CN114203928A

CN114203928A - Electrode and preparation method thereof, OLED device and electronic equipment

Info

Publication number: CN114203928A
Application number: CN202111472666.3A
Authority: CN
Inventors: 秦禄东; 李志林; 魏斌; 廖英杰; 赵婷婷
Original assignee: Guangdong Oppo Mobile Telecommunications Corp Ltd
Current assignee: Guangdong Oppo Mobile Telecommunications Corp Ltd
Priority date: 2021-12-03
Filing date: 2021-12-03
Publication date: 2022-03-18

Abstract

The application provides an electrode, including transparent conducting layer and block copolymer layer, the surface of transparent conducting layer has a plurality of recesses, the block copolymer layer sets up in the recess, the block copolymer layer is the fold form. The electrode can be used in an OLED device, the refraction, reflection, diffraction and the like of light can be improved by the corrugated block copolymer layer, and the waveguide mode and the plasma mode of the OLED device are improved, so that the light extraction is improved, and the light extraction efficiency is improved. The application also provides a preparation method of the electrode, an OLED device and electronic equipment.

Description

Electrode and preparation method thereof, OLED device and electronic equipment

Technical Field

The application belongs to the technical field of electronic products, and particularly relates to an electrode, a preparation method of the electrode, an OLED device and electronic equipment.

Background

An Organic Light-Emitting Diode (OLED) is an Organic electroluminescent device, and has the advantages of self-luminescence, wide viewing angle, high brightness, and low power consumption, however, the current OLED device has low Light-Emitting efficiency, and only about 20% of Light energy exits to the outside of the OLED device. Therefore, the light extraction efficiency of the OLED device needs to be improved.

Disclosure of Invention

In view of this, the application provides an electrode, a preparation method thereof, an OLED device and an electronic device, so that the light emitting efficiency of the OLED device is improved, and the application of the OLED device is facilitated.

In a first aspect, the present application provides an electrode, including a transparent conductive layer and a block copolymer layer, wherein a surface of the transparent conductive layer has a plurality of grooves, the block copolymer layer is disposed in the grooves, and the block copolymer layer is corrugated.

In a second aspect, the present application provides a method of preparing an electrode, comprising:

forming a plurality of through grooves on the surface of the transparent conductive substrate to obtain a transparent conductive base;

coating a block copolymer solution in the through grooves, and obtaining a block copolymer layer after self-assembly, wherein the block copolymer layer is in a wrinkle shape;

and forming a transparent conductive material film on the surface of the block copolymer layer, wherein the transparent conductive material film is connected with the transparent conductive substrate to obtain the electrode.

In a third aspect, the present application provides a method for preparing an electrode, comprising:

forming a plurality of non-through grooves on the surface of the transparent conductive substrate to obtain a transparent conductive substrate;

and coating a block copolymer solution in the non-through groove, and performing self-assembly to obtain a block copolymer layer, wherein the block copolymer layer is in a wrinkle shape to obtain the electrode.

In a fourth aspect, the present application provides an OLED device comprising a substrate, an anode, an organic light-emitting layer and a cathode, which are stacked, wherein at least one of the anode and the cathode comprises the electrode of the first aspect or the electrode prepared by the preparation method of the second aspect or the electrode prepared by the preparation method of the third aspect.

In a fifth aspect, the present application provides an electronic device comprising a housing and a display device connected to the housing, wherein the display device comprises the OLED device of the fourth aspect.

The application provides an electrode and a preparation method of the electrode, the electrode can be used in an OLED device, the refraction, reflection, diffraction and the like of light can be improved by the corrugated block copolymer layer, and the waveguide mode and the plasma mode of the OLED device are improved at the same time, so that the light extraction is improved, and the light extraction efficiency is improved; the OLED device with the electrode has excellent light-emitting efficiency, and the corrugated block copolymer can effectively increase the carrier injection of the OLED device, broaden the carrier recombination zone and improve the current efficiency of the OLED device, so that the light-emitting efficiency of the OLED device is improved; the electronic equipment with the OLED device has excellent luminous efficiency and can better meet the use requirement.

Drawings

In order to more clearly explain the technical solution in the embodiments of the present application, the drawings that are required to be used in the embodiments of the present application will be described below.

Fig. 1 is a flowchart of a method for manufacturing an electrode according to an embodiment of the present disclosure.

Fig. 2 is a schematic structural diagram of a transparent conductive substrate according to an embodiment of the present disclosure.

Fig. 3 is a schematic diagram of S102 according to an embodiment of the present disclosure.

Fig. 4 is a schematic diagram of S103 according to an embodiment of the present disclosure.

Fig. 5 is a schematic diagram of S103 according to another embodiment of the present application.

Fig. 6 is a schematic diagram of S103 according to yet another embodiment of the present application.

Fig. 7 is a flow chart of a method for manufacturing an electrode according to another embodiment of the present disclosure.

Fig. 8 is a schematic view of a transparent conductive substrate according to an embodiment of the present disclosure.

Fig. 9 is a schematic diagram of S202 according to an embodiment of the present application.

Fig. 10 is a flow chart of a method for manufacturing an electrode according to yet another embodiment of the present disclosure.

Fig. 11 is a schematic diagram of S203 according to an embodiment of the present application.

Fig. 12 is a schematic diagram of S203 according to another embodiment of the present application.

Fig. 13 is a schematic diagram of a process for preparing an electrode according to an embodiment of the present disclosure.

Fig. 14 is a schematic diagram of a process for preparing an electrode according to another embodiment of the present disclosure.

Fig. 15 is a schematic structural diagram of an electrode according to an embodiment of the present application.

Fig. 16 is an enlarged view of the dashed area in fig. 15.

Fig. 17 is a schematic top view of a transparent conductive layer according to an embodiment of the present disclosure.

Fig. 18 is a schematic top view of a transparent conductive layer according to another embodiment of the present disclosure.

Fig. 19 is a schematic top view of a transparent conductive layer according to still another embodiment of the present disclosure.

Fig. 20 is a schematic structural diagram of an electrode according to another embodiment of the present disclosure.

Fig. 21 is an enlarged view of the dashed area of fig. 20 provided in accordance with an embodiment of the present application.

FIG. 22 is an enlarged view of the area of FIG. 20 in phantom provided in accordance with another embodiment of the present application.

Fig. 23 is a schematic structural diagram of an OLED device according to an embodiment of the present application.

Description of reference numerals:

the organic light-emitting diode comprises a transparent conducting layer-11, a groove-111, a block copolymer layer-12, a transparent conducting film-13, an electrode-10, a transparent conducting substrate-20, a transparent conducting substrate-21, a through groove 211, a transparent conducting base plate-21 ', a non-through groove-211', a transparent conducting material film-22, a substrate-30, an anode-40, an organic light-emitting layer-50, a cathode-60 and an OLED device-100.

Detailed Description

The following is a preferred embodiment of the present application, and it should be noted that, for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present application, and these improvements and modifications are also considered as the protection scope of the present application.

The following disclosure provides many different embodiments or examples for implementing different features of the application. In order to simplify the disclosure of the present application, specific example components and arrangements are described below. Of course, they are merely examples and are not intended to limit the present application. Moreover, the present application may repeat reference numerals and/or letters in the various examples, such repetition is for the purpose of simplicity and clarity and does not in itself dictate a relationship between the various embodiments and/or configurations discussed. In addition, examples of various specific processes and materials are provided herein, but one of ordinary skill in the art may recognize applications of other processes and/or use of other materials.

Referring to fig. 1, a flow chart of a method for manufacturing an electrode according to an embodiment of the present disclosure includes:

s101: and forming a plurality of through grooves on the surface of the transparent conductive substrate to obtain the transparent conductive substrate.

S102: and coating a block copolymer solution in the through grooves, and performing self-assembly to obtain a block copolymer layer, wherein the block copolymer layer is in a wrinkle shape.

S103: and forming a transparent conductive material film on the surface of the block copolymer layer, and connecting the transparent conductive material film with the transparent conductive substrate to obtain the electrode.

In the related art, the efficiency of the OLED device is divided into internal quantum efficiency and external quantum efficiency. The internal quantum efficiency is the number of photons generated by injecting one hole-electron pair per average in the OLED device, and currently, nearly 100% internal quantum efficiency can be achieved. The external quantum efficiency is the ratio of the total number of photons emitted by the OLED device to the number of injected electrons, and due to the difference of refractive indexes of layers and total reflection of interfaces among the layers, loss can be generated when photons are radiated outside the device, such as metal surface plasma loss, waveguide mode loss and the like, most of light emitted by the organic light emitting layer is limited inside the OLED device or is emitted from the side surface, so that the light emitting efficiency is low, namely the ratio of the number of photons emitted from the front surface to the total number of photons generated in the device is low; therefore, the lower light extraction efficiency brought by the device structure results in low external quantum efficiency of the device. The electrode provided by the application can be used in photoelectric devices, such as OLED devices, and the transmission direction and path of light can be changed by arranging the corrugated block copolymer layer in the electrode, so that the refraction, reflection, diffraction and the like of light are improved, such as total reflection loss reduction, interference effect formation and the like, the light extraction in a waveguide mode and a plasma mode is facilitated, and the light extraction efficiency is improved; the electrode is beneficial to improving the external quantum efficiency of the OLED device and is more beneficial to the use of the OLED device.

In S101, a plurality of through grooves are formed on the surface of the transparent conductive substrate to obtain a transparent conductive base, which is beneficial to the arrangement of the subsequent block copolymer layer. It is understood that the surface of the transparent conductive substrate has a plurality of through slots.

In the application, the transparent conductive substrate is transparent, so that the radiation of light is ensured, and the influence of the transmittance of the transparent conductive substrate on the light emitting efficiency is avoided; the transparent conductive substrate has conductive performance, thereby ensuring the use of the electrode. In the embodiment of the present application, the material of the transparent conductive substrate includes at least one of a simple metal, an alloy, and a non-metal conductive material. In an embodiment of the present application, a material of the transparent conductive substrate includes at least one of Indium Tin Oxide (ITO), indium zinc oxide, silver nanowires, and graphene. The transparent conductive substrate with high transmittance can be prepared by adopting the material. It can be understood that the material of the transparent conductive substrate can also be selected from other materials that can meet the use requirement of the transparent conductive substrate.

In the embodiment of the present application, the through groove may be formed by at least one of a physical etching method and a chemical etching method. In one embodiment of the application, photoresist is coated on the surface of a transparent conductive substrate to form a photoresist layer, and the photoresist layer covers the surface of the through groove which is not required to be formed; and coating chemical etching liquid on the surface of the transparent conductive substrate, and forming a plurality of through grooves on the surface of the transparent conductive substrate after etching to obtain the transparent conductive base. The distribution, etching time and temperature of the through grooves can be set as required, and chemical etching liquid capable of chemically reacting with the transparent conductive substrate is selected. Specifically, the through grooves may be the same in size or different in size; the etching temperature may be at normal temperature, such as 15-30 ℃. In one embodiment, the through grooves are formed by etching with aqua regia. In one embodiment, through grooves are formed on the surface of the ITO layer by aqua regia. In another embodiment of the present application, the through groove may be formed by laser etching.

Referring to fig. 2, a schematic view of a transparent conductive substrate according to an embodiment of the present disclosure is shown, wherein a surface of the transparent conductive substrate 21 has a plurality of through grooves 211. In this application embodiment, the interval between the adjacent logical groove 211 is 10nm-100nm, so, guarantee that the interval between the logical groove 211 differs not greatly, and then when block copolymer layer improved light transmission route and direction, make the change of electrode surface light transmission route and direction more even unanimous, guarantee to improve the homogeneity of light-emitting everywhere when promoting luminous efficiency, and be favorable to forming interference light, improve luminous efficiency. In the embodiment of the present application, the through grooves 211 are periodically arranged, so that the uniformity of the light emission can be further improved. Specifically, be periodic variation through setting up the interval between leading to groove 211, further promote the light-emitting homogeneity, be favorable to forming simultaneously and interfere light, improve light-emitting efficiency. In an embodiment of the present application, the distances between the adjacent through grooves 211 are equal, so that the light emitting efficiency and the light emitting uniformity can be greatly improved.

In S102, the block copolymer solution is applied to the through-grooves 211, thereby forming a wrinkled block copolymer layer after self-assembly. It can be understood that self-assembly is a phenomenon of molecular aggregates or supramolecular structures which are clear and stable in structure and have certain specific functions or performances and are formed by spontaneous combination of blocks with different properties in the block copolymer through non-covalent interaction; the self-assembly of the block copolymer prevents complete separation between blocks with different properties, and simultaneously realizes microscopic phase separation, thereby obtaining a wrinkled appearance. By coating the block copolymer solution, a stable and regularly arranged wrinkle structure is formed after self-assembly, and the wrinkle structure is densely arranged in the through groove 211. In the present application, the orthographic projection of the block copolymer layer in the depth direction of the through-groove 211 completely covers the opening of the through-groove 211. Referring to fig. 3, which is a schematic view of S102 according to an embodiment of the present disclosure, the block copolymer layer 12 is formed in the through groove 211 on the transparent conductive substrate 21 shown in fig. 2, and the block copolymer layer 12 is corrugated.

In an embodiment of the present application, the block copolymer solution includes a block copolymer and a solvent. Wherein the block copolymer is selected from substances capable of self-assembling to form a wrinkled morphology, and the solvent is selected from substances capable of dissolving and dispersing the block copolymer. Specifically, the solvent comprises at least one of halogenated hydrocarbons, ethers, amides and sulfoxides, such as dichloromethane, dimethylformamide, dimethyl sulfoxide and the like, and the block copolymer is dissolved and dispersed by adopting an organic solvent, so that the volatilization of the solvent during self-assembly is facilitated, and the self-assembly efficiency is improved. In the present application, the concentration of the block copolymer solution may be selected as desired. In embodiments of the present application, the block copolymer solution is applied by a suspension coating process. The suspension coating process is more beneficial to the self-assembly of the block copolymer and the formation of a more regular fold structure. In the present application, self-assembly may be performed at normal temperature, such as 15 ℃ to 30 ℃. In the present application, the block copolymer layer 12 is formed to be connected to the transparent conductive substrate 21.

In S103, by molding a transparent conductive material film on the surface of the block copolymer layer 12, the electrode is ensured to be conductive everywhere in the thickness direction. In the present application, the material of the transparent conductive material film may be selected from the material of the transparent conductive substrate, and of course, the material of the transparent conductive material film and the material of the transparent conductive substrate may be the same or different. In the present embodiment, a transparent conductive material film may be formed on the surface of the block copolymer layer 12 by deposition or coating. Specifically, the transparent conductive material film may be formed by, but not limited to, sputtering.

Referring to fig. 4, a schematic view of S103 according to an embodiment of the present disclosure is provided, in which a transparent conductive material film 22 is formed on the surface of the block copolymer layer 12 shown in fig. 3. In the present embodiment, the surface of the transparent conductive material film 22 on the side away from the block copolymer layer 12 is a flat surface, which is beneficial for the arrangement of the subsequent flat layer structure of the electrode during application. Of course, the surface of the transparent conductive material film 22 on the side away from the block copolymer layer 12 may also be a non-flat surface such as a wrinkle or the like having the same shape as the block copolymer layer 12.

In one embodiment of the present application, the transparent conductive material film 22 covers only the block copolymer layer 12. Referring to fig. 4, the transparent conductive material film 22 covers only the block copolymer layer 12. Further, the direction from the block copolymer layer 12 to the transparent conductive material film 22 is a first direction, the transparent conductive substrate 21 has a first surface and a second surface which are oppositely arranged, the direction from the first surface to the second surface is the first direction, and a side surface of the transparent conductive material film 22 away from the block copolymer layer 12 is flush with the second surface of the transparent conductive substrate 21, which is beneficial to the arrangement of a subsequent leveling layer structure of the electrode during application. In another embodiment of the present application, the transparent conductive material film 22 covers not only the block copolymer layer 12 but also the transparent conductive substrate 21. Referring to fig. 5, which is a schematic view of S103 according to another embodiment of the present disclosure, a transparent conductive material film 22 covers the block copolymer layer 12 and the transparent conductive substrate 21. In an embodiment, the orthographic projection of the transparent conductive material film 22 on the block copolymer layer 12 completely covers the block copolymer layer 12. In another embodiment, the orthographic projection of the transparent conductive material film 22 on the block copolymer layer 12 completely covers the block copolymer layer 12, and the orthographic projection of the transparent conductive material film 22 on the transparent conductive substrate 21 completely covers the transparent conductive substrate 21.

In the present application, the block copolymer layer 12 has two surfaces disposed oppositely in the direction in which the through-groove 211 extends, and the transparent conductive material film 22 is molded at least on one side surface of the block copolymer layer 12. Referring to fig. 4, a transparent conductive material film 22 is formed on one side surface of the block copolymer layer 12; referring to fig. 6, a schematic diagram of S103 according to yet another embodiment of the present disclosure is provided, wherein a transparent conductive material film 22 is formed on two opposite surfaces of the block copolymer layer 12, so as to further ensure the electrical conductivity everywhere in the extending direction of the through-trench 211, and the electrical properties are similar, which is beneficial for the use of electrodes.

In the present embodiment, etching the block copolymer layer 12 is further included before forming the transparent conductive material film 22. By etching the block copolymer layer 12, the wrinkle appearance of the block copolymer layer 12 is further improved, and the wrinkle degree and the surface area of the wrinkle structure are increased, so that the consistency of the wrinkle structure and the distribution uniformity are improved, and meanwhile, the surface area of the block copolymer layer 12 is increased, and the light extraction efficiency is further improved. In the embodiment of the present application, the block copolymer layer 12 may be etched by at least one of a physical etching method and a chemical etching method, so that the wrinkle morphology of the block copolymer layer 12 is more apparent. In an embodiment of the present application, the block copolymer layer 12 is etched by a chemical etching liquid. Specifically, the chemical etching solution is selected according to the properties of the block copolymer. In another embodiment of the present application, the block copolymer layer 12 is etched by a laser.

Referring to fig. 7, a flow chart of a method for manufacturing an electrode according to another embodiment of the present application includes:

s201: and forming a plurality of non-through grooves on the surface of the transparent conductive substrate to obtain the transparent conductive substrate.

S202: and coating the block copolymer solution in the non-through groove, and performing self-assembly to obtain a block copolymer layer, wherein the block copolymer layer is in a wrinkle shape, so as to obtain the electrode.

The difference between S201 and S101 is that in S201, a non-through groove is formed on the surface of the transparent conductive substrate, so that the obtained transparent conductive substrate is ensured to be conductive at each position in the extending direction of the non-through groove, and the usability of the electrode is ensured.

In the present application, the material of the transparent conductive substrate is selected as described in S101, and the block copolymer layer 12 is formed as described in S102; the method for forming the non-through grooves, the distance between adjacent non-through grooves, and the arrangement manner of the non-through grooves refer to the corresponding description of the through groove 211, and it can be understood that the forming method, the distance arrangement, and the arrangement manner of the non-through grooves and the through groove 211 may be the same or different, and are not described herein again. In the present application, the surface of the transparent conductive substrate may be formed with only the non-through groove, may be formed with only the through groove 211, and may be formed with both the non-through groove and the through groove 211. In this application, at least one of the through groove 211 and the non-through groove may be referred to as a groove structure, that is, the groove structure is formed on the surface of the transparent conductive substrate, so as to obtain the transparent conductive base 21 or the transparent conductive substrate. Fig. 8 is a schematic view of a transparent conductive substrate according to an embodiment of the present disclosure, in which a surface of a transparent conductive substrate 21 'has a plurality of non-through grooves 211'. Referring to fig. 9, which is a schematic view of S202 according to an embodiment of the present disclosure, the block copolymer layer 12 is formed in the non-through groove 211 'on the surface of the transparent conductive substrate 21' shown in fig. 8.

In the embodiment of the application, the preparation method of the electrode further includes etching the block copolymer layer 12, further improving the wrinkle morphology of the block copolymer layer 12, and increasing the wrinkle degree and the surface area of the wrinkle structure, so that the consistency and the distribution uniformity of the wrinkle structure are improved, and meanwhile, the surface area of the block copolymer layer 12 is increased, which is beneficial to further improving the light extraction efficiency. The etching method for the block copolymer layer 12 is as described above and will not be described in detail here.

Referring to fig. 10, a flow chart of a method for manufacturing an electrode according to another embodiment of the present application includes:

s201': and forming a plurality of non-through grooves on the surface of the transparent conductive substrate to obtain the transparent conductive substrate.

S202': and coating the block copolymer solution in the non-through groove, and performing self-assembly to obtain a block copolymer layer, wherein the block copolymer layer is in a wrinkle shape.

S203: and forming a transparent conductive material film on the surface of the block copolymer layer, and connecting the transparent conductive material film with the transparent conductive substrate to obtain the electrode.

For S201 'and S202', reference may be made to the discussion of S201 and S202, which is not described herein again.

In S203, by providing the transparent conductive material film 22, the thickness of the conductive layer in the extending direction of the non-through groove 211' is increased, thereby ensuring that the working performance is similar everywhere on the electrode.

Referring to fig. 11, a schematic view of S203 according to an embodiment of the present disclosure is shown, in which a transparent conductive material film 22 is formed on the surface of the block copolymer layer 12 shown in fig. 9. For the arrangement of the transparent conductive material film 22, please refer to the above description, which is not repeated herein. In one embodiment of the present application, the transparent conductive material film 22 covers only the block copolymer layer 12. Referring to fig. 11, the transparent conductive material film 22 covers only the block copolymer layer 12. Further, the surface of the side of the transparent conductive material film 22 away from the block copolymer layer 12 is flush with the surface of the transparent conductive substrate 21 'having the non-through groove 211', which is beneficial to the arrangement of the subsequent planarization layer structure of the electrode during application. In another embodiment of the present application, the transparent conductive material film 22 covers not only the block copolymer layer 12 but also the transparent conductive substrate 21'. Referring to fig. 12, which is a schematic view of S203 according to another embodiment of the present disclosure, a transparent conductive material film 22 covers the block copolymer layer 12 and the transparent conductive substrate 21'. In an embodiment, the orthographic projection of the transparent conductive material film 22 on the block copolymer layer 12 completely covers the block copolymer layer 12. In another embodiment, the orthographic projection of the transparent conductive material film 22 on the block copolymer layer 12 completely covers the block copolymer layer 12, and the orthographic projection of the transparent conductive material film 22 on the transparent conductive substrate 21 'completely covers the transparent conductive substrate 21'.

In an embodiment of the present application, the method of preparing an electrode further comprises providing a transparent conductive substrate. In an embodiment of the present application, providing the transparent conductive substrate includes molding the transparent conductive substrate on a base plate, which may be, but not limited to, molding the transparent conductive substrate by deposition, coating, or the like, where the base plate plays a role of bearing and supporting the transparent conductive substrate. In one embodiment, the transparent conductive substrate is formed on the substrate and then peeled off. In another embodiment, the surface of the transparent conductive substrate on the substrate is directly processed to form a plurality of groove structures without stripping, so that the process flow is simplified and the operation is more convenient.

In an embodiment of the present application, the method for preparing an electrode further includes cleaning the transparent conductive substrate. In one embodiment, the transparent conductive substrate is sequentially placed in water, acetone and isopropanol solution for cleaning, and then cleaned in an ultraviolet ozone environment after being dried; specifically, the ultraviolet ozone cleaning may be, but not limited to, 10min, 12min, 15min, 20min, or the like.

Referring to fig. 13, a schematic diagram of a process for manufacturing an electrode according to an embodiment of the present disclosure includes: providing a transparent conductive substrate 20 → forming a plurality of through grooves 211 on the surface of the transparent conductive substrate 20 to obtain a transparent conductive base 21 → coating a block copolymer solution in the through grooves 211, and obtaining a block copolymer layer 12 after self-assembly, wherein the block copolymer layer 12 is in a corrugated shape → forming a transparent conductive material film 22 on the surface of the block copolymer layer 12, and the transparent conductive material film 22 is connected with the transparent conductive base 21 to obtain the electrode. Wherein, in the extending direction of the through-groove 211, the block copolymer layer 12 has two surfaces oppositely arranged, and the transparent conductive material film 22 is molded at least on one side surface of the block copolymer layer 12. Further, the block copolymer layer 12 may be etched to increase the surface area of the block copolymer layer 12.

Referring to fig. 14, a schematic diagram of a process for preparing an electrode according to another embodiment of the present application is shown, including: providing a transparent conductive substrate 20 → forming a plurality of non-through grooves 211 ' on the surface of the transparent conductive substrate 20 to obtain a transparent conductive substrate 21 ' → coating the block copolymer solution in the non-through grooves 211 ', and self-assembling to obtain a block copolymer layer 12, wherein the block copolymer layer 12 is wrinkled to obtain an electrode. Further, a transparent conductive material film 22 may be formed on the surface of the block copolymer layer 12, and the transparent conductive material film 22 may be connected to the transparent conductive substrate 21'. Further, the block copolymer layer 12 may be etched to increase the surface area of the block copolymer layer 12.

The preparation method of the electrode is simple, the operation is convenient, the electrode capable of improving the light emitting efficiency of the device can be prepared, and the large-scale use of the electrode is facilitated.

Referring to fig. 15, which is a schematic structural diagram of an electrode according to an embodiment of the present disclosure, an electrode 10 includes a transparent conductive layer 11 and a block copolymer layer 12, a surface of the transparent conductive layer 11 has a plurality of grooves 111, and the block copolymer layer 12 is disposed in the grooves 111; referring to fig. 16, an enlarged view of the dotted area of fig. 15 is shown, wherein the block copolymer layer 12 is corrugated.

In the present application, the transparent conductive layer 11 is transparent, so as to ensure the radiation of light and avoid the influence of the transmittance of the transparent conductive layer on the light extraction efficiency; the transparent conductive layer 11 has conductivity to ensure the use of the electrode 10.

In the present application, when the electrode 10 is applied to an OLED device, the requirement for the transparency of the electrode 10 is different according to the light emitting manner of the OLED device and the position of the electrode 10. In an embodiment of the present application, when the electrode 10 is used as an anode of a bottom-emitting OLED device, the transparent conductive layer 11 has high light transmittance, and in particular, the visible light transmittance of the transparent conductive layer 11 may be, but is not limited to, above 90%. In another embodiment of the present application, when the electrode 10 is used as a cathode of a top-emitting OLED device, the transparent conductive layer 11 has a semi-light-transmitting property, and particularly, the visible light transmittance of the transparent conductive layer 11 may be, but is not limited to, above 50%. It is understood that the transmittance of the transparent conductive layer 11 can be selected according to the need, and is not limited thereto.

In the embodiment of the present application, the material of the transparent conductive layer 11 includes at least one of a simple metal, an alloy, and a non-metal conductive material. In an embodiment of the present disclosure, the material of the transparent conductive layer 11 includes at least one of Indium Tin Oxide (ITO), indium zinc oxide, silver nanowires, and graphene. The transparent conductive layer 11 having a high transmittance can be obtained by using the above materials. It is understood that the material of the transparent conductive layer 11 can also be selected from other materials that can meet the use requirement of the transparent conductive layer 11. In the present application, when the transparent conductive layer 11 is composed of a plurality of materials, the plurality of materials may be mixed to form the transparent conductive layer 11, or each material may be separately formed into a film and then stacked together to form the transparent conductive layer 11. In one embodiment, the transparent conductive layer 11 is an ito layer. In another embodiment, the transparent conductive layer 11 is formed by mixing indium tin oxide and indium zinc oxide. In yet another embodiment, the transparent conductive layer 11 comprises a layer of indium tin oxide and a layer of silver nanowires arranged in a stack.

In the present application, the thickness of the transparent conductive layer 11 can be selected according to application requirements, and the thickness of the transparent conductive layer 11 is greater than the depth of the groove 111. In an embodiment of the present application, the thickness of the transparent conductive layer 11 is greater than or equal to 100nm, which is beneficial to reducing the thickness of the electrode 10 and increasing the application range of the electrode 10. Further, the thickness of the transparent conductive layer 11 is 100nm to 5 μm. Further, the thickness of the transparent conductive layer 11 is 100nm to 200nm, 100nm to 500nm, 500nm to 1 μm, 500nm to 2 μm, or 3 μm to 5 μm. In the embodiment of the application, the sheet resistance of the transparent conductive layer 11 is 5 Ω/□ -15 Ω/□, which is beneficial to improving the conductivity of the electrode 10; specifically, the sheet resistance of the transparent conductive layer 11 may be, but is not limited to, 5 Ω/□, 8 Ω/□, 10 Ω/□, 13 Ω/□, or 15 Ω/□.

In the present application, the whole block copolymer layer 12 is corrugated, so as to change refraction, reflection, diffraction, etc. of light, thereby facilitating the extraction of light inside the device and improving the light extraction efficiency. It can be understood that the surface of the block copolymer layer 12 has a corrugated structure, so that total reflection of light can be reduced, loss of the waveguide mode to light can be reduced, and light extraction capability can be improved. In the present application, the corrugated structure may include, but is not limited to, a sphere, a spheroid, a cylinder-like body, and the like.

In the present embodiment, the thickness of the block copolymer layer 12 is 10nm to 100 nm. Thus, the improvement of the light extraction efficiency of the wrinkled block copolymer layer 12 can be ensured, and the thickness of the electrode 10 is not excessively increased, which is more beneficial to the use of the electrode 10. In one embodiment of the present application, the thickness of the block copolymer layer 12 is 15nm to 30nm, 15nm to 90nm, 20nm to 50nm, 20nm to 80nm, 35nm to 60nm, 35nm to 76nm, 50nm to 80nm, 65nm to 90nm, 70nm to 100nm, or the like. Specifically, the thickness of the block copolymer layer 12 may be, but is not limited to, 10nm, 20nm, 30nm, 40nm, 55nm, 65nm, 70nm, 85nm, 95nm, or the like.

In the present application, the block copolymer is coated and self-assembled to obtain the corrugated block copolymer layer 12, that is, the material of the block copolymer layer 12 includes a block copolymer, which is also called a mosaic copolymer, and is a special polymer prepared by connecting two or more polymer segments with different properties. The block copolymers may include random multi-block copolymers, diblock copolymers, triblock copolymers, graft copolymers, star copolymers, and the like. In an embodiment of the present application, the block copolymer includes at least two polymer blocks, the polymer blocks including at least one of a Polystyrene (PS) block, a Polymethylmethacrylate (PMMA) block, a Polydimethylsilane (PDMS) block, a polyvinylpyrrolidone (PVP) block, a polyethylene oxide (PEO) block, and a Polybutadiene (PB) block. It is understood that the block copolymer comprises at least two polymer blocks, i.e. the material of the block copolymer layer 12 comprises at least two polymer blocks, the polymer blocks in the block copolymer having different properties. In a specific embodiment, the block copolymer comprises at least one of PS-b-PMMA, PS-b-PEO, PEO-b-PS-b-PEO, PMMA-b-PDMS-b-PMMA, PS-b-PDMS-b-PS, and PVP-b-PDMS-b-PVP. It is understood that other materials capable of self-assembling to form a wrinkled morphology can be selected for the block copolymer, and the specific material and molecular weight of the block copolymer are not limited in the present application.

In the present application, the block copolymer layer 12 is disposed in the grooves 111 of the transparent conductive layer 11, and since the surface of the transparent conductive layer 11 has a plurality of grooves 111, the block copolymer layer 12 is divisionally disposed in the grooves 111. In the present embodiment, the block copolymer layer 12 includes a plurality of block copolymer sublayers, and one block copolymer sublayer is disposed in one groove 111. It is understood that the surface of the transparent conductive layer 11 has a plurality of grooves 111, each groove 111 has a block copolymer sub-layer disposed therein, or some grooves 111 have a block copolymer sub-layer disposed therein. In the embodiment of the present application, at least more than 80% of the grooves 111 are provided with the block copolymer sublayers, thereby ensuring effective improvement of the light extraction efficiency. It is understood that a direction perpendicular to the depth direction of the groove 111 is defined as a first direction. In the embodiment of the present application, in the first direction, the groove 111 is completely filled with the block copolymer sublayer, which is beneficial to further improving the light extraction efficiency of the device.

In this application embodiment, the surface of transparent conducting layer 11 is provided with a plurality of recesses 111, and the interval between adjacent recess 111 is 10nm-100nm, so, guarantee that the interval between recess 111 is not big, and then when block copolymer layer 12 improves light transmission path and direction, make the change of the light transmission path and the direction of electrode 10 surface more even unanimous, guarantee to improve the homogeneity of light-emitting everywhere when promoting light-emitting efficiency, and be favorable to forming interference light, improve light-emitting efficiency. It will be appreciated that the grooves 111 are non-through grooves. In the embodiment of the present application, the distance between adjacent grooves 111 is 10nm to 30nm, 10nm to 50nm, 20nm to 45nm, 20nm to 55nm, 30nm to 50nm, 30nm to 65nm, 45nm to 60nm, 45nm to 70nm, 50nm to 75nm, 50nm to 80nm, 65nm to 80nm, 70nm to 90nm, or 85nm to 100 nm. Specifically, the spacing between adjacent grooves 111 may be, but is not limited to, 10nm, 20nm, 25nm, 40nm, 55nm, 60nm, 70nm, 75nm, 80nm, 95nm, or the like. In the embodiment of the present application, the grooves 111 are periodically arranged, so that the uniformity of the emitted light can be further improved. Specifically, be periodic variation through setting up the interval between the recess 111, further promote the light-emitting homogeneity, be favorable to forming simultaneously and interfere light, improve light-emitting efficiency. In an embodiment of the present application, the distances between the adjacent grooves 111 are equal, so that the light emitting efficiency and the light emitting uniformity can be greatly improved.

In the present embodiment, the depth of the groove 111 is 100nm to 200 nm. In this way, the block copolymer layer 12 can be advantageously provided without excessively affecting the performance of the transparent conductive layer 11. Further, the depth of the groove 111 is 100nm-130nm, 100nm-150nm, 120nm-160nm, 125nm-155nm, 130nm-165nm, 150nm-170nm, 155nm-175nm or 170nm-200 nm. Specifically, the depth of the groove 111 may be, but is not limited to, 100nm, 120nm, 135nm, 150nm, 160nm, 175nm, 180nm, 195nm, or the like. In the embodiment of the present application, the opening of the groove 111 has a micro-nano level in a transverse dimension. Therefore, the grooves 111 are favorably arranged on the surface of the transparent conductive layer 11, and the uniformity of light emission is improved. It will be appreciated that the lateral dimension of the opening of the recess 111 is the dimension of the opening of the recess 111 in the first direction. In one embodiment of the present application, the lateral dimension of the opening of the groove 111 is less than 10 μm. Therefore, the preparation process difficulty is reduced while the light-emitting uniformity and the light-emitting efficiency of the device are improved. Further, the lateral dimension of the opening of the groove 111 is less than 5 μm. Further, the lateral dimension of the opening of the groove 111 is less than 1 μm. Therefore, the uniformity and the light emitting efficiency of the device can be improved.

In the present application, the shape of the opening of the groove 111 may be selected as desired. In the present embodiment, the opening of the groove 111 has at least one of a polygonal shape, a circular shape, and a ring shape. Fig. 17 is a schematic top view of a transparent conductive layer according to an embodiment of the present application, in which an opening of the groove 111 is polygonal. Specifically, the polygon includes a triangle, a quadrangle, a pentagon, and the like. Fig. 18 is a schematic top view of a transparent conductive layer according to another embodiment of the present application, in which an opening of the groove 111 is circular. Fig. 19 is a schematic top view of a transparent conductive layer according to yet another embodiment of the present application, in which an opening of the groove 111 is annular. In an embodiment of the present application, the opening of the groove 111 is polygonal or circular, so that it is easier to match the electrodes 10 with different surface shapes, thereby improving the light emitting efficiency and uniformity. In the embodiments of the present application, the concave groove is a cylindrical groove, an annular groove, a polygonal groove, or the like.

Referring to fig. 20, which is a schematic structural diagram of an electrode according to another embodiment of the present disclosure, an electrode 10 includes a transparent conductive layer 11, a block copolymer layer 12, and a transparent conductive film 13, a plurality of grooves 111 are formed on a surface of the transparent conductive layer 11, the block copolymer layer 12 is disposed in the grooves 111, and the transparent conductive film 13 is disposed on a surface of the block copolymer layer 12 and connected to the transparent conductive layer 11. By arranging the transparent conductive film 13, the thickness of the conductive layer in the groove 111 area is increased, thereby ensuring that the working performance of each part of the electrode 10 is similar. In the present application, the transparent conductive film 13 is transparent and has a conductive capability, and the light transmittance of the transparent conductive film 13 can be selected according to the light emitting mode of the device and the position of the electrode 10, which can be specifically referred to the selection of the material of the transparent conductive layer 11, and is not described herein again; the transparent conductive layer 11 and the transparent conductive layer 13 may be made of the same material or different materials. In one embodiment, the transparent conductive layer 11 and the transparent conductive film 13 are made of ito. In another embodiment, the transparent conductive layer 11 is made of ito, and the transparent conductive film 13 is made of ag nanowires. In the present embodiment, the transparent conductive film 13 completely covers the block copolymer layer 12, thereby ensuring the working performance of the electrode 10. Fig. 21 is an enlarged view of the dotted area in fig. 20 according to an embodiment of the present disclosure, wherein a surface of the transparent conductive film 13 away from the block copolymer layer 12 is corrugated. That is, both opposite surfaces of the transparent conductive film 13 are provided to match the surface of the block copolymer layer 12, and both are wrinkled. Referring to fig. 22, an enlarged view of the dotted area in fig. 20 is provided according to another embodiment of the present application, wherein the transparent conductive film 13 is away from the surface flatness of the block copolymer layer 12. That is, the surface of the transparent conductive film 13 away from the block copolymer layer 12 does not have a wrinkled structure at this time, so that the electrode 10 facilitates the subsequent arrangement of a relatively flat layer structure when used in a device. In the present embodiment, the surface of the transparent conductive film 13 away from the block copolymer layer 12 is horizontal, and the surface of the transparent conductive film 13 away from the block copolymer layer 12 and one surface of the transparent conductive layer 11 are on the same horizontal plane. That is, the transparent conductive layer 11 has a first surface and a second surface which are oppositely arranged, the first surface has a groove 111, and the surface of the transparent conductive film 13 far away from the block copolymer layer 12 is on the same horizontal plane with the first surface; therefore, the groove 111 on the transparent conductive layer 11 is filled with the transparent conductive film 13, so that the existence of the groove 111 cannot be seen on the surface of the electrode 10, the smoothness of the surface of the electrode 10 is ensured, and further, when the electrode 10 is used in a device, the setting of a subsequent flat layer structure is more facilitated, and the influence of the uneven surface on the setting of the subsequent layer structure and the performance of the device can be effectively avoided. In the embodiment of the present application, the sum of the thicknesses of the transparent conductive layer 11 and the transparent conductive film 13 is greater than or equal to 200nm in the depth direction of the groove 111, so that the conductivity of the electrode 10 can be more favorably improved. In the present application, the surface of the transparent conductive layer 11 has a plurality of grooves 111, and the block copolymer layer 12 includes a plurality of block copolymer sublayers, one block copolymer sublayer being disposed in each groove 111; it is understood that the transparent conductive film 13 includes a plurality of transparent conductive films, and each of the block copolymer sub-layers is provided with a transparent conductive film on the surface.

In the present embodiment, when the electrode 10 is prepared by the method shown in fig. 1, when the transparent conductive material film 22 covers a surface of the block copolymer layer 12, the transparent conductive substrate 21 and the transparent conductive material film 22 together form the transparent conductive layer 11 in the electrode 10; when the transparent conductive material film 22 is covered on the opposite surfaces of the block copolymer layer 12, the transparent conductive substrate 21 and a part of the transparent conductive material film 22 together form the transparent conductive layer 11 in the electrode 10, and a part of the transparent conductive material film 22 forms the transparent conductive film 13 in the electrode 10. Referring to fig. 4, the transparent conductive substrate 21 and the transparent conductive material film 22 together form the transparent conductive layer 11 of the electrode 10; referring to fig. 6, wherein the transparent conductive substrate 21 and the partial transparent conductive material film 22 jointly form the transparent conductive layer 11 in the electrode 10, and the partial transparent conductive material film 22 forms the transparent conductive film 13 in the electrode 10, for example, as shown in the orientation of fig. 6, the transparent conductive material film 22 under the block copolymer layer 12 and the transparent conductive substrate 21 jointly form the transparent conductive layer 11 in the electrode 10, and the transparent conductive material film 22 over the block copolymer layer 12 forms the transparent conductive film 13.

In the present embodiment, when the electrode 10 is prepared by the method shown in fig. 10, when the transparent conductive material film 22 covers only the surface of the block copolymer layer 12, the transparent conductive substrate 21' becomes the transparent conductive layer 11 in the electrode 10, and the transparent conductive material film 22 becomes the transparent conductive film 13 in the electrode 10; when the transparent conductive material film 22 covers not only the surface of the block copolymer layer 12 but also the transparent conductive substrate 21 ', the transparent conductive material film 22 covering the surface of the transparent conductive substrate 21 ' forms the transparent conductive layer 11 in the electrode 10 together with the transparent conductive substrate 21 ', and the transparent conductive material film 22 covering the surface of the block copolymer layer 12 becomes the transparent conductive film 13 in the electrode 10. Referring to fig. 11, a transparent conductive substrate 21' forms a transparent conductive layer 11 of an electrode 10, and a transparent conductive material film 22 forms a transparent conductive film 13 of the electrode 10; referring to fig. 12, in which the transparent conductive layer 11 in the electrode 10 is formed on the portion of the transparent conductive material film 22 covering the transparent conductive substrate 21 'and the transparent conductive substrate 21', the portion of the transparent conductive material film 22 covering the surface of the block copolymer layer 12 becomes the transparent conductive film 13 in the electrode 10.

The electrode 10 provided herein can be used in optoelectronic devices, particularly organic optoelectronic devices, such as OLED devices. The present application provides an OLED device comprising an electrode 10 according to any of the embodiments described above. The OLED device with the electrode 10 has excellent light extraction efficiency, and is beneficial to the application of the OLED device in a display device. Referring to fig. 23, which is a schematic structural diagram of an OLED device according to an embodiment of the present disclosure, an OLED device 100 includes a substrate 30, an anode 40, an organic light emitting layer 50, and a cathode 60, which are stacked, and at least one of the anode 40 and the cathode 60 includes the electrode 10. That is, the electrode 10 provided in the present application may serve as the anode 40 or the cathode 60. In the present application, the substrate 30 may have, but is not limited to, light transmitting properties such as a glass substrate, a plastic substrate, etc.; the organic light emitting layer 50 may further include a hole transport layer, an organic material layer, and an electron transport layer, which are stacked, the hole transport layer being disposed between the anode 40 and the organic light emitting material layer, and the electron transport layer being disposed between the organic material layer and the cathode 60. The light emitting process of the OLED device 100 includes carrier injection, carrier transmission, carrier recombination, exciton migration and exciton radiation de-excitation to emit photons, the electrode 10 provided by the application can improve the light emitting efficiency of the OLED device 100, and can effectively increase the carrier injection of the OLED device 100, widen a carrier recombination region, improve the current efficiency of the OLED device 100, and improve the light emitting efficiency of the OLED device 100.

In an embodiment of the present application, the anode 40 in the OLED device 100 is the electrode 10, ITO is used as the anode 40 in a comparative example, and the rest structures are the same, and a comparison of the light extraction efficiencies of the anode 40 and the ITO shows that the light extraction efficiency of the OLED device 100 having the electrode 10 of the present application is improved by more than 5%. Further, the light extraction efficiency of the OLED device 100 with the electrode 10 is improved by 5% -10%, and the application of the OLED device 100 is facilitated.

The application also provides a display device, which comprises the OLED device 100, thereby being beneficial to improving the service performance of the display device. The present application also provides an electronic device comprising an OLED device 100 of any of the embodiments described above. It is understood that the electronic device may be, but is not limited to, a cell phone, a tablet, a laptop, a watch, MP3, MP4, GPS navigator, digital camera, etc. In an embodiment of the present application, an electronic device includes a housing and a display device connected to the housing, the display device including the OLED device 100 described above. The electronic equipment has excellent display performance and can meet the use requirement.

The foregoing detailed description has provided for the embodiments of the present application, and the principles and embodiments of the present application have been presented herein for purposes of illustration and description only and to facilitate understanding of the methods and their core concepts; meanwhile, for a person skilled in the art, according to the idea of the present application, there may be variations in the specific embodiments and the application scope, and in summary, the content of the present specification should not be construed as a limitation to the present application.

Claims

1. The electrode is characterized by comprising a transparent conductive layer and a block copolymer layer, wherein the surface of the transparent conductive layer is provided with a plurality of grooves, the block copolymer layer is arranged in the grooves, and the block copolymer layer is in a corrugated shape.

2. The electrode of claim 1, wherein the spacing between adjacent grooves is between 10nm and 100 nm.

3. The electrode of claim 1, wherein the grooves are in a periodic arrangement.

4. The electrode of claim 3, wherein the spacing between adjacent grooves is equal.

5. The electrode of claim 1, wherein the block copolymer layer has a thickness of 10nm to 100 nm.

6. The electrode according to claim 1, further comprising a transparent conductive film disposed on a surface of the block copolymer layer and connected to the transparent conductive layer.

7. The electrode of claim 1, wherein the block copolymer layer comprises at least two polymer blocks, the polymer blocks comprising at least one of a polystyrene block, a polymethylmethacrylate block, a polydimethylsiloxane block, a polyvinylpyrrolidone block, a polyethylene oxide block, and a polybutadiene block.

8. The electrode of claim 1, wherein the depth of the groove is 100nm to 200nm, and the lateral dimension of the opening of the groove is in micro-nano scale.

9. The electrode of claim 1, wherein the opening of the recess is at least one of polygonal, circular, and annular.

10. A method of making an electrode, comprising:

11. The method according to claim 10, further comprising etching the block copolymer layer before forming the transparent conductive material film.

12. A method of making an electrode, comprising:

13. An OLED device comprising a substrate, an anode, an organic light-emitting layer and a cathode, which are arranged in a stacked manner, wherein at least one of the anode and the cathode comprises the electrode according to any one of claims 1 to 9 or the electrode produced by the production method according to any one of claims 10 to 12.

14. An electronic device comprising a housing and a display device coupled to the housing, the display device comprising the OLED device of claim 13.