WO2020173203A1 - 电子传输层及其制备方法、发光器件和显示装置 - Google Patents

电子传输层及其制备方法、发光器件和显示装置 Download PDF

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WO2020173203A1
WO2020173203A1 PCT/CN2019/128231 CN2019128231W WO2020173203A1 WO 2020173203 A1 WO2020173203 A1 WO 2020173203A1 CN 2019128231 W CN2019128231 W CN 2019128231W WO 2020173203 A1 WO2020173203 A1 WO 2020173203A1
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Prior art keywords
electron transport
film
transport film
layer
light emitting
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PCT/CN2019/128231
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English (en)
French (fr)
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张昭
刘瑞超
张小凤
王学路
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京东方科技集团股份有限公司
鄂尔多斯市源盛光电有限责任公司
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Priority to US16/963,777 priority Critical patent/US11502268B2/en
Publication of WO2020173203A1 publication Critical patent/WO2020173203A1/zh

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting layers
    • H10K50/166—Electron transporting layers comprising a multilayered structure
    • 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
    • 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
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/301—Details of OLEDs
    • H10K2102/351—Thickness
    • 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
    • H10K71/16—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering

Definitions

  • the present disclosure relates to the field of display technology, and in particular to an electron transport layer and a preparation method thereof, a light emitting device and a display device.
  • Organic light-emitting diode (Organic Light-Emitting Diode, abbreviated as OLED) display is a display device that uses current to drive light-emitting devices to achieve image display. It has self-luminous, no backlight, high contrast, thin thickness, wide viewing angle, and response. Excellent features such as high speed.
  • an electron transport layer is provided.
  • the electron transport layer is applied to a light emitting device, the light emitting device includes a light emitting layer, and the electron transport layer is disposed on one side of the light emitting layer.
  • the electron transport layer includes: a first electron transport film; and a second electron transport film laminated on a side of the first electron transport film close to the light-emitting layer, and the second electron transport film is configured Is in contact with the light-emitting layer.
  • the conduction band energy level of the material contained in the second electron transport film is greater than the conduction band energy level of the material contained in the first electron transport film, and the conduction band energy level of the material contained in the second electron transport film It is smaller than the conduction band energy level of the material contained in the light-emitting layer.
  • the valence band energy level of the material contained in the second electron transport film is less than the valence band energy level of the material contained in the first electron transport film.
  • the thickness of the second electron transport film is less than the thickness of the first electron transport film.
  • the molar ratio of the material contained in the second electron transport film to the material contained in the first electron transport film ranges from 1:5 to 1:3.
  • the first electron transport film includes a ZnO film, a TiO 2 film, or a SnO 2 film.
  • the second electron transport film includes a ZrO 2 film, a La 2 O 3 film, or a LaTi 2 O 7 film.
  • the preparation method is used to prepare the electron transport layer as described in some of the above embodiments.
  • the preparation method includes: stacking a first electron transport film and a second electron transport film together.
  • the first electron transport film is located on the side of the second electron transport film layer close to the light-emitting layer; the conduction band energy level of the material contained in the first electron transport film is smaller than that of the second electron transport film.
  • the conduction band energy level of the material contained in the second electron transport film is smaller than the conduction band energy level of the material contained in the light-emitting layer.
  • the laminating the first electron transport film and the second electron transport film together includes: forming the first electron transport film on a substrate using a film forming process; The second electron transport film is formed on the surface of the first electron transport film away from the substrate.
  • the laminating the first electron transport film and the second electron transport film together includes: forming the first electron transport film by a film forming process; forming the second electron transport film by a film forming process Film; The first electron transport film and the second electron transport film are compounded together.
  • the first electron transport film includes a ZnO film.
  • the film forming process to form the first electron transport film includes: adding an ethanol solution of diethanolamine to an ethanol suspension of zinc acetate, and heating the solution to obtain a diethanolamine complex sol solution; removing the diethanolamine Ethanol contained in the complex sol solution; the diethanolamine complex sol solution from which ethanol has been removed is made into a zinc oxide prefabricated film by a film forming process; the diethanolamine complex contained in the zinc oxide prefabricated film is oxidized to form a ZnO film .
  • the molar ratio of diethanolamine contained in the ethanol solution of diethanolamine to zinc acetate contained in the ethanol suspension of zinc acetate ranges from 1:1.5 to 1:1.
  • the second electron transport film includes a ZrO 2 film.
  • the film forming process to form the second electron transport film includes: adding ammonia water dropwise to an ethanol suspension of zirconyl chloride octahydrate under heating to obtain a zirconium hydrolyzed sol solution; removing the zirconium hydrolyzed sol The ethanol contained in the liquid; the zirconium hydrolyzed sol solution from which the ethanol is removed is produced by a film forming process to produce a zirconium dioxide prefabricated film; the zirconium dioxide prefabricated film is oxidized to form a ZrO 2 film.
  • the forming of the second electron transport film by a film forming process further includes: before the dropwise addition of ammonia to the ethanol suspension of zirconyl chloride octahydrate, combining anhydrous ethanol with Water is mixed to obtain an aqueous ethanol solution; wherein the volume ratio of the absolute ethanol to the water ranges from 1:4 to 1:2.5; the aqueous ethanol solution and zirconyl chloride octahydrate are mixed to obtain chlorine octahydrate An ethanol suspension of zirconium oxide.
  • a light emitting device in yet another aspect, includes: the electron transport layer as described in some of the above embodiments, the electron transport layer includes a first electron transport film and a second electron transport film that are stacked; and, the second electron transport film is provided on the The light-emitting layer on the side of the film away from the first electron transport film; wherein the conduction band energy level of the material contained in the light-emitting layer is greater than the conduction band energy level of the material contained in the second electron transport film.
  • the light emitting device further includes: an electron injection layer disposed on a side of the electron transport layer away from the light emitting layer; and an electron injection layer disposed on a side of the light emitting layer away from the electron transport layer.
  • An exciton adjusting layer, the exciton adjusting layer is configured to adjust the transport efficiency of holes transported into the light-emitting layer so that the holes and electrons transported into the light-emitting layer are as close as possible to the Exciton recombination occurs in the light-emitting layer; a hole transport layer arranged on the side of the exciton adjusting layer away from the light-emitting layer; and a hole arranged on the side of the hole transport layer away from the light-emitting layer Hole injection layer.
  • a display device in another aspect, includes a plurality of light-emitting devices as described in some of the above embodiments.
  • Fig. 1 is a structural diagram of a light emitting device in the related art
  • Fig. 2 is a structural diagram of an electron transport layer in some embodiments according to the present disclosure
  • FIG. 3 is an energy level diagram of a material contained in an electron transport layer in some embodiments according to the present disclosure
  • FIG. 4 is a flowchart of a method for preparing an electron transport layer in some embodiments of the present disclosure
  • FIG. 5 is a flowchart of another method for preparing an electron transport layer in some embodiments of the present disclosure
  • Fig. 6 is a flow chart of a method for preparing a first electron transport layer in some embodiments of the present disclosure
  • Fig. 7 is a flow chart of a method for preparing a second electron transport film in some embodiments of the present disclosure
  • Fig. 8 is a structural diagram of a light emitting device in some embodiments according to the present disclosure.
  • FIG. 9 is a structural diagram of a display device in some embodiments according to the present disclosure.
  • first and second are only used for descriptive purposes, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of indicated technical features. Thus, the features defined with “first” and “second” may explicitly or implicitly include one or more of these features. In the description of the embodiments of the present disclosure, unless otherwise specified, “plurality” means two or more.
  • the light emitting device in the related art includes an anode 200 ′, a cathode 300 ′, and a light emitting function layer 100 ′ located between the anode 200 ′ and the cathode 300 ′.
  • the light emitting function layer 100' includes a hole injection layer 111', a hole transport layer 112', a light emitting layer 130', an electron transport layer 122', and an electron injection layer 121'.
  • the material used for the electron transport layer 122' is generally a metal oxide such as ZnO.
  • Metal oxides such as ZnO have high conductivity and high transmittance, and play an active role in the development of electron transport materials.
  • the electron transport layer 122' made of metal oxide can effectively promote the electron transport speed, but due to the energy band structure characteristics of the metal oxide, the transfer of the conduction band electrons of the metal oxide to the light emitting layer 130' still has to go beyond a relatively large distance.
  • a large potential barrier which tends to make the electron transport efficiency relatively low compared to the hole transport efficiency, resulting in a mismatch in the number of electrons and holes, which may easily lead to exciton recombination at the interface between the light-emitting layer 130' and the electron transport layer 122', which reduces The efficiency and stability of light-emitting devices.
  • some embodiments of the present disclosure provide a display device 300 including a plurality of light emitting devices 200.
  • the light emitting device 200 includes a hole injection layer 25, a hole transport layer 24, a light emitting layer 21, an electron transport layer 100, and an electron injection layer 22.
  • the light emitting device 200 also includes an exciton adjusting layer 23 disposed between the hole transport layer 24 and the light emitting layer 21, and the exciton adjusting layer 23 can adjust the transmission efficiency of holes to the light emitting layer 21, so that exciton recombination occurs as much as possible.
  • the electron transport layer 100 contained in the light emitting device 200 has a relatively high electron transport efficiency.
  • the electron transport layer 100 provided by the embodiments of the present disclosure will be schematically described below.
  • an embodiment of the present disclosure provides an electron transport layer 100, which is applied to a light emitting device 200, and the light emitting device 200 includes a light emitting layer 21 disposed on one side of the electron transport layer 100 .
  • the electron transport layer 100 includes: a first electron transport film 11 and a second electron transport film laminated on the side of the first electron transport film 11 close to the light emitting layer 21
  • the film 22 and the second electron transport film 22 are configured to be in contact with the light-emitting layer 21.
  • the conduction band energy level of the material contained in the first electron transport film 11 is smaller than the conduction band energy level of the material contained in the second electron transport film 12, and the conduction band energy level of the material contained in the second electron transport film 12 is smaller than the light emitting layer 21 The conduction band energy level of the material contained.
  • the first electron transport film 11 and the second electron transport film 12 can form a heterojunction, which improves the electron transport efficiency of the electron transport layer 100, so that the number of electrons and holes migrated to the light-emitting layer 21 can be matched, and the light-emitting layer 21 is improved. Luminous efficiency.
  • the second electron transport film 12 is located between the light emitting layer 21 and the first electron transport film 11, and the first electron transport film 11 is located on the electron injection layer 22 and the second electron transport film 12.
  • the conduction band electrons of the material contained in the electron injection layer 22 will first migrate to the conduction band of the material contained in the first electron transport film 11, and then from the conduction band of the material contained in the first electron transport film 11
  • the conduction band electrons migrate to the conduction band of the material contained in the second electron transport film 12, and finally from the conduction band of the material contained in the second electron transport film 12 to the conduction band of the material contained in the light-emitting layer 21.
  • the holes will also migrate to the valence band of the material contained in the light-emitting layer 21, so that the holes and electrons can undergo exciton recombination in the light-emitting layer 21, and the energy released by the exciton recombination is in the form of light. Release, thereby causing the light emitting device 200 to emit light.
  • the second electron transport film 12 Based on the structure and application of the electron transport layer 100 provided by the embodiments of the present disclosure, it can be known that by arranging the second electron transport film 12 on the side of the first electron transport film 11 close to the light emitting layer 21, the second electron transport film 12 and the light emitting The layer 31 is in contact with each other so that the conduction band energy level of the material contained in the first electron transport film 11 is smaller than the conduction band energy level of the material contained in the second electron transport film 12, and the conduction band energy level of the material contained in the second electron transport film 12 The band energy level is smaller than the conduction band energy level of the material contained in the light-emitting layer 31, so that the difference in conduction band energy between the material contained in the first electron transport film 11 and the material contained in the second electron transport film 12 will be smaller than the first
  • the conduction band electrons of the material contained in the first electron transport film 11 migrate to the barrier of the conduction band of the material contained in the light-emitting layer 21, and the conduction band electrons of the material contained in the first electron transport film 11 migrate
  • the barrier to the conduction band of the material contained in the second electron transport film 12 will be relatively low, and the barrier of the conduction band of the material contained in the second electron transport film 12 and the material contained in the light-emitting layer 21 will also be relatively low.
  • the conduction band of the material contained in the layer is used as a reference, and it is easier to migrate to the conduction band of the material contained in the light-emitting layer 21 having a higher energy level.
  • the conduction band electrons of the material contained in the first electron transport film 112a can use the conduction band of the material contained in the second electron transport film 12 as a springboard for migration.
  • the electron transport efficiency of the electron transport layer 100 can be effectively improved, so that when holes migrate to the light-emitting layer 21, more electrons can also migrate to the light-emitting layer 21, it can effectively improve the matching of the number of electrons and holes transmitted to the light-emitting layer 21, so that the process of exciton recombination occurs in the light-emitting layer 21 as much as possible, reducing the interface between the electron transport layer 100 and the light-emitting layer 21 The probability of exciton recombination occurs at any location, thereby effectively improving the efficiency and stability of the light emitting device 200.
  • the conduction band electrons of the material contained in the first electron transport film 11 migrate to the conduction band of the material contained in the light-emitting layer 21, the conduction band electrons of the material contained in the first electron transport film 11 migrate
  • the barrier to the conduction band of the material contained in the second electron transport film 12 is relatively low, and the barrier to the conduction band of the material contained in the second electron transport film 12 and the material contained in the light-emitting layer 21 is relatively low.
  • the valence band energy level of the material contained in the second electron transport film 12 is smaller than the valence band energy level of the material contained in the first electron transport film 11.
  • the valence band holes of the material contained in the light-emitting layer 21 migrate to the valence band of the material contained in the second electron transport film 12, and the barrier is higher, so that The difficulty of hole migration to the interface between the light-emitting layer 21 and the electron transport layer 100 can be increased, and the mobility of the hole to the interface between the light-emitting layer 21 and the electron transport layer 100 can be reduced, so that exciton recombination occurs in the light-emitting layer 21.
  • the second electron transport film 12 serves as an intermediate springboard for the conduction band electrons of the material contained in the first electron transport film 11 to migrate to the conduction band of the material contained in the light emitting layer 21, the second electron The thickness of the transmission film 12 can be selected and set according to actual needs, which is not limited in the embodiment of the present disclosure.
  • the thickness of the first electron transport film 11 is greater than the thickness of the second electron transport film 12. In this way, the thickness of the light emitting device 200 applied with the electron transport layer 100 can be kept basically unchanged or the thickness increased less, avoiding the impact on the slim design of the display device (for example, organic electroluminescent display) applied with the light emitting device 4.
  • the molar ratio of the material contained in the second electron transport film 12 to the material contained in the first electron transport film 11 ranges from 1:5 to 1:3. This can ensure that the electrons have a higher transmission rate, so that the conduction band electrons of the material contained in the second electron transport film 12 can migrate to the conduction band of the material contained in the light-emitting layer 21 faster.
  • the molar ratio of the material contained in the second electron transport film 12 to the material contained in the first electron transport film 11 is 1:4, 1:3, or 1:5.
  • the first electron transport film 11 includes a ZnO (zinc oxide) film, a TiO 2 (titanium dioxide) film, or a SnO 2 (tin oxide) film, of course, it is not limited thereto.
  • the material contained in the first electron transport film 11 may include ZnO, TiO 2 or SnO 2 .
  • the second electron transport film 12 includes a ZrO 2 (zirconium dioxide) film, a La 2 O 3 (lanthanum oxide) film, or a LaTi 2 O 7 (lanthanum titanium oxide) film, but of course it is not limited thereto.
  • the material contained in the second electron transport film 12 may include ZrO 2 , La 2 O 3 or LaTi 2 O 7 .
  • the first electron transport film 11 is a ZnO film, and the ZnO film has characteristics such as higher electrical conductivity and higher light transmittance.
  • the second electron transport film 12 is a ZrO 2 film.
  • the second electron transport film 12 may also be a La 2 O 3 film or a LaTi 2 O 7 film.
  • Figure 3 shows the energy level matching relationship diagram of ZnO and ZrO 2 , the energy level unit is eV. It can be seen from Figure 3 that ZrO 2 has a higher conduction band energy level and a lower valence band energy level than ZnO.
  • the conduction band electrons of the material contained in the first electron transport film 11 can be relatively easily transferred to the conduction band of the material contained in the second electron transport film 12, which improves The transport efficiency of electrons from the electron transport layer 100 to the light emitting layer 21.
  • Some embodiments of the present disclosure also provide a method for preparing the electron transport layer, which is used to prepare the electron transport layer as provided in some of the above embodiments.
  • the preparation method includes S100.
  • the first electron transport film is located on the side of the second electron transport film layer close to the light-emitting layer.
  • the conduction band energy level of the material contained in the first electron transport film is smaller than the conduction band energy level of the material contained in the second electron transport film, and the conduction band energy level of the material contained in the second electron transport film is smaller than that of the light emitting layer. The conduction band energy level of the contained material.
  • the materials contained in the first electron transport film include multiple types.
  • the material contained in the first electron transport film may be ZnO, TiO 2 or SnO 2 , of course, it is not limited thereto.
  • the material contained in the second electron transport film includes a variety of materials.
  • the material contained in the second electron transport film may be ZrO 2 , La 2 O 3 or LaTi 2 O 7 , of course, it is not limited thereto.
  • beneficial effects that can be achieved by the method for preparing the electron transport layer provided by the embodiments of the present disclosure are the same as the beneficial effects that can be achieved by the electron transport layer 100 provided in the foregoing embodiments, and will not be repeated here.
  • the above-mentioned method of laminating the first electron transport film and the second electron transport film together is, for example, laminating the two together in the process of preparing the first electron transport film and the second electron transport film; After the first electron transport film and the second electron transport film, the first electron transport film and the second electron transport film are laminated together.
  • the above method is to laminate the first electron transport film and the second electron transport film together in the process of preparing the first electron transport film and the second electron transport film, as shown in FIG.
  • the electron transport films are laminated together, including S110a to S120a.
  • the film forming process is, for example, a sputtering process or an electrodeposition process that can realize the film formation of semiconductor materials (for example, metal oxides such as ZnO, TiO 2 or SnO 2 ).
  • semiconductor materials for example, metal oxides such as ZnO, TiO 2 or SnO 2 .
  • the aforementioned substrate may be, for example, a common glass substrate, or may be a glass substrate formed with an electron injection layer.
  • the substrate is an electron injection layer formed on a glass substrate
  • the preparation of the electron transport layer is completed, the stack of the electron transport layer and the electron injection layer is also completed.
  • the film forming process is, for example, a sputtering process or an electrodeposition process that can realize the film formation of semiconductor materials (for example, metal oxides such as ZrO 2 , La 2 O 3 or LaTi 2 O 7 ).
  • semiconductor materials for example, metal oxides such as ZrO 2 , La 2 O 3 or LaTi 2 O 7 .
  • the above method is to prepare the first electron transport film and the second electron transport film separately, and then laminate the first electron transport film and the second electron transport film together, as shown in FIG. 5 As shown, the first electron transport film and the second electron transport film are laminated together, including S110b to S130b.
  • the film forming process is, for example, a spin coating process, or a sputtering process or an electrodeposition process that can realize the film formation of semiconductor materials (such as metal oxides such as ZnO, TiO 2 or SnO 2 ).
  • semiconductor materials such as metal oxides such as ZnO, TiO 2 or SnO 2 .
  • the film forming process is, for example, a spin coating process, or a sputtering process or an electrodeposition process that can realize the film formation of semiconductor materials (for example, metal oxides such as ZrO 2 , La 2 O 3 or LaTi 2 O 7 ) .
  • semiconductor materials for example, metal oxides such as ZrO 2 , La 2 O 3 or LaTi 2 O 7 .
  • the method of compounding the first electron transport film and the second electron transport film is a process such as sheeting or lamination.
  • the first electron transport film and the second electron transport film should be prevented from being damaged during the recombination process.
  • the first electron transport film includes a ZnO film, that is, the material contained in the first electron transport film includes ZnO, as shown in FIG. 6, a film forming process is used to form the first electron transport film, including S111b ⁇ S114b .
  • the temperature range of the heat treatment is 60°C to 80°C.
  • zinc acetate will undergo a coordination reaction with diethanolamine to form a zinc diethanolamine complex.
  • the temperature range of the coordination reaction is 60°C to 80°C.
  • the ethanol suspension of zinc acetate is always in an excess state relative to the ethanol solution of diethanolamine, so that the zinc acetate Always in an excessive state, so as to ensure that there is no free diethanolamine in the final diethanolamine complex sol.
  • the molar ratio of the diethanolamine contained in the ethanol solution of diethanolamine to the zinc acetate contained in the ethanol suspension of zinc acetate ranges from 1:1.5 to 1:1. In this way, when the diethanolamine zinc complex is formed, the coordination of the diethanolamine and the zinc ion can be made relatively complete, and the obtained diethanolamine complex sol solution is in a clear state.
  • the viscosity of the diethanolamine complex sol solution from which ethanol is removed can be increased.
  • the ethanol removal method is, for example, a drying removal method
  • the drying temperature can be selected as 60° C.
  • the drying time is set according to specific actual conditions, for example, 2 h.
  • the film forming process may be a casting film forming process or a spin coating film forming process.
  • the rotation speed during spin coating can be set according to actual conditions, and the rotation speed during spin coating can be 1000 rpm.
  • the oxidation treatment of the diethanolamine complex contained in the zinc oxide preformed film may be heating treatment, and the temperature range of the heating treatment may be 80°C to 100°C.
  • the two The ethanolamine complex is oxidized so that the zinc oxide pre-film is formed as a ZnO film.
  • the second electron transport film includes a ZrO 2 film, that is, the material contained in the second electron transport film is ZrO 2 , as shown in FIG. 7, the second electron transport film is formed by a film forming process, including S121b ⁇ S124b.
  • the zirconium oxide contained in the zirconium hydrolyzed sol solution is in the form of zirconium hydroxide. And when the zirconium hydrolyzed sol is obtained, the zirconium hydrolyzed sol is in a clear state.
  • the viscosity of the zirconium hydrolyzed sol solution from which ethanol is removed can be increased.
  • the ethanol removal method is, for example, a dry removal method
  • the drying temperature can be selected as 60° C.
  • the drying time is set according to specific actual conditions, for example, 2 hours.
  • the film forming process may be a casting film forming process or a spin coating film forming process.
  • the rotation speed of the spin coating can be set according to the actual situation, for example, the rotation speed of the spin coating is 1000 rpm.
  • the above-mentioned oxidation treatment is heating treatment, and the temperature range of the heating treatment is 80°C-100°C.
  • the zirconium hydroxide contained in the zirconium dioxide prefabricated film will be oxidized, so that the zirconium dioxide prefabricated film is formed into a ZrO 2 film.
  • using a film forming process to form the second electron transport film further includes: before dripping ammonia water into the ethanol solution of zirconyl chloride octahydrate, mixing absolute ethanol with water to obtain an ethanol aqueous solution ; Mix the ethanol aqueous solution with zirconyl chloride octahydrate to obtain an ethanol suspension of zirconyl chloride octahydrate. This can increase the solubility of zirconyl chloride octahydrate in ethanol.
  • the method for preparing the electron transport layer using methods such as S11b to S130b is taken as an example to illustrate the method for preparing the electron transport layer in more detail.
  • the preparation method of the electron transport layer includes the first step to the seventh step.
  • the first step weigh 6.6 g (that is, 0.036 mol) zinc acetate, add zinc acetate to a beaker after grinding, and add 50 mL of absolute ethanol to the beaker, and stir in a water bath at 60°C for 1 hour to obtain ethanol for zinc acetate. Suspension.
  • the ethanol solution of diethanolamine was slowly added dropwise to the ethanol suspension of zinc acetate and heated at 60° C. to obtain a diethanolamine complex sol solution. At this time, the diethanolamine complex sol solution was in a clear state. Then stand at room temperature for 24h.
  • the diethanolamine complex sol solution was dried at 60° C. for 2 hours to remove the ethanol contained in the diethanolamine complex sol solution.
  • a spin-coating process is used to spin-coat the ethanol-removed diethanolamine complex sol solution to obtain a zinc oxide preformed film.
  • the zinc oxide prefabricated film is subjected to three heating treatments, each with a heating temperature of 90° C. and a heating time of 3 minutes to obtain a ZnO film.
  • the absolute ethanol is mixed with water in a volume ratio of 1:3 to obtain an aqueous ethanol solution.
  • ammonia water was added dropwise to the ethanol suspension of zirconyl chloride octahydrate under heating at 85°C until the ethanol suspension of zirconyl chloride octahydrate was in a clear state to obtain clear zirconium octahydrate Hydrolyzed sol liquid.
  • the zirconium octahydrate hydrolyzed sol solution was dried at 60° C. for 2 hours to remove the ethanol contained in the zirconium octahydrate hydrolyzed sol solution.
  • a spin coating process is used to spin-coat the ethanol-removed zirconium hydrolyzed sol solution to obtain a zirconium dioxide prefabricated film.
  • a sixth step pre-film of zirconium dioxide under conditions of 90 deg.] C in the oxidation treatment to obtain the ZrO 2 film, so that the ZrO 2 film of ZrO contained in a molar ratio of 2 ZnO ZnO film contained 1: 4.
  • the ZnO film and the ZrO 2 film are combined together by means of sheeting to obtain an electron transport layer.
  • the preparation method of the electron transport layer includes the first step to the seventh step.
  • the first step weigh 0.045 mol of zinc acetate, add zinc acetate to a beaker after grinding, and add 60 mL of absolute ethanol to the beaker, and stir in a water bath at 60° C. for 2 hours to obtain an ethanol suspension of zinc acetate.
  • the ethanol solution of diethanolamine is slowly added dropwise to the ethanol suspension of zinc acetate and heated at 80° C. to obtain a diethanolamine complex sol solution. At this time, the diethanolamine complex sol solution is in a clear state. Then stand at room temperature for 24h.
  • the diethanolamine complex sol solution was dried at 60° C. for 2 hours to remove the ethanol contained in the diethanolamine complex sol solution.
  • a spin-coating process is used to spin-coat the ethanol-removed diethanolamine complex sol solution to obtain a zinc oxide preformed film.
  • the zinc oxide prefabricated film is subjected to three heating treatments respectively, the heating temperature of each heating treatment is 100 DEG C, and the heating time is 3 min, to obtain a ZnO film.
  • the absolute ethanol is mixed with water in a volume ratio of 1:2.5 to obtain an ethanol aqueous solution.
  • the fifth step is to add ammonia water dropwise to the ethanol suspension of zirconyl chloride octahydrate under heating at 80°C until the ethanol suspension of zirconyl chloride octahydrate is in a clear state to obtain clear zirconium octahydrate Hydrolyzed sol liquid.
  • the zirconium octahydrate hydrolyzed sol solution was dried at 60° C. for 2 hours to remove the ethanol contained in the zirconium octahydrate hydrolyzed sol solution.
  • the ethanol-removed zirconium hydrolyzed sol solution was spin-coated by a spin-coating process to obtain a zirconium dioxide preformed film.
  • a sixth step pre-film of zirconia at 100 °C for oxidation treatment to obtain the ZrO 2 film, so that the ZrO 2 film of ZrO contained in a molar ratio of 2 ZnO ZnO film contained 1: 3.
  • the ZnO film and the ZrO 2 film are combined together by means of sheeting to obtain an electron transport layer.
  • the preparation method of the electron transport layer includes the first step to the seventh step.
  • the first step weigh 0.05 mol of zinc acetate, add zinc acetate to a beaker after grinding, and add 60 mL of absolute ethanol to the beaker, and stir in a water bath at 60° C. for 2 hours to obtain a zinc acetate suspension.
  • the ethanol solution of diethanolamine was slowly added dropwise to the ethanol suspension of zinc acetate and heated at 70° C. to obtain a diethanolamine complex sol solution. At this time, the diethanolamine complex sol solution was in a clear state. Then stand at room temperature for 24h.
  • the diethanolamine complex sol solution was dried at 60° C. for 2 hours to remove the ethanol contained in the diethanolamine complex sol solution.
  • a spin-coating process is used to spin-coat the ethanol-removed diethanolamine complex sol solution to obtain a zinc oxide preformed film.
  • the zinc oxide prefabricated film is subjected to three heating treatments respectively, the heating temperature of each heating treatment is 80 DEG C, and the heating time is 3 minutes, to obtain a ZnO film.
  • the absolute ethanol is mixed with water in a volume ratio of 1:4 to obtain an ethanol aqueous solution.
  • the fifth step is to add ammonia water dropwise to the ethanol suspension of zirconyl chloride octahydrate under heating at 100°C until the ethanol suspension of zirconyl chloride octahydrate is in a clear state to obtain clear zirconium octahydrate Hydrolyzed sol liquid.
  • the zirconium hydrolyzed sol solution was dried at 60° C. for 2 hours to remove the ethanol contained in the zirconium octahydrate hydrolyzed sol solution.
  • a spin coating process is used to spin-coat the ethanol-removed zirconium hydrolyzed sol solution to obtain a zirconium dioxide preformed film.
  • a sixth step pre-film of zirconium dioxide at 80 °C for oxidation treatment to obtain the ZrO 2 film, so that the ZrO 2 film of ZrO contained in a molar ratio of 2 ZnO ZnO film contained 1: 5.
  • the ZnO film and the ZrO 2 film are combined together by means of sheeting to obtain an electron transport layer.
  • the light emitting device 200 includes the electron transport layer 100 as provided in some of the above embodiments, and the electron transport layer 100 includes a first electron transport film 11 and a second electron transport film 12 that are stacked.
  • the light emitting device 200 further includes a light emitting layer 21 provided on the side of the second electron transport film 12 away from the first electron transport film 11.
  • the conduction band energy level of the material contained in the light-emitting layer 21 is greater than the conduction band energy level of the material contained in the second electron transport film 12.
  • the beneficial effects that can be achieved by the light emitting device 200 provided by the embodiments of the present disclosure are the same as the beneficial effects that can be achieved by the electron transport layer 100 provided in the foregoing embodiments, and will not be repeated here.
  • the light emitting device 200 further includes an electron injection layer 22 disposed on the side of the electron transport layer 100 away from the light emitting layer 21, and the first electron transport film 11 in the electron transport layer 100 is located on the electron transport layer 100. Between the injection layer 11 and the second electron transport film 12.
  • the light emitting device 200 further includes an exciton adjustment layer 23, a hole transport layer 24, and a hole injection layer 25.
  • the exciton adjustment layer 23 is disposed on the side of the light emitting layer 21 away from the electron transport layer 100, and the hole transport layer 24 is disposed on the excitation layer.
  • the sub-regulating layer 24 is far away from the light emitting layer 21, and the hole injection layer 25 is disposed on the side of the hole transport layer 24 far away from the light emitting layer 21.
  • the above-mentioned exciton adjusting layer 23 is configured to adjust the transmission efficiency of holes transported into the light-emitting layer 21, so that the holes and the electrons transported into the light-emitting layer 21 will recombine with excitons in the light-emitting layer 21 as much as possible to improve light emission.
  • the luminous efficiency of the device 200 is configured to adjust the transmission efficiency of holes transported into the light-emitting layer 21, so that the holes and the electrons transported into the light-emitting layer 21 will recombine with excitons in the light-emitting layer 21 as much as possible to improve light emission.
  • the above-mentioned light-emitting device 200 further includes an anode A and a cathode K.
  • the anode A is connected to the side of the hole injection layer 25 away from the light-emitting layer 21, and the cathode K is connected to the electron injection layer 22. The side facing away from the light-emitting layer 21 is connected.
  • the anode A and the cathode K are used to provide a driving voltage to the light emitting device 200 to drive the light emitting device 200 to emit light.
  • the structure of the light emitting device 200 is only described by taking the above structure as an example.
  • the light emitting device 200 may not include one of the exciton adjustment layer 23, the hole transport layer 24, or the hole injection layer 25; or, the light emitting device 200 may not include the electron injection layer 22.
  • the display device 300 includes a plurality of light emitting devices 200 as provided in some of the above embodiments.
  • the beneficial effects that can be achieved by the display device 300 provided by the embodiments of the present disclosure are the same as the beneficial effects that can be achieved by the light emitting device 200 provided by some of the above embodiments, and will not be repeated here.
  • the display device 300 provided in the foregoing embodiments may be any product or component with a display function, such as a mobile phone, a tablet computer, a television, a monitor, a notebook computer, a digital photo frame, or a navigator.
  • a display function such as a mobile phone, a tablet computer, a television, a monitor, a notebook computer, a digital photo frame, or a navigator.

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Abstract

一种电子传输层，应用于发光器件，所述发光器件包括设置在所述电子传输层的一侧的发光层。所述电子传输层包括：第一电子传输膜；以及，层叠设置在所述第一电子传输膜的靠近所述发光层的一侧的第二电子传输膜，所述第二电子传输膜被配置为与所述发光层接触。所述第二电子传输膜所含有的材料的导带能级大于所述第一电子传输膜所含有的材料的导带能级，所述第二电子传输膜所含有的材料的导带能级小于所述发光层所含有的材料的导带能级。

Description

电子传输层及其制备方法、发光器件和显示装置
本申请要求于2019年02月28日提交的、申请号为201910150041.1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
本公开涉及显示技术领域，尤其涉及一种电子传输层及其制备方法、发光器件和显示装置。
背景技术
有机发光二极管(Organic Light-Emitting Diode，缩写为OLED)显示器是一种利用电流驱动发光器件实现图像显示的显示设备，其具有自发光、不需背光源、对比度高、厚度薄、视角广、反应速度快等优异特性。
发明内容
一方面，提供一种电子传输层。所述电子传输层应用于发光器件，所述发光器件包括发光层，所述电子传输层设置在所述发光层的一侧。所述电子传输层包括：第一电子传输膜；以及，层叠设置在所述第一电子传输膜的靠近所述发光层的一侧的第二电子传输膜，所述第二电子传输膜被配置为与所述发光层接触。所述第二电子传输膜所含有的材料的导带能级大于所述第一电子传输膜所含有的材料的导带能级，所述第二电子传输膜所含有的材料的导带能级小于所述发光层所含有的材料的导带能级。
在一些实施例中，所述第二电子传输膜所含有的材料的价带能级小于所述第一电子传输膜所含有的材料的价带能级。
在一些实施例中，所述第二电子传输膜的厚度小于所述第一电子传输膜的厚度。
在一些实施例中，所述第二电子传输膜所含有的材料与所述第一电子传输膜所含有的材料的摩尔比的范围为1:5～1:3。
在一些实施例中，所述第一电子传输膜包括ZnO膜、TiO 2膜或SnO 2膜。
在一些实施例中，所述第二电子传输膜包括ZrO 2膜、La 2O 3膜或LaTi 2O 7膜。
另一方面，提供一种电子传输层的制备方法。所述制备方法用于制备如上述一些实施例中所述的电子传输层。所述制备方法包括：将第一电子传输膜和第二电子传输膜层叠在一起。所述第一电子传输膜位于所述第二电子传输膜层的靠近所述发光层的一侧；所述第一电子传输膜所含有的材料的导带能级小于所述第二电子传输膜所含有的材料的导带能级，所述第二电子传输 膜所含有的材料的导带能级小于发光层所含有的材料的导带能级。
在一些实施例中，所述将第一电子传输膜和第二电子传输膜层叠在一起，包括：采用成膜工艺在衬底上形成所述第一电子传输膜；采用成膜工艺在所述第一电子传输膜远离所述衬底的表面形成所述第二电子传输膜。
在一些实施例中，所述将第一电子传输膜和第二电子传输膜层叠在一起，包括：采用成膜工艺形成所述第一电子传输膜；采用成膜工艺形成所述第二电子传输膜；将所述第一电子传输膜和所述第二电子传输膜复合在一起。
在一些实施例中，所述第一电子传输膜包括ZnO膜。所述采用成膜工艺形成所述第一电子传输膜，包括：向醋酸锌的乙醇悬浊液加入二乙醇胺的乙醇溶液，并进行加热处理，获得二乙醇胺配合物溶胶液；去除所述二乙醇胺配合物溶胶液含有的乙醇；采用成膜工艺将去除乙醇的二乙醇胺配合物溶胶液制成氧化锌预制膜；对所述氧化锌预制膜所含有的二乙醇胺配合物进行氧化处理，形成ZnO膜。
在一些实施例中，所述二乙醇胺的乙醇溶液中所含有的二乙醇胺与所述醋酸锌的乙醇悬浊液中所含有的醋酸锌的摩尔比范围为1:1.5～1:1。
在一些实施例中，所述第二电子传输膜包括ZrO 2膜。所述采用成膜工艺形成所述第二电子传输膜，包括：在加热条件下向八水合氯化氧锆的乙醇悬浊液中滴加氨水，获得锆水解溶胶液；去除所述锆水解溶胶液含有的乙醇；采用成膜工艺将去除乙醇的锆水解溶胶液制作二氧化锆预制膜；对所述二氧化锆预制膜进行氧化处理，形成ZrO 2膜。
在一些实施例中，所述采用成膜工艺形成所述第二电子传输膜，还包括：在所述向八水合氯化氧锆的乙醇悬浊液中滴加氨水之前，将无水乙醇与水混合，获得乙醇水溶液；其中，所述无水乙醇与所述水的体积比范围为1:4～1:2.5；将所述乙醇水溶液与八水合氯化氧锆进行混合，获得八水合氯化氧锆的乙醇悬浊液。
又一方面，提供一种发光器件。所述发光器件包括：如上述一些实施例中所述的电子传输层，所述电子传输层包括层叠设置的第一电子传输膜和第二电子传输膜；以及，设置在所述第二电子传输膜远离所述第一电子传输膜的一侧的发光层；其中，所述发光层所含有的材料的导带能级大于所述第二电子传输膜所含有的材料的导带能级。
在一些实施例中，所述发光器件，还包括：设置在所述电子传输层远离所述发光层的一侧的电子注入层；设置在所述发光层远离所述电子传输层的一侧的激子调节层，所述激子调节层被配置为，调节传输至所述发光层内的 空穴的传输效率，以使得所述空穴和传输至所述发光层内的电子尽量在所述发光层内发生激子复合；设置在所述激子调节层远离所述发光层的一侧的空穴传输层；以及，设置在所述空穴传输层远离所述发光层的一侧的空穴注入层。
又一方面，提供一种显示装置。所述显示装置包括：多个如上述一些实施例中所述的发光器件。
附图说明
为了更清楚地说明本公开中的技术方案，下面将对本公开一些实施例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公开的一些实施例的附图，对于本领域普通技术人员来讲，还可以根据这些附图获得其他的附图。此外，以下描述中的附图可以视作示意图，并非对本公开实施例所涉及的产品的实际尺寸、方法的实际流程等的限制。
图1为相关技术中的发光器件的结构图；
图2为根据本公开的一些实施例中的一种电子传输层的结构图；
图3为根据本公开的一些实施例中的一种电子传输层所含有的材料的能级图；
图4为根据本公开的一些实施例中的一种电子传输层的制备方法流程图；
图5为根据本公开的一些实施例中的另一种电子传输层的制备方法流程图；
图6为根据本公开的一些实施例中的一种第一电子传输层的制备方法流程图；
图7为根据本公开的一些实施例中的一种第二电子传输膜的制备方法流程；
图8为根据本公开的一些实施例中的一种发光器件的结构图；
图9为根据本公开的一些实施例中的一种显示装置的结构图。
具体实施方式
下面将结合附图，对本公开一些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公开一部分实施例，而不是全部的实施例。基于本公开所提供的实施例，本领域普通技术人员所获得的所有其他实施例，都属于本公开保护的范围。
除非上下文另有要求，否则，在整个说明书和权利要求书中，术语“包 括(comprise)”及其其他形式例如第三人称单数形式“包括(comprises)”和现在分词形式“包括(comprising)”被解释为开放、包含的意思，即为“包含，但不限于”。在说明书的描述中，术语“一个实施例(one embodiment)”、“一些实施例(some embodiments)”、“示例性实施例(exemplary embodiments)”、“示例(example)”或“一些示例(some examples)”等旨在表明与该实施例或示例相关的特定特征、结构、材料或特性包括在本公开的至少一个实施例或示例中。上述术语的示意性表示不一定是指同一实施例或示例。此外，所述的特定特征、结构、材料或特点可以以任何适当方式包括在任何一个或多个实施例或示例中。
以下，术语“第一”、“第二”仅用于描述目的，而不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量。由此，限定有“第一”、“第二”的特征可以明示或者隐含地包括一个或者更多个该特征。在本公开实施例的描述中，除非另有说明，“多个”的含义是两个或两个以上。
如图1所示，相关技术中的发光器件包括阳极200'、阴极300'以及位于阳极200'和阴极300'之间的发光功能层100'。该发光功能层100'包括空穴注入层111'、空穴传输层112'、发光层130'、电子传输层122'和电子注入层121'。一般来说，利用阳极200'和阴极300'向发光功能层100'施加一定的电压的情况下，空穴会通过空穴注入层111'所含有的材料的价带和空穴传输层112'所含有的材料的价带迁移至发光层130'的价带，同时电子会通过电子注入层121'所含有的材料的导带、电子传输层122'所含有的材料的导带迁移至发光层130'的导带，使得电子和空穴在发光层130'发生激子复合。
在相关技术中，电子传输层122'所使用的材料一般为ZnO等金属氧化物。ZnO等金属氧化物具有高电导率和高透过率，在电子传输材料的发展中起到积极作用。虽然金属氧化物所制作的电子传输层122'可以有效促进电子传输速度，但受制于金属氧化物的能带结构特点，金属氧化物的导带电子向发光层130'的转移仍然要跨过较大的势垒，这样容易使得电子传输效率相对空穴传输效率较低，导致电子空穴数量不匹配，进而容易导致激子复合发生在发光层130'和电子传输层122'的界面处，降低发光器件的效能和稳定性。
基于此，如图9所示，本公开的一些实施例提供了一种显示装置300，该显示装置300包括多个发光器件200。如图8所示，发光器件200包括空穴注入层25、空穴传输层24、发光层21、电子传输层100和电子 注入层22。发光器件200还包括设置在空穴传输层24和发光层21之间的激子调节层23，该激子调节层23能够调节空穴传输至发光层21的传输效率，使得激子复合尽量发生在发光层21中。此处，相对于相关技术中的电子传输层122'，本公开实施例提供的显示装置300中，发光器件200所含有的电子传输层100的电子传输效率比较高。
下面对本公开实施例提供的电子传输层100进行示意性说明。
如图2和图8所示，本公开实施例提供了一种电子传输层100，该电子传输层100应用于发光器件200，发光器件200包括设置在电子传输层100的一侧的发光层21。
在一些实施例中，如图2和图8所示，电子传输层100包括：第一电子传输膜11以及层叠设置在第一电子传输膜11的靠近发光层21的一侧的第二电子传输膜22，第二电子传输膜22被配置为与发光层21接触。第一电子传输膜11所含有的材料的导带能级小于第二电子传输膜12所含有的材料的导带能级，第二电子传输膜12所含有的材料的导带能级小于发光层21所含有的材料的导带能级。
第一电子传输膜11和第二电子传输膜12能够构成异质结，提高电子传输层100的电子传输效率，进而使得迁移至发光层21的电子和空穴的数量能够匹配，提高发光层21发光效率。
在将本公开实施例提供的电子传输层100应用于发光器件200中时，第二电子传输膜12位于发光层21与第一电子传输膜11之间，第一电子传输膜11位于电子注入层22与第二电子传输膜12之间。当发光器件200发光时，电子注入层22所含有的材料的导带电子会先迁移至第一电子传输膜11所含有的材料的导带，接着从第一电子传输膜11所含有的材料的导带电子迁移至第二电子传输膜12所含有的材料的导带，最后从第二电子传输膜12所含有的材料的导带电子迁移至发光层21所含有的材料的导带。相应的，空穴也会迁移至发光层21所含有的材料的价带，这样就能够使得空穴和电子在发光层21中发生激子复合，激子复合所释放出的能量以光的形式释放，从而使得发光器件200发光。
基于本公开实施例提供的电子传输层100的结构和应用可知，通过在第一电子传输膜11的靠近发光层21的一侧设置第二电子传输膜12，使得第二电子传输膜12与发光层31接触，并使得第一电子传输膜11所含有的材料的导带能级小于第二电子传输膜12所含有的材料的导带能级，第二电子传输膜12所含有的材料的导带能级小于发光层31所含有 的材料的导带能级，这样第一电子传输膜11所含有的材料与第二电子传输膜12所含有的材料的导带能级差值会小于第一电子传输膜11所含有的材料与发光层21所含有的材料的导带能级差值，第二电子传输膜12所含有的材料与发光层21所含有的材料的导带能级差值也会小于第一电子传输膜11所含有的材料与发光层21所含有的材料的导带能级差值。
此时，相对于第一电子传输膜11所含有的材料的导带电子迁移至发光层21所含有的材料的导带的势垒，第一电子传输膜11所含有的材料的导带电子迁移至第二电子传输膜12所含有的材料的导带的势垒会相对较低，且第二电子传输膜12所含有的材料与发光层21所含有的材料的导带的势垒也会相对较低，这样会使得第一电子传输膜11所含有的材料的导带电子能够比较容易的迁移至第二电子传输膜12所含有的材料的导带上，然后再以第二电子传输膜12层所含有的材料的导带为基准，较为容易地迁移至能级较高的发光层21所含有的材料的导带上。
由此，本公开实施例提供的电子传输层100中，第一电子传输膜112a所含有的材料的导带电子能够以第二电子传输膜12所含有的材料的导带作为迁移的跳板，快速的向发光层21所含有的材料的导带迁移，使得电子传输层100的电子传输效率能够得到有效提高，这样在空穴迁移至发光层21内时，较多的电子也能迁移至发光层21内，也就可以有效提高传输至发光层21内的电子和空穴的数目的匹配性，使得激子复合的过程尽量发生在发光层21内，降低电子传输层100与发光层21的界面处发生激子复合的机率，从而可以有效提高发光器件200的效能和稳定性。
此外，由于相对于第一电子传输膜11所含有的材料的导带电子迁移至发光层21所含有的材料的导带的势垒，第一电子传输膜11所含有的材料的导带电子迁移至第二电子传输膜12所含有的材料的导带的势垒会相对较低，且第二电子传输膜12所含有的材料与发光层21所含有的材料的导带的势垒相对较低，这样在未对发光器件200施加较大电压的情况下，即可提高电子的传输效率，同时阻碍空穴从发光层21所含有的材料的价带向电子传输层100的迁移，从而能够降低第二电子传输膜12与发光层21的界面处发生激子复合的机率，提高发光器件200的发光效率。
在一些实施例中，如图8所示，上述第二电子传输膜12所含有的材料的价带能级小于第一电子传输膜11所含有的材料的价带能级。这样在将上述电子传输层100应用于发光器件200中时，发光层21所含有的材 料的价带空穴迁移至第二电子传输膜12所含有的材料的价带的势垒较高，从而可以提高空穴向发光层21与电子传输层100的界面迁移的难度，降低空穴向发光层21与电子传输层100的界面处的迁移率，使得激子复合发生在发光层21内。
在一些实施例中，由于第二电子传输膜12是作为第一电子传输膜11所含有的材料的导带电子迁移至发光层21所含有的材料的导带的中间跳板，因此，第二电子传输膜12的厚度根据实际需要选择设置即可，本公开实施例对此不做限定。
在一些示例中，第一电子传输膜11的厚度大于第二电子传输膜12的厚度。这样可以使得应用有电子传输层100的发光器件200的厚度基本保持不变或厚度增加较少，避免对应用有发光器件4的显示装置(例如有机电致发光显示器)的轻薄化设计产生影响。
在一些实施例中，第二电子传输膜12所含有的材料与第一电子传输膜11所含有的材料的摩尔比的范围为1:5～1:3。这样可以确保电子具有较高的传输速率，使得第二电子传输膜12所含有的材料的导带电子能够较快地迁移至发光层21所含有的材料的导带。此处，示例性的，第二电子传输膜12所含有的材料与第一电子传输膜11所含有的材料的摩尔比为1:4、1:3或1:5。
在一些实施例中，第一电子传输膜11包括ZnO(氧化锌)膜、TiO 2(二氧化钛)膜或SnO 2(氧化锡)膜，当然不仅限于此。此时，第一电子传输膜11所含有的材料可以包括ZnO、TiO 2或SnO 2。
在一些实施例中，第二电子传输膜12包括ZrO 2(二氧化锆)膜、La 2O 3(氧化镧)膜或LaTi 2O 7(镧钛氧化物)膜，当然不仅限于此。此时，第二电子传输膜12所含有的材料可以包括ZrO 2、La 2O 3或LaTi 2O 7。
示例性的，第一电子传输膜11为ZnO膜，ZnO膜具有较高的电导率以及较高的透光率等特性。第二电子传输膜12为ZrO 2膜，当然第二电子传输膜12也可以为La 2O 3膜或LaTi 2O 7膜。图3示出了ZnO与ZrO 2的能级匹配关系图，能级单位为eV。从图3可以看出，相对ZnO来说，ZrO 2具有较高的导带能级，较低的价带能级。第二电子传输膜12采用ZrO 2膜时，可以使得第一电子传输膜11所含有的材料的导带电子能够比较容易的迁移至第二电子传输膜12所含有的材料的导带上，提高电子从电子传输层100至发光层21的传输效率。
本公开的一些实施例还提供了一种电子传输层的制备方法，该制备 方法用于制备如上述一些实施例中提供的电子传输层。该制备方法包括S100。
S100，将第一电子传输膜和第二电子传输膜层叠在一起。第一电子传输膜位于第二电子传输膜层的靠近发光层的一侧。第一电子传输膜所含有的材料的导带能级小于该第二电子传输膜所含有的材料的导带能级，且第二电子传输膜所含有的材料的导带能级小于发光层所含有的材料的导带能级。
第一电子传输膜所含有的材料包括多种。示例性的，第一电子传输膜所含有的材料可以为ZnO、TiO 2或SnO 2，当然不仅限于此。
第二电子传输膜所含有的材料包括多种。示例性的，第二电子传输膜所含有的材料可以为ZrO 2、La 2O 3或LaTi 2O 7，当然不仅限于此。
本公开实施例提供的电子传输层的制备方法所能实现的有益效果与上述实施例中提供的电子传输层100所能实现的有益效果相同，在此不做赘述。
上述S100中，将第一电子传输膜和第二电子传输膜层叠在一起的方法包括多种，本公开实施例对此不做限定，可以根据实际需要选择设置。
上述将第一电子传输膜和第二电子传输膜层叠在一起的方法，例如为在制备第一电子传输膜和第二电子传输膜的过程中即将两者层叠在一起；又如为在分别制备第一电子传输膜和第二电子传输膜之后，再将第一电子传输膜和第二电子传输膜层叠在一起。
下面对上述两种将第一电子传输膜和第二电子传输膜层叠在一起的方法进行示意性说明。
在一些示例中，在上述方法为在制备第一电子传输膜和第二电子传输膜的过程中即将两者层叠在一起的情况下，如图4所示，将第一电子传输膜和第二电子传输膜层叠在一起，包括S110a～S120a。
S110a，采用成膜工艺在衬底上形成第一电子传输膜。
此处，成膜工艺例如为溅射工艺或电沉积工艺等可实现半导体材料(例如ZnO、TiO 2或SnO 2等金属氧化物)成膜的工艺。
上述衬底例如可以为普通的玻璃基板，又如可以为形成有电子注入层的玻璃基板。
在衬底为形成在玻璃基板上的电子注入层的情况下，在完成电子传输层的制备时，也就完成了电子传输层与电子注入层的层叠。
S120a，采用成膜工艺在第一电子传输膜远离衬底的表面形成第二电 子传输膜。
此处，成膜工艺例如为溅射工艺或电沉积工艺等可实现半导体材料(例如ZrO 2、La 2O 3或LaTi 2O 7等金属氧化物)成膜的工艺。
在另一些示例中，在上述方法为在分别制备第一电子传输膜和第二电子传输膜之后，再将第一电子传输膜和第二电子传输膜层叠在一起的情况下，如图5所示，将第一电子传输膜和第二电子传输膜层叠在一起，包括S110b～S130b。
S110b，采用成膜工艺形成第一电子传输膜。
此处，成膜工艺例如为旋涂工艺，又如为溅射工艺或电沉积工艺等可实现半导体材料(例如ZnO、TiO 2或SnO 2等金属氧化物)成膜的工艺。
S120b，采用成膜工艺形成第二电子传输膜.
此处，成膜工艺例如为旋涂工艺，又如为溅射工艺或电沉积工艺等可实现半导体材料(例如ZrO 2、La 2O 3或LaTi 2O 7等金属氧化物)成膜的工艺。
S130b，将第一电子传输膜和第二电子传输膜复合在一起。
示例性的，复合第一电子传输膜和第二电子传输膜的方法为压片或层压等工艺。此处，应当避免第一电子传输膜和第二电子传输膜在复合过程中发生损伤。
在上述S110b中，若第一电子传输膜包括ZnO膜，也即第一电子传输膜所含有的材料包括ZnO，如图6所示，采用成膜工艺形成第一电子传输膜，包括S111b～S114b。
S111b，向醋酸锌的乙醇悬浊液中加入二乙醇胺的乙醇溶液，并进行加热处理，获得二乙醇胺配合物溶胶液。
在上述S111b中，加热处理的温度范围为60℃～80℃。在加热处理的过程中，醋酸锌会与二乙醇胺发生配位反应，生成二乙醇胺锌配合物，配位反应的温度范围也即为60℃～80℃。
在一些示例中，在向醋酸锌的乙醇悬浊液中加入二乙醇胺的乙醇溶液时，相对于二乙醇胺的乙醇溶液，向醋酸锌的乙醇悬浊液一直处在过量的状态，以使得醋酸锌始终处在过量的状态，从而保证最终所制作的二乙醇胺配合物溶胶液中不存在游离的二乙醇胺。
在一些示例中，上述二乙醇胺的乙醇溶液所含有的二乙醇胺与醋酸锌的乙醇悬浊液所含有的醋酸锌的摩尔比范围为1:1.5～1:1。这样在生成二乙醇胺锌配合物时，可以使得二乙醇胺与锌离子的配位较为完全，所 获得的二乙醇胺配合物溶胶液呈现澄清状态。
S112b，去除二乙醇胺配合物溶胶液含有的乙醇。
去除二乙醇胺配合物溶胶液含有的乙醇后，可以增加去除乙醇的二乙醇胺配合物溶胶液的粘度。此处，乙醇的去除方式例如为干燥去除方式，干燥的温度可以选择为60℃，干燥时间根据具体实际情况设定，例如为2h。
S113b，采用成膜工艺将去除乙醇的二乙醇胺配合物溶胶液制成氧化锌预制膜。
示例性的，成膜工艺可以为流延法成膜工艺或者旋涂法成膜工艺。例如，采用旋涂法成膜工艺时，旋涂时的转速可根据实际情况设定，旋涂时的转速可以为1000rpm。
S114b，对氧化锌预制膜所含有的二乙醇胺配合物进行氧化处理，形成ZnO膜。
示例性的，对氧化锌预制膜所含有的二乙醇胺配合物进行的氧化处理可以为加热处理，加热处理的温度范围可以为80℃～100℃，此时，得氧化锌预制膜所含有的二乙醇胺配合物会被氧化，使得氧化锌预制膜形成为ZnO膜。
在上述S120b中，若第二电子传输膜包括ZrO 2膜，也即第二电子传输膜所含有的材料为ZrO 2，如图7所示，采用成膜工艺形成第二电子传输膜，包括S121b～S124b。
S121b，在加热条件下向八水合氯化氧锆的乙醇悬浊液中滴加氨水，获得锆水解溶胶液。
上述锆水解溶胶液中所含有的氧化锆是以氢氧化锆的形式存在。且在获得锆水解溶胶液时，锆水解溶胶液呈现澄清状态。
S122b，去除锆水解溶胶液含有的乙醇。
去除乙醇后，可以使得去除乙醇的锆水解溶胶液的粘度增加。
此处，乙醇的去除方式例如为干燥去除方式，干燥温度可以选择为60℃，干燥时间根据具体实际情况设定，例如2h。
S123b，采用成膜工艺将所述去除乙醇的锆水解溶胶液制作二氧化锆预制膜。
示例性的，成膜工艺可以为流延法成膜工艺或者旋涂法成膜工艺。在采用旋涂法成膜工艺形成二氧化锆预制膜时，旋涂的转速可根据实际情况设定，例如旋涂时的转速为1000rpm。
S124b，将二氧化锆预制膜进行氧化处理，形成ZrO 2膜。
示例性的，上述氧化处理为加热处理，加热处理的温度范围为80℃～100℃。
在氧化处理过程中，二氧化锆预制膜所含有的氢氧化锆会发生氧化，使得二氧化锆预制膜形成为ZrO 2膜。
在一些示例中，上述S120b中，采用成膜工艺形成第二电子传输膜还包括：在向八水合氯化氧锆的乙醇溶液中滴加氨水之前，将无水乙醇与水混合，获得乙醇水溶液；将乙醇水溶液与八水合氯化氧锆进行混合，获得八水合氯化氧锆的乙醇悬浊液。这样可以增加八水合氯化氧锆在乙醇中的溶解度。
下面以采用如S11b～S130b的方法制备电子传输层为例，对电子传输层的制备方法进行较为详细的示意性说明。
在一些示例中，电子传输层的制备方法包括第一步～第七步。
第一步，称取6.6g(也即0.036mol)醋酸锌，经研磨后将醋酸锌加入烧杯中，并向烧杯中加入50mL无水乙醇，于60℃条件下水浴搅拌1h得到醋酸锌的乙醇悬浊液。
将5mL(也即0.052mol)的二乙醇胺溶于15mL的无水乙醇中，获得二乙醇胺的乙醇溶液。
向醋酸锌的乙醇悬浊液中缓慢滴加二乙醇胺的乙醇溶液，并在60℃的条件下进行加热处理，获得二乙醇胺配合物溶胶液，此时二乙醇胺配合物溶胶液呈澄清状态。然后室温静置24h。
第二步，将二乙醇胺配合物溶胶液在60℃条件下干燥2h，以去除二乙醇胺配合物溶胶液中所含有的乙醇。
在1000rpm的转速下，采用旋涂工艺对去除乙醇的二乙醇胺配合物溶胶液进行旋涂处理，获得氧化锌预制膜。
第三步，将氧化锌预制膜进行分别3次加热处理，每次加热处理的加热温度为90℃，加热时间为3min，得到ZnO膜。
第四步，按照1:3的体积比将无水乙醇与水混合，获得乙醇水溶液。
将25mL的乙醇水溶液与12.88g(也即0.04mol)的八水合氯化氧锆混合搅拌30min，获得八水合氯化氧锆的乙醇悬浊液。
第五步，在85℃的加热条件下向八水合氯化氧锆的乙醇悬浊液中滴加氨水，直到八水合氯化氧锆的乙醇悬浊液呈澄清状态，获得澄清的八水合锆水解溶胶液。
将八水合锆水解溶胶液在60℃条件下干燥2h，以去除八水合锆水解溶胶液所含有的乙醇。
在1000rpm的转速下，采用旋涂工艺对去除乙醇的锆水解溶胶液进行旋涂处理，获得二氧化锆预制膜。
第六步，在90℃条件下对二氧化锆预制膜进行氧化处理，获得ZrO 2膜，使得ZrO 2膜中所含有的ZrO 2与ZnO膜中所含有的ZnO的摩尔比为1:4。
第七步，采用压片的方式将ZnO膜与ZrO 2膜复合在一起，获得电子传输层。
在另一些示例中，电子传输层的制备方法包括第一步～第七步。
第一步，称取0.045mol醋酸锌，经研磨后将醋酸锌加入烧杯中，并向烧杯中加入60mL无水乙醇，于60℃条件下水浴搅拌2h得到醋酸锌的乙醇悬浊液。
将0.045mol的二乙醇胺溶于20mL的无水乙醇中，获得二乙醇胺的乙醇溶液。
向醋酸锌的乙醇悬浊液中缓慢滴加二乙醇胺的乙醇溶液，并在80℃的条件下进行加热处理，获得二乙醇胺配合物溶胶液，此时二乙醇胺配合物溶胶液呈澄清状态。然后室温静置24h。
第二步，将二乙醇胺配合物溶胶液在60℃条件下干燥2h，以去除二乙醇胺配合物溶胶液所含有的乙醇。
在1000rpm的转速下，采用旋涂工艺对去除乙醇的二乙醇胺配合物溶胶液进行旋涂处理，获得氧化锌预制膜。
第三步，将氧化锌预制膜进行分别3次加热处理，每次加热处理的加热温度为100℃，加热时间为3min，得到ZnO膜。
第四步，按照1:2.5的体积比将无水乙醇与水混合，获得乙醇水溶液。
将25mL的乙醇水溶液与0.36mol的八水合氯化氧锆混合搅拌30min，获得八水合氯化氧锆的乙醇悬浊液。
第五步，在80℃的加热条件下向八水合氯化氧锆的乙醇悬浊液中滴加氨水，直到八水合氯化氧锆的乙醇悬浊液呈澄清状态，获得澄清的八水合锆水解溶胶液。
将八水合锆水解溶胶液在60℃条件下干燥2h，以去除八水合锆水解溶胶液所含有的乙醇。
在1000rpm的转速下，采用旋涂工艺对去除乙醇的锆水解溶胶液进 行旋涂处理，获得二氧化锆预制膜。
第六步，在100℃条件下对二氧化锆预制膜进行氧化处理，获得ZrO 2膜，使得ZrO 2膜中所含有的ZrO 2与ZnO膜中所含有的ZnO的摩尔比为1:3。
第七步，采用压片的方式将ZnO膜与ZrO 2膜复合在一起，获得电子传输层。
在又一些示例中，电子传输层的制备方法包括第一步～第七步。
第一步，称取0.05mol醋酸锌，经研磨后将醋酸锌加入烧杯中，并向烧杯中加入60mL无水乙醇，于60℃条件下水浴搅拌2h，得到醋酸锌悬浊液。
将0.068mol的二乙醇胺溶于30mL的无水乙醇中，获得二乙醇胺的乙醇溶液。
向醋酸锌的乙醇悬浊液中缓慢滴加二乙醇胺的乙醇溶液，并在70℃的条件下进行加热处理，获得二乙醇胺配合物溶胶液，此时二乙醇胺配合物溶胶液呈澄清状态。然后室温静置24h。
第二步，将二乙醇胺配合物溶胶液在60℃条件下干燥2h，以去除二乙醇胺配合物溶胶液所含有的乙醇。
在1000rpm的转速下，采用旋涂工艺对去除乙醇的二乙醇胺配合物溶胶液进行旋涂处理，获得氧化锌预制膜。
第三步，将氧化锌预制膜进行分别3次加热处理，每次加热处理的加热温度为80℃，加热时间为3min，得到ZnO膜。
第四步，按照1:4的体积比将无水乙醇与水混合，获得乙醇水溶液。
将37mL的乙醇水溶液与0.30mol的八水合氯化氧锆混合搅拌30min，获得八水合氯化氧锆的乙醇悬浊液。
第五步，在100℃的加热条件下向八水合氯化氧锆的乙醇悬浊液中滴加氨水，直到八水合氯化氧锆的乙醇悬浊液呈澄清状态，获得澄清的八水合锆水解溶胶液。
将锆水解溶胶液在60℃条件下干燥2h，以去除八水合锆水解溶胶液所含有的乙醇。
在1000rpm的转速下，采用旋涂工艺对去除乙醇的锆水解溶胶液进行旋涂处理，获得二氧化锆预制膜。
第六步，在80℃条件下对二氧化锆预制膜进行氧化处理，获得ZrO 2膜，使得ZrO 2膜中所含有的ZrO 2与ZnO膜中所含有的ZnO的摩尔比为 1:5。
第七步，采用压片的方式将ZnO膜与ZrO 2膜复合在一起，获得电子传输层。
本公开的一些实施例还提供了提供一种发光器件200。如图8所示，发光器件200包括如上述一些实施例中提供的电子传输层100，该电子传输层100包括层叠设置的第一电子传输膜11和第二电子传输膜12。发光器件200还包括设置在第二电子传输膜12远离第一电子传输膜11的一侧的发光层21。发光层21所含有的材料的导带能级大于第二电子传输膜12所含有的材料的导带能级。
本公开实施例提供的发光器件200所能实现的有益效果与上述实施例中提供的电子传输层100所能实现的有益效果相同，在此不做赘述。
在一些实施例中，如图8所示，发光器件200还包括设置在电子传输层100远离发光层21的一侧的电子注入层22，电子传输层100中的第一电子传输膜11位于电子注入层11与第二电子传输膜12之间。
发光器件200还包括激子调节层23、空穴传输层24和空穴注入层25，激子调节层23设置在发光层21远离电子传输层100的一侧，空穴传输层24设置在激子调节层24远离发光层21的一侧，空穴注入层25设置在空穴传输层24远离发光层21的一侧。上述激子调节层23被配置为，调节传输至发光层21内的空穴的传输效率，以使得空穴和传输至发光层21内的电子尽量在发光层21内发生激子复合，提高发光器件200的发光效率。
在一些实施例中，如图8所示，上述发光器件200还包括阳极A和阴极K，阳极A与空穴注入层25的背离发光层21的一侧连接，阴极K与电子注入层22的背离发光层21的一侧连接。这样利用阳极A和阴极K向发光器件200提供驱动电压，以驱动发光器件200发光。
发光器件200的结构仅以上述结构为例进行说明。在一些实施例中，发光器件200可以不包括激子调节层23、空穴传输层24或空穴注入层25中的一者；或，发光器件200可以不包括电子注入层22。
本公开的一些实施例还提供了一种显示装置300。如图9所示，该显示装置300包括多个如上述一些实施例中提供的发光器件200。
本公开实施例提供的显示装置300所能实现的有益效果与上述一些实施例提供的发光器件200所能实现的有益效果相同，在此不做赘述。
在一些实施例中，上述实施例提供的显示装置300可以为手机、平板电脑、电视机、显示器、笔记本电脑、数码相框或导航仪等任何具有 显示功能的产品或部件。
以上所述，仅为本公开的具体实施方式，但本公开的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本公开揭露的技术范围内，想到变化或替换，都应涵盖在本公开的保护范围之内。因此，本公开的保护范围应以所述权利要求的保护范围为准。

Claims (16)

  1. 一种电子传输层，应用于发光器件，所述发光器件包括发光层，所述电子传输层设置在所述发光层的一侧；
    所述电子传输层包括：
    第一电子传输膜；以及，
    层叠设置在所述第一电子传输膜的靠近所述发光层的一侧的第二电子传输膜，所述第二电子传输膜被配置为与所述发光层接触；其中，
    所述第二电子传输膜所含有的材料的导带能级大于所述第一电子传输膜所含有的材料的导带能级，所述第二电子传输膜所含有的材料的导带能级小于所述发光层所含有的材料的导带能级。
  2. 根据权利要求1所述的电子传输层，其中，所述第二电子传输膜所含有的材料的价带能级小于所述第一电子传输膜所含有的材料的价带能级。
  3. 根据权利要求1所述的电子传输层，其中，所述第二电子传输膜的厚度小于所述第一电子传输膜的厚度。
  4. 根据权利要求1～3中任一项所述的电子传输层，其中，所述第二电子传输膜所含有的材料与所述第一电子传输膜所含有的材料的摩尔比的范围为1:5～1:3。
  5. 根据权利要求1～4中任一项所述的电子传输层，其中，所述第一电子传输膜包括ZnO膜、TiO 2膜或SnO 2膜。
  6. 根据权利要求1～5中任一项所述的电子传输层，其中，所述第二电子传输膜包括ZrO 2膜、La 2O 3膜或LaTi 2O 7膜。
  7. 一种电子传输层的制备方法，用于制备如权利要求书1～5中任一项所述的电子传输层；
    所述制备方法包括：
    将第一电子传输膜和第二电子传输膜层叠在一起；其中，
    所述第一电子传输膜位于所述第二电子传输膜层的靠近所述发光层的一侧；所述第一电子传输膜所含有的材料的导带能级小于所述第二电子传输膜所含有的材料的导带能级，所述第二电子传输膜所含有的材料的导带能级小于发光层所含有的材料的导带能级。
  8. 根据权利要求7所述的制备方法，其中，所述将第一电子传输膜和第二电子传输膜层叠在一起，包括：
    采用成膜工艺在衬底上形成所述第一电子传输膜；
    采用成膜工艺在所述第一电子传输膜远离所述衬底的表面形成所述第二电子传输膜。
  9. 根据权利要求7所述的制备方法，其中，所述将第一电子传输膜和第二电子传输膜层叠在一起，包括：
    采用成膜工艺形成所述第一电子传输膜；
    采用成膜工艺形成所述第二电子传输膜；
    将所述第一电子传输膜和所述第二电子传输膜复合在一起。
  10. 根据权利要求9所述的制备方法，其中，所述第一电子传输膜包括ZnO膜；
    所述采用成膜工艺形成所述第一电子传输膜，包括：
    向醋酸锌的乙醇悬浊液加入二乙醇胺的乙醇溶液，并进行加热处理，获得二乙醇胺配合物溶胶液；
    去除所述二乙醇胺配合物溶胶液含有的乙醇；
    采用成膜工艺将去除乙醇的二乙醇胺配合物溶胶液制成氧化锌预制膜；
    对所述氧化锌预制膜所含有的二乙醇胺配合物进行氧化处理，形成ZnO膜。
  11. 根据权利要求10所述的制备方法，其中，
    所述二乙醇胺的乙醇溶液中所含有的二乙醇胺与所述醋酸锌的乙醇悬浊液中所含有的醋酸锌的摩尔比范围为1:1.5～1:1。
  12. 根据权利要求9～11中任一项所述的制备方法，其中，所述第二电子传输膜包括ZrO 2膜；
    所述采用成膜工艺形成所述第二电子传输膜，包括：
    在加热条件下向八水合氯化氧锆的乙醇悬浊液中滴加氨水，获得锆水解溶胶液；
    去除所述锆水解溶胶液含有的乙醇；
    采用成膜工艺将去除乙醇的锆水解溶胶液制作二氧化锆预制膜；
    对所述二氧化锆预制膜进行氧化处理，形成ZrO 2膜。
  13. 根据权利要求12所述的制备方法，其中，所述采用成膜工艺形成所述第二电子传输膜，还包括：
    在所述向八水合氯化氧锆的乙醇悬浊液中滴加氨水之前，
    将无水乙醇与水混合，获得乙醇水溶液；其中，所述无水乙醇与所述水的体积比范围为1:4～1:2.5；
    将所述乙醇水溶液与八水合氯化氧锆进行混合，获得八水合氯化氧锆的乙醇悬浊液。
  14. 一种发光器件，包括：
    如权利要求1～6中任一项所述的电子传输层，所述电子传输层包括层叠设置的第一电子传输膜和第二电子传输膜；以及，
    设置在所述第二电子传输膜远离所述第一电子传输膜的一侧的发光层；其中，所述发光层所含有的材料的导带能级大于所述第二电子传输膜所含有的材料的导带能级。
  15. 根据权利要求14所述的发光器件，还包括：
    设置在所述电子传输层远离所述发光层的一侧的电子注入层；
    设置在所述发光层远离所述电子传输层的一侧的激子调节层，所述激子调节层被配置为，调节传输至所述发光层内的空穴的传输效率，以使得所述空穴和传输至所述发光层内的电子尽量在所述发光层内发生激子复合；
    设置在所述激子调节层远离所述发光层的一侧的空穴传输层；以及，
    设置在所述空穴传输层远离所述发光层的一侧的空穴注入层。
  16. 一种显示装置，包括：多个如权利要求14或15所述的发光器件。
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