has the correct It has the characteristics of high exciton migration rate and can avoid the phenomenon of exciton dissociation.
  • the functional materials suitable for the embodiments of the present application can meet the following three characteristics: 1) can be processed in solution; 2) have electron donating groups, which can form similar to charge transport materials "Oligomer” to achieve the desired effect; 3) easy to be cleared.
  • the 1) and 2) features should be the basic requirements, and the 3) is optional. Therefore, in one embodiment, the above-mentioned functional material includes triethylamine.
  • the volume ratio of the functional materials and the solvent contained in the first solution in step S02, step S04 and step S07 is 1: (1 ⁇ 50) .
  • the solvent contained in the first solution includes at least one of acetone, n-butanol, tetrahydrofuran, and methyl formate.
  • the functional material relative to the charge transport material is controlled in sufficient amount , so that the functional material and the metal cation dangling bonds on the surface of the charge transport material are combined to achieve the effect of end capping, and the charge transport material is fully ordered in the formed charge transport layer, thereby further reducing or completely eliminating defects in the charge transport layer to further The transfer efficiency of the charge transport layer to excitons is formed. Therefore, in one embodiment, the molar ratio of the functional material in the first film layer 3 to the charge transport material in the second film layer 2 is 1.5-3:1. Alternatively, in the mixed solution in step S07, that is, in the mixed film layer 4, the molar ratio of the functional material to the charge transport material is 1.5-3:1.
  • the formation method of the first film layer 3 in steps S02 and S04 can be formed according to the existing solution film formation method.
  • the first film layer 3 can be formed with reference to the film formation method of the charge transport layer, as in the specific embodiment.
  • the formation method of the first film layer 3 includes spin coating, ink jet printing, spray coating, blade coating and other methods.
  • the second solution in step S01 , step S05 and step S07 may be a conventional second solution used for preparing a charge transport layer.
  • the second solution contains a charge transport material.
  • the charge transport material includes metal oxide nanomaterials (metal oxide nanocrystalline materials), that is, the second solution in step S01 , step S05 and step S07 contains metal oxide nanomaterials.
  • the second solution in step S01 , step S05 and step S07 may be an electron transport material ink or a hole transport material ink.
  • the electron transport material contained in the electron transport material ink includes metal oxide nanomaterials, and the metal oxide nanomaterials are nano metal oxides Electron transport material.
  • the nano-metal oxide electron transport material includes at least one of ZnO, SnO, TiO 2 and ZrO 2 , or includes at least one of metal-doped ZnO, SnO, TiO 2 and ZrO 2 wherein the doping metal used for doping at least one of ZnO, SnO, TiO 2 and ZrO 2 includes at least one of Li, Al, Mg, Cs, In, Ga, and Zr.
  • the selection of the nano metal oxide electron transport material can not only make the formed electron transport layer have good continuity, no pinholes and overall thickness and high electron transport efficiency, but more importantly, it can be compatible with the steps in steps S02, S04 and S07.
  • the functional materials contained in the first solution interact with each other as described above, thereby improving the electron transport layer formed with fewer or no defects, and with high electron transport efficiency.
  • the hole transport material contained in the hole transport material ink includes metal oxide nanomaterials, and the metal oxide nanomaterials are nanomaterials.
  • the nano-metal oxide hole transport material includes at least one of MoO 3 , NiO, V 2 O 5 and WO 3 , or includes metal-doped MoO 3 , NiO, V 2 O 5 and at least one of WO 3 ; wherein, the doping metal used for doping at least one of MoO 3 , NiO, V 2 O 5 and WO 3 includes Li, Al, Mg, Cs, In, Ga, at least one of Zr.
  • the concentration of the second solution in step S01 , step S05 and step S07 can be adjusted according to the requirements of the method of forming the charge transport wet film layer such as the second film layer 2 and the mixed film layer 4 .
  • the preparation method of the charge transport layer is when the charge transport layer is prepared according to the first or second preparation method above. , after the second film layer 2 is formed in step S01, it should be formed immediately and then step S02 is also formed; The second film layer 2, so that the second film layer 2 and the first film layer 3 have sufficient fusion time.
  • the formation methods of the second film layer 2 in step S01, the second film layer 2 in step S05 and the mixed film layer 4 in step S07 can be formed according to the existing solution film formation method.
  • the formation methods of the second film layer 2 and the mixed film layer 4 include spin coating, ink jet printing, spray coating, blade coating and other methods.
  • the solvents of the second film layer 2 and the first film layer 3 are mutually soluble and have similar polarities.
  • the second film layer 2 is formed by the spin coating process, due to the characteristics of the spin coating process , a small thickness of the second film layer 3 may be peeled off, which can be compensated by pre-stating and calculating the loss amount and adjusting the thickness of the second film layer 2, etc.
  • the substrate 1 in step S01, step S04 and step S07 can be any substrate that needs to form a charge transport layer on the surface of the corresponding component or device.
  • the substrate can be a corresponding component contained in an electroluminescent device (such as a light emitting diode), such as a positive electrode, a negative electrode, an electron injection layer, a hole injection layer, the surface of the light emitting layer, depending on the corresponding electrical The order of preparation of the luminescent devices varies.
  • the method for removing the functional material to obtain the charge transport layer in the above-mentioned embodiments includes the first film layer 3 and the second film layer 2 or the
  • the mixed film layer 4 is subjected to a drying treatment step to effectively remove the functional material in the composite wet film layer or the mixed film layer 4 and simultaneously remove the solvent to form a charge transport layer.
  • the method of drying comprises the following steps:
  • the composite wet film layer or the mixed film layer 4 is heat-treated in an inert gas atmosphere.
  • the temperature of the heat treatment is 90°C to 150°C.
  • the solvent and functional material of the composite wet film layer or the mixed film layer 4 are volatilized and cured to form a charge transport layer.
  • the drying treatment such as the heat treatment time at 90°C to 150°C, should be sufficient, and the specific heat treatment time should be 5 mins to 24 hrs.
  • the thickness and solvent properties of the composite wet film layer or the mixed film layer 4 can be adjusted according to the actual situation.
  • the preparation method of the charge transport layer in the embodiment of the present application can not only enable the functional material contained in the first solution to interact with the charge transport material in the second solution, so that the charge transport material is in the prepared charge transport layer. It can be arranged in an orderly manner, so that the charge transport layer has few or no defects, so that the charge transport layer has the characteristics of high exciton migration rate and can avoid the phenomenon of dissociation of excitons.
  • the formation conditions of the layer structure in the preparation method of the charge transport layer are controllable, which effectively ensures the stability of the preparation performance of the charge transport layer, and the efficiency is high.
  • an embodiment of the present application further provides a light emitting diode.
  • the light emitting diode contains an electron transport layer and a hole transport layer.
  • the light emitting diode also contains other necessary layer structures of the light emitting diode, such as a light emitting layer, an anode and a cathode.
  • the electron transport layer contained in the light-emitting diode is an electron transport layer prepared according to the preparation method of the charge transport layer above.
  • the charge transport material contained in the second solution used is the electron transport material.
  • the hole transport layer contained in the light-emitting diode is a hole transport layer prepared according to the above-mentioned preparation method of the charge transport layer.
  • the charge transport material contained in the second solution used is a hole transport material.
  • the electron transport layer and the hole transport layer contained in the light-emitting diode can be prepared according to the above-mentioned preparation method of the charge transport layer at the same time.
  • the preparation method of the charge transport layer is formed.
  • the electron transport layer and the hole transport layer may be prepared according to the preparation method of the charge transport layer above, which can improve the electron transport efficiency and hole transport efficiency at the same time, thereby improving the excitation efficiency in the light-emitting layer. Therefore, the luminous efficiency of light-emitting diodes can be improved, such as improving the external quantum efficiency (EQE) of light-emitting diodes.
  • EQE external quantum efficiency
  • the light-emitting diode in the embodiment of the present application may be a quantum dot light-emitting diode (QLED) or an organic electroluminescent diode (OLED).
  • QLED quantum dot light-emitting diode
  • OLED organic electroluminescent diode
  • the light emitting diode in the embodiment of the present application may be a positive light emitting diode or an inversion light emitting diode.
  • the structure of the positive light emitting diode is shown in FIG. 2 , which includes a stacked structure of an anode 10 and a cathode 50 disposed opposite to each other, wherein the anode 10 can be stacked on the substrate 01 .
  • a light-emitting functional layer is laminated and bonded to the cathode 50 .
  • the light-emitting functional layer includes a light-emitting layer 30, a hole transport layer 20 and an electron transport layer 40. From the anode 10 to the cathode 50, the hole transport layer 20, the light-emitting functional layer 30, and the electron transport layer 40 are stacked in sequence.
  • a hole injection layer (not shown in FIG. 2 ) may also be arranged between the hole transport layer 20 and the anode 10
  • an electron injection layer (not shown in FIG. 2 ) may be arranged between the electron transport layer 40 and the cathode 50 .
  • the hole transport layer 20 is prepared by the above method for preparing the charge transport layer, the formed anode 10 is used as the matrix 1, and the hole transport material ink is used as the second solution on the outer surface of the anode 10 according to the above method.
  • Preparation method of charge transport layer The hole transport layer 20 is prepared.
  • the positive light-emitting diode shown in FIG. 2 contains a hole injection layer
  • the formed hole injection layer is used as the matrix 1
  • the hole transport material ink is used as the second solution on the outer surface of the hole injection layer.
  • the hole transport layer 20 is prepared according to the above preparation method of the charge transport layer. Then, the light emitting layer 30 , the electron transport layer 40 , (or the hole injection layer is further formed) and the cathode 50 are sequentially formed on the outer surface of the hole transport layer 20 according to the existing method.
  • the electron transport layer 40 is prepared by the above-mentioned preparation method of the charge transport layer, the formed light-emitting layer 30 is used as the matrix 1, and the electron transport material ink is used as the second solution on the outer surface of the light-emitting layer 30 according to the above method.
  • the electron transport layer 40 is prepared by the method for preparing the charge transport layer.
  • FIG. 3 the structure of an inversion-type light-emitting diode is shown in FIG. 3 , which includes a stacked structure of an anode 10 and a cathode 50 arranged oppositely, wherein the cathode 50 can be stacked on the substrate 01, and the anode 50 can be stacked on the substrate 01.
  • a light-emitting functional layer is laminated and bonded between the cathode 10 and the cathode 50 .
  • the light-emitting functional layer includes a light-emitting layer 30, a hole transport layer 20 and an electron transport layer 40. From the anode 10 to the cathode 50, the hole transport layer 20, the light-emitting functional layer 30, and the electron transport layer 40 are stacked in sequence.
  • a hole injection layer (not shown in FIG. 2 ) may also be arranged between the hole transport layer 20 and the anode 10
  • an electron injection layer (not shown in FIG. 2 ) may be arranged between the electron transport layer 40 and the cathode 50 .
  • the electron transport layer 40 is prepared by the above method for preparing the charge transport layer, the formed cathode 50 is used as the substrate 1, and on the outer surface of the cathode 50, the electron transport material ink is used as the second solution, according to the above charge Preparation Method of Transport Layer
  • the electron transport layer 40 is prepared.
  • the inversion light-emitting diode shown in FIG. 2 contains an electron injection layer
  • the formed electron injection layer is used as the substrate 1
  • the electron transport material ink is used as the second solution on the outer surface of the electron injection layer.
  • Preparation Method of Transport Layer The electron transport layer 40 is prepared. Then, the light emitting layer 30 , the hole transport layer 20 , (or further form the hole injection layer) and the anode 10 are sequentially formed on the outer surface of the electron transport layer 40 according to the existing method.
  • the hole transport layer 20 is prepared by the above-mentioned preparation method of the charge transport layer, the formed light-emitting layer 30 is used as the matrix 1, and the hole transport material ink is used as the second solution on the outer surface of the light-emitting layer 30 according to The above preparation method of the charge transport layer prepares the hole transport layer 20 .
  • QLED is used as an example for description.
  • the structure of QLED is ITO/hole transport layer (30nm)/CdSe/ZnS (40nm)/electron transport layer (40nm)/Ag (120nm). It should be understood that the structure of the QLED is only exemplary, and the present application is not limited thereto.
  • This embodiment provides a QLED light-emitting diode and a manufacturing method thereof.
  • the structure of the QLED light-emitting diode is shown in Figure 2.
  • the positive quantum dot light-emitting diode has the structure of ITO/PEDOT:PSS (30nm) hole transport layer (30nm)/CdSe/ZnS (40nm)/electron transport layer (40nm) /Ag (120nm).
  • ITO/PEDOT:PSS (30nm) hole transport layer (30nm)/CdSe/ZnS (40nm)/electron transport layer (40nm) /Ag (120nm).
  • "/" expresses the connection relationship of the layer structure of the layered bonding.
  • S1 provide a substrate, and form a bottom electrode (anode) on the substrate;
  • S3 First deposit a zinc oxide-ethanol solution on the surface of the quantum dot light-emitting layer to form a zinc oxide electron transport wet film layer, which is also the second film layer; then continue to deposit triethylamine-acetone on the surface of the zinc oxide electron transport wet film layer solution to form a first film layer containing triethylamine, thereby forming a composite wet film layer of zinc oxide-triethylamine, and then heat treatment in an inert atmosphere on a heating table at 120 ° C for 50 mins to form a zinc oxide electron transport layer; wherein , in the composite wet film layer of zinc oxide-triethylamine, the molar ratio of triethylamine and zinc oxide is 2:1;
  • a top electrode is deposited on the zinc oxide electron transport layer.
  • This embodiment provides a QLED light-emitting diode and a manufacturing method thereof.
  • the structure of the QLED light-emitting diode is the positive quantum dot light-emitting diode shown in FIG. 2 , and its structure is the same as that of the first embodiment.
  • S1 provide a substrate, and form a bottom electrode (anode) on the substrate;
  • S3 deposit triethylamine-acetone solution on the surface of the quantum dot light-emitting layer first to form a first film layer of triethylamine; then deposit zinc oxide-ethanol solution on the surface of the first film layer to form a zinc oxide electron transport wet film
  • the zinc oxide-triethylamine composite wet film layer was formed, and then heat-treated on a heating table at 150 °C for 30 mins in an inert atmosphere to form a zinc oxide electron transport layer; among them, the zinc oxide-triethylamine composite wet film was In the layer, the molar ratio of triethylamine and zinc oxide is 2:1;
  • a top electrode is deposited on the zinc oxide electron transport layer.
  • This embodiment provides a QLED light-emitting diode and a manufacturing method thereof.
  • the structure of the QLED light-emitting diode is shown in Figure 2 as a positive quantum dot light-emitting diode, which includes ITO/NiO hole transport layer (30nm)/CdSe/ZnS (40nm)/zinc oxide electron transport layer (40nm)/Ag (120nm) ).
  • ITO/NiO hole transport layer (30nm)/CdSe/ZnS (40nm)/zinc oxide electron transport layer (40nm)/Ag (120nm)
  • "/" expresses the connection relationship of the layer structure of the layered bonding.
  • S1 provide a substrate, and form a bottom electrode (anode) on the substrate;
  • S2 spin-coat NiO-water solution on the bottom electrode to form a NiO hole transport wet film layer; then continue to deposit triethylamine-n-butanol solution on the surface of the NiO hole transport wet film layer to form a triethylamine functional wet film layer to form a composite wet film layer of NiO-triethylamine, and then heat treatment on a heating table at 120 °C for 30 mins to form a NiO hole transport layer;
  • S4 First deposit a zinc oxide-ethanol solution on the surface of the quantum dot light-emitting layer to form a zinc oxide electron transport wet film layer; then heat the zinc oxide electron transport wet film layer directly in an inert atmosphere on a heating table at 100 °C for 50 mins to form Zinc oxide electron transport layer;
  • a top electrode is deposited on the zinc oxide electron transport layer.
  • This comparative example provides a QLED light-emitting diode and a preparation method thereof.
  • the structure of the QLED light-emitting diode of this comparative example is the same as that of Example 1.
  • the zinc oxide electron transport layer contained in the QLED light-emitting diode is different from that in Example 1, and is prepared according to step S3 of the following preparation method of the QLED light-emitting diode.
  • the preparation method of this comparative example QLED comprises the following steps:
  • S1 provide a substrate, and form a bottom electrode (anode) on the substrate;
  • S3 deposit a zinc oxide-ethanol solution on the quantum dot light-emitting layer to form a zinc oxide electron transport wet film layer; then heat the zinc oxide electron transport wet film layer directly on a heating table at 120°C for 15 mins to form an electron transport layer;
  • a top electrode is deposited on the zinc oxide electron transport layer.
  • This comparative example provides a QLED light-emitting diode and a preparation method thereof.
  • the structure of the QLED light-emitting diode of this comparative example is the same as that of Example 1.
  • the zinc oxide electron transport layer contained in the QLED light-emitting diode is different from that in Example 1, and is prepared according to step S3 of the following preparation method of the QLED light-emitting diode.
  • the preparation method of this comparative example QLED comprises the following steps:
  • S1 provide a substrate, and form a bottom electrode (anode) on the substrate;
  • S3 first deposit a zinc oxide-ethanol solution on the surface of the quantum dot light-emitting layer to form a zinc oxide electron transport wet film layer; then continue to deposit n-butylamine-acetone solution on the surface of the electron transport wet film layer to form a n-butylamine first film layer, thereby forming a composite wet film layer of zinc oxide-n-butylamine, and then heat treatment in an inert atmosphere on a heating table at 120 °C for 50 mins to form a zinc oxide electron transport layer;
  • This comparative example provides a QLED light-emitting diode and a preparation method thereof.
  • the structure of the QLED light-emitting diode is the positive quantum dot light-emitting diode shown in FIG. 2 , and its structure is the same as that of the first embodiment.
  • the zinc oxide electron transport layer contained in the QLED light-emitting diode is different from that of Examples 1 and 2, and is prepared according to step S3 of the following preparation method of a QLED light-emitting diode.
  • S1 provide a substrate, and form a bottom electrode (anode) on the substrate;
  • S3 First deposit a zinc oxide-ethanol solution on the surface of the quantum dot light-emitting layer to form a zinc oxide electron transport wet film layer; then continue to deposit a tripropylphosphine-methyl formate solution on the surface of the electron transport wet film layer to form a tripropyl phosphine phosphine first film layer to form a composite wet film layer of zinc oxide-tripropylphosphine, and then heat treatment on a heating table at 100 °C for 50 mins in an inert atmosphere to form a zinc oxide electron transport layer; among them, zinc oxide-tripropylphosphine In the composite wet film layer of phosphine, the mass ratio of tripropyl phosphine to zinc oxide is 2:1;
  • a top electrode is deposited on the zinc oxide electron transport layer.
  • This comparative example provides a QLED light-emitting diode and a preparation method thereof.
  • the structure of the QLED light-emitting diode of this comparative example is the same as that of Example 1.
  • the zinc oxide electron transport layer contained in the QLED light-emitting diode is different from that in Example 1, and is prepared according to step S3 of the following preparation method of the QLED light-emitting diode.
  • the preparation method of this comparative example QLED comprises the following steps:
  • S1 provide a substrate, and form a bottom electrode (anode) on the substrate;
  • S3 firstly deposit a zinc oxide-ethanol solution on the surface of the quantum dot light-emitting layer to form a zinc oxide electron transport wet film layer; then continue to deposit a tripropylamine-acetone solution on the surface of the electron transport wet film layer to form a tripropylamine first film layer, Thereby, a composite wet film layer of zinc oxide-tripropylamine was formed, and then the zinc oxide electron transport layer was formed by heat treatment on a heating table at 120 °C for 50 mins in a vacuum environment of -0.1 MPa;
  • a top electrode is deposited on the zinc oxide electron transport layer.
  • This comparative example provides a QLED light-emitting diode and a preparation method thereof.
  • the structure of the QLED light-emitting diode of this comparative example is the same as that of the third embodiment.
  • the NiO hole transport layer contained in the QLED light-emitting diode is different from that in Example 3, and is prepared according to step S2 of the following preparation method of the QLED light-emitting diode.
  • the preparation method of this comparative example QLED comprises the following steps:
  • S1 provide a substrate, and form a bottom electrode (anode) on the substrate;
  • S4 First deposit a zinc oxide-ethanol solution on the surface of the quantum dot light-emitting layer to form a zinc oxide electron transport wet film layer; then heat the zinc oxide electron transport wet film layer directly on a heating table at 100 °C for 50 mins in an inert atmosphere to form Zinc oxide electron transport layer;
  • a top electrode is deposited on the zinc oxide electron transport layer.
  • Example 1 the EL profiles of the QLED devices prepared in Example 1, Example 2, and Comparative Example 3 were tested at a current density of 50 mA ⁇ cm ⁇ 2 , and the results are shown in FIG. 4 , respectively.
  • Example 3 Comparing the EQE of the QLED provided by Example 3 with the EQE of the QLED device provided by Comparative Example 5, the EQE value of Example 3 is also significantly higher than that of Comparative Example 5.
  • the electron transport layer formed by triethylamine as a functional material not only has small defects but also uniformity, so that the EQE of the QLED in Example 1 and Example 2 is higher than In Comparative Example 1, the EQE of the QLED in Example 3 is higher than that in Comparative Example 5.
  • Example 1 and Example 2 Comparing the EQE of the QLED provided by Example 1 and Example 2 with the EQE of the QLED device provided by Comparative Example 3, the EQE value of Example 1 and Example 2 is significantly higher than that of Comparative Example 3.
  • the reason may be due to the strong bond energy between phosphine compounds and metal oxide nanocrystals. It is difficult to remove in the subsequent process, which affects the film-forming property of the composite wet film layer of zinc oxide-tripropylphosphine, which leads to the unevenness of the formed zinc oxide electron transport layer to form the film as shown in Fig. 4(c)
  • the EL morphology of the QLED also affects the luminous efficiency of the QLED and reduces the EQE value of the QLED.
  • the EQE values of Example 1 and Example 2 are also significantly higher than those of Comparative Example 2 and Comparative Example 4.
  • the EQE value of n-butylamine and tripropylamine as functional materials cannot realize the orderly arrangement of metal oxide nanocrystals in the electron transport layer to reduce the defects of the electron transport layer.
  • n-butylamine has an electron-donating group like triethylamine, it may be that the steric hindrance effect of n-butylamine is weak, and it cannot prevent the agglomeration of the capped metal oxide nanocrystals, that is, in the The metal oxide nanocrystal material in the electron transport layer of Example 2 is agglomerated, so that the ordered arrangement of the metal oxide nanocrystal material cannot be achieved. Therefore, the EQE of the QLED of Comparative Example 2 is close to that of Comparative Example 1. In Comparative Example 4, tripropylamine as a functional material did not achieve the expected effect.

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Abstract

本申请公开了一种电荷传输层的制备方法和发光二极管。电荷传输层的制备方法包括使用含有功能性材料的第一溶液形成第一膜层，使用含有电荷传输材料的第二溶液形成第二膜层，第一膜层与第二膜层彼此接触，或者使用第一溶液和第二溶液的混合溶液形成混合膜层；去除功能性材料，得到电荷传输层；功能性材料为含有供电子基团的有机物，电荷传输材料的表面具有金属阳离子悬挂键，供电子基团能够与金属阳离子悬挂键结合。发光二极管包括电子传输层和/或空穴传输层，且电子传输层和/或空穴传输层按照电荷传输层的制备方法制备形成。

Description

电荷传输层的制备方法和发光二极管
本申请要求于2020年12月24日在中国专利局提交的、申请号为202011552242.3、申请名称为“电荷传输层的制备方法和发光二极管”的中国申请专利的优先权。
技术领域
本申请属于光电技术领域，尤其涉及一种电荷传输层的制备方法和发光二极管。
 背景技术
对于先进的溶液处理光电器件来说，电荷传输层(CTL)，即电子传输层(ETL)和空穴传输层(HTL)是必不可少的组件。CTL不仅影响到有源层内的电荷注入，而且还影响器件运作的许多其他基本物理过程，例如LED(或太阳能电池)中界面电荷复合和光提取(或光吸收)。
近年来，胶体金属氧化物纳米晶体作为CTL引起了人们的极大兴趣。例如基于胶体ZnO纳米晶体的ETL，它已经被用于几个性能良好的原型器件。此外，胶体氧化物纳米晶与大规模工业生产完全相容，从而显示出高性能、低成本和大面积器件的光明前景。
目前针对胶体金属氧化物纳米晶体在光电器件中的应用研究主要集中在胶体氧化物纳米晶的合成化学、可能适用于胶体氧化物纳米晶的配体化学，与沉积后处理相关的化学。其中关于沉积后处理，目前的墨水方案采用正交溶剂系统来沉积相邻功能层，另外通过调节墨水的粘度、表面张力基本可实现CTL薄膜的连续、无针孔和整体厚度可控。
实际应用中，按照现有沉积的CTL薄膜依然存在一定的不足，例如胶体金属氧化物纳米晶体在薄膜局部的团聚造成的缺陷不仅降低CTL的激子迁移率，而且已经形成的激子也可能会在缺陷处发生解离而导致器件效率降低。导致局部缺陷的很主要的原因就是不加以控制的沉积过程，针对该CTL薄膜的局部缺陷的研究目前鲜有报导。
 技术问题
本申请提供一种电荷传输层的制备方法和发光二极管，以解决现有胶体金属氧化物纳米晶体形成电荷传输层存在局部缺陷而使得激子迁移率低或解离现象的技术问题。
 技术解决方案
本申请一方面提供了一种电荷传输层的制备方法。电荷传输层的制备方法包括如下步骤：
使用含有功能性材料的第一溶液形成第一膜层，使用含有电荷传输材料的第二溶液形成第二膜层，第一膜层与第二膜层彼此邻接，或者使用第一溶液和第二溶液的混合溶液形成混合膜层；
去除功能性材料，得到电荷传输层；
功能性材料为含有供电子基团的有机物，电荷传输材料的表面具有金属阳离子悬挂键，供电子基团能够与金属阳离子悬挂键结合。
进一步地，使第一膜层与第二膜层彼此接触的方法包括如下步骤：
将第二溶液在基体上形成第二膜层；
将第一溶液在第二膜层表面形成第一膜层。
进一步地，使第一膜层与第二膜层彼此接触的方法包括如下步骤：
将第一溶液在基体上形成第一膜层；
将第二溶液在第一膜层表面形成第二膜层。
进一步地，第一溶液和第二溶液的混合溶液形成混合膜层的方法包括如下步骤：
将第一溶液和第二溶液的混合溶液在基体上形成混合膜层。
进一步地，在彼此接触的第一膜层与第二膜层中或混合膜层中，功能性材料与电荷传输材料的摩尔比为1.5~3：1。
进一步地，功能性材料包括三乙胺。
进一步地，第一溶液中，功能材料与溶剂的体积比为1：（1~50）。
进一步地，第一溶液的溶剂包括丙酮、正丁醇、四氢呋喃、甲酸甲酯中的至少一种。
进一步地，当第一膜层与第二膜层彼此接触时，第一溶液和第二溶液的溶剂互溶或极性相近。
进一步地，去除功能性材料的方法包括如下步骤：
在惰性气体氛围中，对第一膜层与第二膜层或混合膜层进行热处理，使得功能性材料挥发除去。
更进一步地，热处理的温度为90℃~150℃。
更进一步地，在热处理的温度为90℃~150℃的基础上，热处理的时间为5 min ~ 24 h。
进一步地，电荷传输材料为空穴传输材料或电子传输材料。
更进一步地，空穴传输材料包括MoO 3、NiO、V 2O 5和WO 3中的至少一种，或包括被Li、Al、Mg、Cs、In、Ga、Zr中的至少一种金属掺杂的MoO 3、NiO、V 2O 5和WO 3中的至少一种。
更进一步地，电子传输材料包括ZnO、SnO、TiO 2和ZrO 2中的至少一种，或包括被Li、Al、Mg、Cs、In、Ga、Zr中的至少一种金属掺杂的ZnO、SnO、TiO 2和ZrO 2中的至少一种。
本申请的又一方面，提供了一种发光二极管。发光二极管包括电子传输层，电子传输层按照本申请电荷传输层的制备方法制备形成，其中，电荷传输材料为电子传输材料。
或，发光二极管包括空穴传输层，空穴传输层按照本申请电荷传输层的制备方法制备形成，其中，电荷传输材料为空穴传输材料。
或，发光二极管包括电子传输层和空穴传输层，电子传输层按照本申请电荷传输层的制备方法制备形成，其中，电荷传输材料为电子传输材料；空穴传输层按照本申请电荷传输层的制备方法制备形成，其中，电荷传输材料为空穴传输材料。
进一步地，发光二极管为QLED或OLED。
与现有技术相比，本申请具有以下的技术效果：
本申请电荷传输层的制备方法将第二溶液和第一溶液在分别形成膜层或者先形成混合物后再成膜后，这样，功能性材料会与金属氧化物纳米材料表面的金属阳离子悬挂键结合，达到封端的效果，当电荷传输湿膜层中溶剂在挥发的过程中，表面结合有功能性材料的金属氧化物纳米材料会先形成一种类似与“寡聚体”的稳定状态，并在沉积过程中这些“寡聚体”会发生类似于高分子聚合的有序排列，使金属氧化物纳米材料在沉积过程中变得有序，减少成膜过程产生缺陷的机会，这样，制备的电荷传输层中金属氧化物纳米材料能够有序排列，电荷传输层缺陷少或者不存在缺陷，从而使得电荷传输层对激子迁移速率高，且能够避免激子发生解离的现象。另外，电荷传输层制备方法形成层结构条件可控，有效保证了制备电荷传输层性能的稳定，而且效率高。
本申请发光二极管由于含有上述本申请电荷传输层的制备方法制备的电荷传输层，按照上述本申请电荷传输层的制备方法制备的电子传输层和/或空穴传输层，这样，发光二极管所含的电子传输层和/或空穴传输层所含的金属氧化物纳米材料能够有序排列，电荷传输层缺陷小或者不存在缺陷，从而赋予电荷传输层具有对激子迁移速率高的特性，从而赋予本申请发光二极管高的发光效率。
 附图说明
为了更清楚地说明本申请实施例中的技术方案，下面将对实施例或示范性技术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，对于本领域普通技术人员来讲，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它的附图。
图1是本申请实施例电荷传输层的制备方法的工艺流程示意图；其中，图a为本申请实施例电荷传输层的第一种制备方法，图b为本申请实施例电荷传输层的第二种制备方法，图c为本申请实施例电荷传输层的第三种制备方法；
图2是本申请实施例提供的一种正型构型的发光二极管结构示意图；
图3是本申请实施例提供的一种反型构型的发光二极管结构示意图；
图4是本申请实施例1至实施例2和对比例3提供的正型发光二极管的EL形貌图；其中，图4（a）为实施例1提供的正型发光二极管的EL形貌图；图4（b）为实施例2提供的正型发光二极管的EL形貌图；图4（c）为对比例3提供的正型发光二极管的EL形貌图。
 本发明的实施方式
为了使本申请要解决的技术问题、技术方案及有益效果更加清楚明白，以下结合实施例，对本申请进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本申请，并不用于限定本申请，基于本申请中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本申请保护的范围。
一方面，本申请实施例提供了电荷传输层的制备方法。电荷传输层的制备方法包括使用含有功能性材料的第一溶液形成第一膜层和使用含有电荷传输材料的第二溶液形成第二膜层，并使得第一膜层与第二膜层彼此邻接，再去除功能性材料得到电荷传输层的步骤；或使用第一溶液和第二溶液的混合溶液形成混合膜层，再去除功能性材料得到电荷传输层的步骤。因此，实施例中，电荷传输层的制备方法至少包括如下三种电荷传输层的制备方法：
电荷传输层的第一种制备方法：
第一种制备方法工艺流程如图1（a）所示，包括如下步骤：
S01：将使用含有电荷传输材料的第二溶液在基体1上形成第二膜层2；
S02：将使用含有功能性材料的第一溶液在第二膜层2表面形成第一膜层3；
S03：将第二膜层2和第一膜层3形成的复合湿膜层所含的功能性材料进行除去处理，形成电荷传输层。
第二种制备方法工艺流程如图1（b）所示，包括如下步骤：
S04：使用含有功能性材料的第一溶液在基体1上形成第一膜层3；
S05：将使用含有电荷传输材料的第二溶液在第一膜层3上形成第一膜层2；
S06：将第二膜层2和第一膜层3形成的复合湿膜层所含的功能性材料进行除去处理，形成电荷传输层。
第三种制备方法工艺流程如图1（c）所示，包括如下步骤：
S07：将含有功能性材料的第一溶液和含有电荷传输材料的第二溶液的混合溶液在基体1上形成混合膜层4；
S08：将混合膜层4所含的功能性材料进行除去处理，形成电荷传输层。
其中，上述电荷传输层的制备方法的步骤S02、步骤S04和步骤S07中第一溶液所含的功能性材料为含有供电子基团的有机物，步骤S01、步骤S05和步骤S07中第二溶液所含的电荷传输材料的表面具有金属阳离子悬挂键，且功能性材料所含的供电子基团能够与电荷传输材料表面的金属阳离子悬挂键结合。这样，当将含有功能性材料的第一溶液和含有电荷传输材料的第二溶液在如步骤S01至S02、步骤S04至S05分别形成第一膜层3和第二膜层2由于是湿膜层，两者溶剂会发生融合，此时功能性材料会与电荷传输材料在复合湿膜层中直接接触，从而使得功能性材料所含的供电子基团能够与电荷传输材料表面的金属阳离子悬挂键结合。在步骤S07的混合溶液中功能性材料与电荷传输材料在混合膜层4中直接接触。这样，功能性材料所含的供电子基团与电荷传输材料表面的金属阳离子悬挂键结合，达到封端的效果。当在步骤S03、步骤S06和步骤S08中对所含的功能性材料进行除去处理的过程中，复合湿膜层或混合膜层4中溶剂在挥发过程中，表面结合有功能性材料的电荷传输材料会先形成一种类似与“寡聚体”的稳定状态，并在沉积过程中这些“寡聚体”会发生类似于高分子聚合的有序排列，使电荷传输材料在沉积过程中变得有序，减少成膜过程产生缺陷的机会。因此，本申请实施例通过在相应工艺步骤中设置含有功能性材料，使得制备的电荷传输层中电荷传输材料能够有序排列，电荷传输层缺陷少或者不存在缺陷，从而使得电荷传输层具有对激子迁移速率高的特性，且能够避免激子发生解离的现象。
经申请人对功能性材料的研究发现，适于本申请实施例的功能性材料可以是满足以下三个特点：1）可溶液加工；2）具有供电子基团，能够与电荷传输材料形成类似“寡聚体”，以达到预期效果；3）易被清除。其中，第1）和第2）特点应该是基本要求特点，第3）为可选特点。因此，在一实施例中，上述功能性材料包括三乙胺。
基于上述功能性材料的作用和作为举例的种类，在一实施例中，步骤S02、步骤S04和步骤S07中第一溶液所含的功能性材料与溶剂的体积比为1：（1~50）。另一实施例中，第一溶液所含的溶剂包括丙酮、正丁醇、四氢呋喃、甲酸甲酯中的至少一种。通过控制和优化功能性材料在第一溶液中的浓度和对溶剂的选择优化，提高第一膜层3或混合膜层4的成膜均匀性，从而使得功能性材料能够与电荷传输材料能够充分发挥作用，从而提高电荷传输材料在形成的电荷传输层中的有序排列，使得电荷传输层缺陷少或者不存在缺陷。
在另一实施例中，通过控制步骤S02、步骤S04中第一膜层3厚度或步骤S07中混合溶液所含功能性材料与电荷传输材料混合比例，从而使得功能性材料相对电荷传输材料足量，使得功能性材料与电荷传输材料表面的金属阳离子悬挂键结合达到封端的效果，并使得电荷传输材料在形成的电荷传输层充分有序排列，从而进一步减少或完全消除电荷传输层中缺陷以进一步形成电荷传输层对激子的传输效率。因此，在一实施例中，第一膜层3中的功能性材料与第二膜层2中的电荷传输材料的摩尔比为1.5~3：1。或者骤S07的混合溶液也即是混合膜层4中，功能性材料与电荷传输材料的摩尔比为1.5~3：1。
另外，步骤S02、步骤S04中第一膜层3的形成方法可以按照现有溶液成膜方法成膜即可，具体可以参照电荷传输层成膜方法形成第一膜层3，如具体实施例中，第一膜层3的形成方法包括旋涂、喷墨打印、喷涂、刮刀涂布等方法。
步骤S01、步骤S05和步骤S07中第二溶液可以是现有用于制备电荷传输层的常用第二溶液，理所当然的是，第二溶液是含有电荷传输材料。在本申请实施例中，电荷传输材料包括金属氧化物纳米材料（金属氧化物纳米晶体材料），也既是说，在步骤S01、步骤S05和步骤S07中的第二溶液含有金属氧化物纳米材料。
由于电荷包括电子和空穴，因此，步骤S01、步骤S05和步骤S07中的第二溶液可以是电子传输材料墨水或空穴传输材料墨水。当步骤S01、步骤S05和步骤S07中的第二溶液为电子传输材料墨水时，那么电子传输材料墨水所含的电子传输材料包括金属氧化物纳米材料，且金属氧化物纳米材料为纳米金属氧化物电子传输材料。如在一实施例中，纳米金属氧化物电子传输材料包括ZnO、SnO、TiO 2和ZrO 2中的至少一种，或包括被金属掺杂的ZnO、SnO、TiO 2和ZrO 2中的至少一种；其中，用于掺杂ZnO、SnO、TiO 2和ZrO 2中的至少一种的掺杂金属包括Li、Al、Mg、Cs、In、Ga、Zr中的至少一种。选用该纳米金属氧化物电子传输材料不仅能够使得形成的电子传输层具有良好的连续、无针孔和整体厚度以及电子传输效率高，更重要的是能够与步骤S02、步骤S04和步骤S07中的第一溶液所含的功能性材料之间发生如上文的两者之间的作用，从而提高形成的电子传输层缺陷少或者不存在缺陷，对电子传输效率高。
当步骤S01、步骤S05和步骤S07中的第二溶液为空穴传输材料墨水时，那么空穴传输材料墨水所含的空穴传输材料包括金属氧化物纳米材料，且金属氧化物纳米材料为纳米金属氧化物空穴传输材料。如在一实施例中，纳米金属氧化物空穴传输材料包括MoO 3、NiO、V 2O 5和WO 3中的至少一种，或包括被金属掺杂的MoO 3、NiO、V 2O 5和WO 3中的至少一种；其中，用于掺杂MoO 3、NiO、V 2O 5和WO 3中的至少一种中的掺杂金属包括Li、Al、Mg、Cs、In、Ga、Zr中的至少一种。
另外，步骤S01、步骤S05和步骤S07中的第二溶液的浓度可以根据形成电荷传输湿膜层如第二膜层2和混合膜层4方法的要求进行调整。为了保证第二膜层2和第一膜层3能够充分融合以提高复合湿膜层的质量，如电荷传输层的制备方法是按照上文第一种或第二种制备方法制备电荷传输层时，在步骤S01中形成第二膜层2后应该是立即形成进行步骤S02也既是形成第一膜层3；或在步骤S04中形成第一膜层3后应该是立即形成进行步骤S05也既是形成第二膜层2，使得第二膜层2和第一膜层3有充分的融合时间。
另外，步骤S01、步骤S05中第二膜层2和步骤S07中混合膜层4形成方法可以按照现有溶液成膜方法成膜即可。如具体实施例中，第二膜层2和混合膜层4的形成方法包括旋涂、喷墨打印、喷涂、刮刀涂布等方法。当采用旋涂工艺形成第二膜层2时，第二膜层2和第一膜层3的溶剂互溶，极性相近，在采用旋涂工艺形成第二膜层2时，由于旋涂工艺特点，可能会有少量厚度的第二膜层3被剥离掉，这可以通过前期统计和计算损失量和调节成第二膜层2厚度等即可弥补。
其次，步骤S01、步骤S04和步骤S07中的基体1可以是需要在相应部件或者器件表面形成电荷传输层的任何基体。基于电荷传输层常规的应用，该基体可以是电致发光器件（如发光二极管）所含的相应部件，如正极、负极、电子注入层、空穴注入层、发光层的表面，具体根据相应电致发光器件制备的先后顺序而不同。
上述各实施例中去除功能性材料得到电荷传输层的方法如步骤S03、步骤S06和步骤S08中去除功能性材料得到电荷传输层的方法包括对第一膜层3和第二膜层2或对混合膜层4进行干燥处理的步骤，以有效去除复合湿膜层或混合膜层4中功能性材料的同时去除溶剂以形成电荷传输层。在一实施例中，干燥处理的方法包括如下步骤：
在惰性气体氛围中，对复合湿膜层或混合膜层4进行热处理。
在具体实施例中，该热处理的温度为90℃~150℃。通过该干燥处理，使复合湿膜层或混合膜层4的溶剂和功能性材料挥发，固化形成电荷传输层。另外，该干燥处理如90℃~150℃的热处理时间应该是充分的，具体的热处理时间应可以为5 mins ~ 24 hrs。具体可以根据复合湿膜层或混合膜层4的厚度、溶剂特性根据实际调整。
因此，本申请实施例电荷传输层的制备方法不仅能够使得第一溶液中所含的功能性材料与第二溶液中的电荷传输材料之间发生作用，使得电荷传输材料在制备的电荷传输层中能够有序排列，使得电荷传输层缺陷少或者不存在缺陷，从而使得电荷传输层具有激子迁移速率高特性，且能够避免激子发生解离的现象。另外，电荷传输层制备方法形成层结构条件可控，有效保证了制备电荷传输层性能的稳定，而且效率高。
另一方面，基于上文电荷传输层的制备方法，本申请实施例还提供了一种发光二极管。发光二极管所含电子传输层和空穴传输层，当然发光二极管还含有发光二极管必要的其他层结构，如发光层、阳极和阴极等。其中，发光二极管所含的电子传输层为是按照上文电荷传输层的制备方法制备形成的电子传输层。那么理所当然的是，按照上文电荷传输层的制备方法制备形成的电子传输层时，所用的第二溶液所含的电荷传输材料为电子传输材料。
或发光二极管所含的空穴传输层为是按照上文电荷传输层的制备方法制备形成的空穴传输层。那么理所当然的是，按照上文电荷传输层的制备方法制备形成的空穴传输层时，所用的第二溶液所含的电荷传输材料为空穴传输材料。
另外，发光二极管所含的电子传输层和空穴传输层可以同时分别按照上文电荷传输层的制备方法制备形成，当然也可以是其中任一种如电子传输层或空穴传输层按照上文电荷传输层的制备方法制备形成。在本申请实施例中，可以是电子传输层和空穴传输层均分别按照上文电荷传输层的制备方法制备形成，这样能够同时提高电子传输效率和空穴传输效率，从而提高发光层中激子的含量，从而提高发光二极管的发光效率，如提高发光二极管的外量子效率（EQE）。
其次，根据发光层所含的发光材料，本申请实施例发光二极管可以是量子点发光二极管（QLED）或有机电致发光二极管（OLED）。根据发光二极管的结构设置，本申请实施例发光二极管可以正型发光二极管，也可以是反型发光二极管。
如在一种实施方式中，正型发光二极管的结构如图2所示，其包括相对设置的阳极10和阴极50的层叠结构，其中，阳极10可以层叠结合在衬底01上，在阳极10和阴极50之间层叠结合有发光功能层。发光功能层包括发光层30和空穴传输层20以及电子传输层40，由阳极10至阴极50的方向，空穴传输层20、发光功能层30、电子传输层40依次层叠，进一步地，在空穴传输层20与阳极10之间还可以设置空穴注入层（图2未显示），在电子传输层40与阴极50之间还可以设置电子注入层（图2未显示）。
当空穴传输层20为上文电荷传输层的制备方法制备形成时，是以形成的阳极10作为基体1，在阳极10的外表面上，以空穴传输材料墨水为第二溶液，按照上文电荷传输层的制备方法制备空穴传输层20。当图2所示正型发光二极管含有空穴注入层时，那么是以形成的空穴注入层作为基体1，在空穴注入层的外表面上，以空穴传输材料墨水为第二溶液，按照上文电荷传输层的制备方法制备空穴传输层20。然后按照现有方法在空穴传输层20外表面依次形成发光层30、电子传输层40、（或进一步形成空穴注入层）、阴极50。
当电子传输层40为上文电荷传输层的制备方法制备形成时，是以形成的发光层30作为基体1，在发光层30的外表面上，以电子传输材料墨水为第二溶液，按照上文电荷传输层的制备方法制备电子传输层40。
在另一种实施方式中，反型结构发光二极管的结构如图3所示，其包括相对设置的阳极10和阴极50的层叠结构，其中，阴极50可以层叠结合在衬底01上，在阳极10和阴极50之间层叠结合有发光功能层。发光功能层包括发光层30和空穴传输层20以及电子传输层40，由阳极10至阴极50的方向，空穴传输层20、发光功能层30、电子传输层40依次层叠，进一步地，在空穴传输层20与阳极10之间还可以设置空穴注入层（图2未显示），在电子传输层40与阴极50之间还可以设置电子注入层（图2未显示）。
当电子传输层40为上文电荷传输层的制备方法制备形成时，是以形成的阴极50作为基体1，在阴极50的外表面上，以电子传输材料墨水为第二溶液，按照上文电荷传输层的制备方法制备电子传输层40。当图2所示反型发光二极管含有电子注入层时，那么是以形成的电子注入层作为基体1，在电子注入层的外表面上，以电子传输材料墨水为第二溶液，按照上文电荷传输层的制备方法制备电子传输层40。然后按照现有方法在电子传输层40外表面依次形成发光层30、空穴传输层20、（或进一步形成空穴注入层）、阳极10。
当空穴传输层20为上文电荷传输层的制备方法制备形成时，是以形成的发光层30作为基体1，在发光层30的外表面上，以空穴传输材料墨水为第二溶液，按照上文电荷传输层的制备方法制备空穴传输层20。
为使本申请上述实施细节和操作能清楚地被本领域技术人员理解，以及本申请实施例电荷传输层的制备方法和发光二极管及其制备方法的进步性能显著的体现，以下通过多个实施例来举例说明上述技术方案。
在以下实施例中，以QLED作为示例进行描述。其中，QLED的结构为ITO/空穴传输层（30nm）/CdSe/ZnS（40nm）/电子传输层（40nm）/Ag（120nm）。应当理解，该QLED的结构仅是示例性的，本申请不限于此。
实施例1
本实施例提供一种QLED发光二极管及其制备方法。
QLED发光二极管的结构如图2所示的正型量子点发光二极管，其结构为ITO/PEDOT:PSS（30nm）空穴传输层（30nm）/CdSe/ZnS（40nm）/电子传输层（40nm）/Ag（120nm）。其中，“/”表述层叠结合的层结构连接关系。
本实施例QLED的制备方法包括如下步骤：
S1：提供一衬底，在衬底上形成底电极（阳极）；
S2：在底电极上依次沉积有机空穴注入层、有机空穴传输层、量子点发光层；
S3：在量子点发光层表面先沉积氧化锌-乙醇溶液，形成氧化锌电子传输湿膜层，也既是第二膜层；再在该氧化锌电子传输湿膜层表面继续沉积三乙胺-丙酮溶液，形成含三乙胺的第一膜层，从而形成氧化锌-三乙胺的复合湿膜层，然后在惰性气氛中于120℃的加热台上热处理50 mins形成氧化锌电子传输层；其中，氧化锌-三乙胺的复合湿膜层中，三乙胺与氧化锌的摩尔比为2：1；
S4：在氧化锌电子传输层上沉积顶电极。
实施例2
本实施例提供一种QLED发光二极管及其制备方法。
QLED发光二极管的结构如图2所示的正型量子点发光二极管，其结构与实施例1相同。
本实施例QLED的制备方法包括如下步骤：
S1：提供一衬底，在衬底上形成底电极（阳极）；
S2：在底电极上依次沉积有机空穴注入层、有机空穴传输层、量子点发光层；
S3：在量子点发光层表面先沉积三乙胺-丙酮溶液，形成三乙胺的第一膜层；再在该第一膜层表面上沉积氧化锌-乙醇溶液，形成氧化锌电子传输湿膜层，从而形成氧化锌-三乙胺的复合湿膜层，然后在惰性气氛中于150℃的加热台上热处理30 mins形成氧化锌电子传输层；其中，氧化锌-三乙胺的复合湿膜层中，三乙胺与氧化锌的摩尔比为2：1；
S4：在氧化锌电子传输层上沉积顶电极。
实施例3
本实施例提供一种QLED发光二极管及其制备方法。
QLED发光二极管的结构如图2所示的正型量子点发光二极管，其包括ITO/NiO空穴传输层（30nm）/CdSe/ZnS（40nm）/氧化锌电子传输层（40nm）/Ag（120nm）。其中，“/”表述层叠结合的层结构连接关系。
本实施例QLED的制备方法包括如下步骤：
S1：提供一衬底，在衬底上形成底电极（阳极）；
S2：在底电极上旋涂NiO-水溶液，形成NiO空穴传输湿膜层；再在该NiO空穴传输湿膜层表面继续沉积沉积三乙胺-正丁醇溶液、形成三乙胺功能性湿膜层，从而形成NiO-三乙胺的复合湿膜层，然后在120℃的加热台上热处理30 mins形成NiO空穴传输层；
S3：在NiO空穴传输层表面形成量子点发光层；
S4：在量子点发光层表面先沉积氧化锌-乙醇溶液，形成氧化锌电子传输湿膜层；然后将氧化锌电子传输湿膜层直接在惰性气氛中于100℃的加热台上热处理50 mins形成氧化锌电子传输层；
S5：在氧化锌电子传输层上沉积顶电极。
对比例1
本对比例提供一种QLED发光二极管及其制备方法。本对比例QLED发光二极管的结构与实施例1相同。其中，QLED发光二极管所含的氧化锌电子传输层与实施例1不同，是按照如下QLED发光二极管的制备方法的步骤S3制备。
本对比例QLED的制备方法包括如下步骤：
S1：提供一衬底，在衬底上形成底电极（阳极）；
S2：在底电极上依次沉积有机空穴注入层、有机空穴传输层、量子点发光层；
S3：在量子点发光层上沉积氧化锌-乙醇溶液，形成氧化锌电子传输湿膜层；再将氧化锌电子传输湿膜层直接在120℃的加热台上热处理15 mins形成电子传输层；
S4：在氧化锌电子传输层上沉积顶电极。
对比例2
本对比例提供一种QLED发光二极管及其制备方法。本对比例QLED发光二极管的结构与实施例1相同。其中，QLED发光二极管所含的氧化锌电子传输层与实施例1不同，是按照如下QLED发光二极管的制备方法的步骤S3制备。
本对比例QLED的制备方法包括如下步骤：
S1：提供一衬底，在衬底上形成底电极（阳极）；
S2：在底电极上依次沉积有机空穴注入层、有机空穴传输层、量子点发光层；
S3：在量子点发光层表面先沉积氧化锌-乙醇溶液，形成氧化锌电子传输湿膜层；再在该电子传输湿膜层表面继续沉积正丁胺-丙酮溶液，形成正丁胺第一膜层，从而形成氧化锌-正丁胺的复合湿膜层，然后在惰性气氛中于120℃的加热台上热处理50 mins形成氧化锌电子传输层；
对比例3
本对比例提供一种QLED发光二极管及其制备方法。
QLED发光二极管的结构如图2所示的正型量子点发光二极管，其结构与实施例1相同。其中，QLED发光二极管所含的氧化锌电子传输层与实施例1和2不同，是按照如下QLED发光二极管的制备方法的步骤S3制备。
本实施例QLED的制备方法包括如下步骤：
S1：提供一衬底，在衬底上形成底电极（阳极）；
S2：在底电极上依次沉积有机空穴注入层、有机空穴传输层、量子点发光层；
S3：在量子点发光层表面先沉积氧化锌-乙醇溶液，形成氧化锌电子传输湿膜层；再在该电子传输湿膜层表面继续沉积三丙基膦-甲酸甲酯溶液，形成三丙基膦第一膜层，从而形成氧化锌-三丙基膦的复合湿膜层，然后在惰性气氛中于100℃的加热台上热处理50 mins形成氧化锌电子传输层；其中，氧化锌-三丙基膦的复合湿膜层中，三丙基膦与氧化锌的质量比为2：1；
S4：在氧化锌电子传输层上沉积顶电极。
对比例4
本对比例提供一种QLED发光二极管及其制备方法。本对比例QLED发光二极管的结构与实施例1相同。其中，QLED发光二极管所含的氧化锌电子传输层与实施例1不同，是按照如下QLED发光二极管的制备方法的步骤S3制备。
本对比例QLED的制备方法包括如下步骤：
S1：提供一衬底，在衬底上形成底电极（阳极）；
S2：在底电极上依次沉积有机空穴注入层、有机空穴传输层、量子点发光层；
S3：在量子点发光层表面先沉积氧化锌-乙醇溶液，形成氧化锌电子传输湿膜层；再在该电子传输湿膜层表面继续沉积三丙胺-丙酮溶液，形成三丙胺第一膜层，从而形成氧化锌-三丙胺的复合湿膜层，然后在-0.1 MPa的真空环境中于120℃的加热台上热处理50 mins形成氧化锌电子传输层；
S4：在氧化锌电子传输层上沉积顶电极。
对比例5
本对比例提供一种QLED发光二极管及其制备方法。本对比例QLED发光二极管的结构与实施例3相同。其中，QLED发光二极管所含的NiO空穴传输层与实施例3不同，是按照如下QLED发光二极管的制备方法的步骤S2制备。
本对比例QLED的制备方法包括如下步骤：
S1：提供一衬底，在衬底上形成底电极（阳极）；
S2：在底电极上旋涂NiO-水溶液，形成NiO空穴传输湿膜层；然后直接将NiO空穴传输湿膜层在120℃的加热台上热处理30 mins形成NiO空穴传输层；
S3：在NiO空穴传输层表面形成量子点发光层；
S4：在量子点发光层表面先沉积氧化锌-乙醇溶液，形成氧化锌电子传输湿膜层；然后将氧化锌电子传输湿膜层直接在惰性气氛中于100℃的加热台上热处理50 mins形成氧化锌电子传输层；
S5：在氧化锌电子传输层上沉积顶电极。
量子点发光二极管相关光电性能测试
分别测试实施例1至实施例4、对比例1至对比例4制备的QLED器件在50mA·cm -2电流密度下的EQE，结果分别如表1所示，从表中可以看出经过三乙胺处理后的器件的EQE得到提升，说明三乙胺优化了电子传输层的薄膜状态。
表1
Figure dest_path_image001
进一步地，分别测试实施例1、实施例2、对比例3制备的QLED器件在50 mA·cm -2电流密度下的EL形貌图，结果分别如图4所示。
由表1中EQE数据，将实施例1和实施例2提供QLED的EQE与对比例1提供的QLED器件的EQE相比，实施例1和实施例2的EQE值明显高于对比例1的EQE值。
将实施例3提供QLED的EQE与对比例5提供的QLED器件的EQE相比，实施例3的EQE值也明显高于对比例5的EQE值。
这说明采用三乙胺作为功能性材料能够有效与金属氧化物纳米晶体表面的金属阳离子悬挂键结合，达到封端的效果，致使墨水溶剂挥发的过程中金属氧化物纳米晶体会先形成一种类似与“寡聚体”的稳定状态，在金属氧化物纳米晶体的沉积过程中这些“寡聚体”会发生类似于高分子聚合的有序排列，使沉积过程变得更为有序，减少成膜过程产生缺陷的机会，且当溶剂挥发结束时，三乙胺也容易被清除。而且结合图4（a）和图4（b）可知，三乙胺作为功能性材料形成的电子传输层膜层不仅缺陷小而且均匀，从而使得实施例1和实施例2中QLED的EQE高于对比例1，实施例3中QLED的EQE高于对比例5。
将实施例1和实施例2提供QLED的EQE与对比例3提供的QLED器件的EQE相比，实施例1和实施例2的EQE值明显高于对比例3的EQE值。
结合图4，并对比图4（a）、图4（b）和图4（c），究其原因，可能是由于膦化合物与金属氧化物纳米晶体成键后的键能较强，导致其在后续过程中难以清除，从而影响了氧化锌-三丙基膦的复合湿膜层的成膜性，从而导致形成的氧化锌电子传输层膜层不均匀以形成如图4（c）所示的EL形貌，也就影响了QLED的发光效率，降低了QLED的EQE值。
将实施例1和实施例2提供QLED的EQE与对比例2和对比例4提供的QLED器件的EQE相比，实施例1和实施例2的EQE值也明显高于对比例2和对比例4的EQE值，这说明正丁胺、三丙胺作为功能性材料不能够实现金属氧化物纳米晶体在电子传输层中有序排列以减小电子传输层的缺陷。究其原因可能是正丁胺虽然与三乙胺一样带有供电子基团，有可能是正丁胺的空间位阻效应弱，不能够阻止被封端的金属氧化物纳米晶体团聚，也即是在对比例2的电子传输层中金属氧化物纳米晶体材料发生了团聚，从而无法实现金属氧化物纳米晶体材料的有序排列，因此，对比例2的 QLED的EQE与对比例1的接近。对比例4中三丙胺作为功能性材料也未达到预期效果，推测可能是由于三丙胺与金属氧化物的结合能力较弱，使其难以达到“寡聚体”的稳定状态，从而不能“指导”其完成有序排列，因此，对比例3的 QLED的EQE与对比例1的也接近。
以上所述仅为本申请的可选实施例，并不用以限制本申请，凡在本申请的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本申请的保护范围之内。

Claims (19)

  1. 一种电荷传输层的制备方法，其中，包括如下步骤：
    使用含有功能性材料的第一溶液形成第一膜层，使用含有电荷传输材料的第二溶液形成第二膜层，所述第一膜层与所述第二膜层彼此接触，或者使用所述第一溶液和所述第二溶液的混合溶液形成混合膜层；
    去除所述功能性材料，得到所述电荷传输层；
    所述功能性材料为含有供电子基团的有机物，所述电荷传输材料的表面具有金属阳离子悬挂键，所述供电子基团能够与所述金属阳离子悬挂键结合。
  2. 如权利要求1所述的制备方法，其中，使所述第一膜层与所述第二膜层彼此接触的方法包括如下步骤：
    将所述第二溶液在基体上形成所述第二膜层；
    将所述第一溶液在所述第二膜层表面形成所述第一膜层。
  3. 如权利要求1所述的制备方法，其中，使所述第一膜层与所述第二膜层彼此接触的方法包括如下步骤：
    将所述第一溶液在基体上形成所述第一膜层；
    将所述第二溶液在所述第一膜层表面形成所述第二膜层。
  4. 如权利要求1所述的制备方法，其中，所述第一溶液和所述第二溶液的混合溶液形成混合膜层的方法包括如下步骤：
    将所述第一溶液和所述第二溶液的混合溶液在基体上形成所述混合膜层。
  5. 如权利要求1-4任一项所述的制备方法，其中，在彼此接触的所述第一膜层与所述第二膜层中或所述混合膜层中，所述功能性材料与所述电荷传输材料的摩尔比为1.5~3：1。
  6. 如权利要求1-4任一项所述的制备方法，其中，所述功能性材料包括三乙胺。
  7. 如权利要求1-4任一项所述的制备方法，其中，所述第一溶液中，所述功能材料与溶剂的体积比为1：（1~50）。
  8. 如权利要求1-4任一项所述的制备方法，其中，所述第一溶液的溶剂包括丙酮、正丁醇、四氢呋喃、甲酸甲酯中的至少一种。
  9. 如权利要求1-4任一项所述的制备方法，其中，当所述第一膜层与所述第二膜层彼此接触时，所述第一溶液和所述第二溶液的溶剂互溶或极性相近。
  10. 如权利要求1-4任一项所述的制备方法，其中，去除所述功能性材料的方法包括如下步骤：
    在惰性气体氛围中，对所述第一膜层与所述第二膜层或所述混合膜层进行热处理，使得所述功能性材料挥发除去。
  11. 如权利要求10所述的制备方法，其中，所述热处理的温度为90℃~150℃。
  12. 如权利要求11所述的制备方法，其中，所述热处理的时间为5 min ~ 24 h。
  13. 如权利要求1-11任一项所述的制备方法，其中，所述电荷传输材料为空穴传输材料和/或电子传输材料。
  14. 如权利要求13所述的制备方法，其中，所述空穴传输材料包括MoO 3、NiO、V 2O 5和WO 3中的至少一种，或包括被Li、Al、Mg、Cs、In、Ga、Zr中的至少一种金属掺杂的MoO 3、NiO、V 2O 5和WO 3中的至少一种。
  15. 如权利要求13所述的制备方法，其中，所述电子传输材料包括ZnO、SnO、TiO 2和ZrO 2中的至少一种，或包括被Li、Al、Mg、Cs、In、Ga、Zr中的至少一种金属掺杂的ZnO、SnO、TiO 2和ZrO 2中的至少一种。
  16. 一种发光二极管，其中，包括电子传输层，所述电子传输层按照权利要求1-12任一项所述的制备方法制备形成，所述电荷传输材料为电子传输材料。
  17. 一种发光二极管，其中，包括空穴传输层，所述空穴传输层按照权利要求1-12任一项所述的制备方法制备形成，所述电荷传输材料为空穴传输材料。
  18. 一种发光二极管，其中，包括电子传输层和空穴传输层，所述电子传输层按照权利要求1-12任一项所述的制备方法制备形成，所述空穴传输层按照权利要求1-12任一项所述的制备方法制备形成，所述电荷传输材料为电子传输材料和空穴传输材料。
  19. 根据权利要求16-18任一项所述的发光二极管，其中，所述发光二极管为QLED或OLED。
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