Composite electrode, photoelectric device and display device

Abstract

The invention discloses a composite electrode, a photoelectric device and a display device, the composite electrode comprises a conductive nanowire layer and a graphene layer which are stacked, and the conductive nanowire layer comprises conductive nanowires and a first conductive polymer arranged in gaps between the conductive nanowires. The composite electrode comprises the conductive nanowire layer, and a large number of contact points can be formed between the conductive nanowires in the conductive nanowire layer and the first conductive polymer filled in the gaps of the conductive nanowires, so that the contact area between the conductive nanowires and the first conductive polymer is increased; and more charge transmission interfaces are provided, so that the charge transmission efficiency of the composite electrode is improved.

Description

Technical Field

[0001] The present application relates to the technical field of electrodes, and particularly to a composite electrode, an optoelectronic device, and a display device. Background Art

[0002] Electrodes are widely used in various electronic devices to input or output current, enabling the devices to operate under the drive of electric energy.

[0003] Currently, commonly used electrode materials include transparent oxide electrodes, metal electrodes, composite electrodes of transparent oxides and metals, graphene electrodes, carbon nanotube electrodes, and alloy electrodes, etc. These electrodes have good electrical conductivity, but there is still a problem of low charge transfer efficiency.

[0004] Therefore, there is an urgent need to provide an electrode with high charge transfer efficiency. Summary of the Invention

[0005] In view of this, the present application provides a composite electrode, an optoelectronic device, and a display device.

[0006] The composite electrode according to an embodiment of the present application is realized as follows: It includes a stacked conductive nanowire layer and a graphene layer, and the conductive nanowire layer includes conductive nanowires and a first conductive polymer disposed in the gaps between the conductive nanowires.

[0007] Optionally, in some embodiments of the present application, the conductive nanowires are arranged in an array; and / or

[0008] The material of the conductive nanowires includes a first conductive metal oxide, and the first conductive metal oxide includes one or more of zinc oxide, calcium oxide, gallium oxide, indium oxide, tin oxide, lead oxide, and cadmium oxide.

[0009] Optionally, in some embodiments of the present application, the first conductive metal oxide further includes a first doping element, and the first doping element includes one or more of thorium, scandium, lanthanum, cerium, copper, iron, cobalt, lithium, and potassium.

[0010] Optionally, in some embodiments of the present application, the first conductive polymer includes one or more of polycarbazole, polythiophene, polyacrylonitrile, polybenzimidazole, and polyacetylene.

[0011] Optionally, in some embodiments of the present application, the conductive nanowires are perpendicular to, intersect with, or parallel to the graphene layer in their length direction; and / or

[0012] The average diameter of the conductive nanowires is 1 - 10 nm; and / or

[0013] The average length of the conductive nanowires is 10 - 100 nm; and / or

[0014] The spacing between the conductive nanowires is 1 to 80 nm; and / or

[0015] The thickness of the conductive nanowire layer is 30 to 100 nm; and / or

[0016] The thickness of the graphene layer is 10 to 50 nm.

[0017] Optionally, in some embodiments of the present application, the composite electrode further includes an interface modification layer located between the conductive nanowire layer and the graphene layer. The interface modification layer includes one or more of conductive metal oxide particles and carbon nanotubes. The material of the conductive metal oxide particles includes a second conductive metal oxide, and the second conductive metal oxide includes TiO 2 、SnO 2 、ITO, FTO, IZO, AgO, or a combination thereof.

[0018] Optionally, in some embodiments of the present application, the second conductive metal oxide is further doped with a second doping element, and the second doping element includes one or more of thorium, scandium, lanthanum, cerium, copper, iron, cobalt, lithium, and potassium; and / or

[0019] The thickness of the interface modification layer is 5 to 15 nm.

[0020] Optionally, in some embodiments of the present application, the composite electrode further includes a conductive polymer layer located between the conductive nanowire layer and the interface modification layer, or the conductive polymer layer is disposed on the surface of the conductive nanowire layer away from the interface modification layer.

[0021] Optionally, in some embodiments of the present application, the conductive polymer layer includes a second conductive polymer, and the second conductive polymer includes one or more of polycarbazole, polythiophene, polyacrylonitrile, polybenzimidazole, and polyacetylene; and / or

[0022] The thickness of the conductive polymer layer is 5 to 20 nm.

[0023] Correspondingly, an embodiment of the present application further provides an optoelectronic device, including a stacked anode, a functional layer, and a cathode, where at least one of the anode and the cathode is a composite electrode. The composite electrode includes a stacked conductive nanowire layer and a graphene layer. The conductive nanowire layer includes conductive nanowires and a first conductive polymer filled in the gaps between the conductive nanowires, and the conductive nanowire layer is close to the functional layer.

[0024] Optionally, the conductive nanowires are arranged in an array; and / or

[0025] The material of the conductive nanowires includes a first conductive metal oxide, and the first conductive metal oxide includes one or more of zinc oxide, calcium oxide, gallium oxide, indium oxide, tin oxide, lead oxide, and cadmium oxide; and / or

[0026] The first conductive polymer includes one or more of polycarbazole, polythiophene, polyacrylonitrile, polybenzimidazole, and polyacetylene; and / or

[0027] The conductive nanowires are perpendicular to, intersect with, or parallel to the graphene layer.

[0028] Optionally, the composite electrode further includes an interface modification layer, the interface modification layer is located between the conductive nanowire layer and the graphene layer, and the interface modification layer includes one or more of conductive metal oxide particles and carbon nanotubes. The material of the conductive metal oxide particles includes a second conductive metal oxide, and the second conductive metal oxide includes TiO 2 、SnO 2 、ITO, FTO, IZO, AgO, etc. one or more of them.

[0029] Optionally, the composite electrode further includes a conductive polymer layer, the conductive polymer layer is located between the conductive nanowire layer and the interface modification layer, and the conductive nanowire layer is bonded to the functional layer; or,

[0030] The conductive polymer layer is disposed on the surface of the conductive nanowire layer away from the interface modification layer, and the conductive polymer layer is bonded to the functional layer.

[0031] Optionally, in some embodiments of the present application, the conductive nanowire layer of the composite electrode is bonded to the functional layer; or,

[0032] The conductive polymer layer of the composite electrode is bonded to the functional layer.

[0033] Optionally, in some embodiments of the present application, the functional layer includes a hole injection layer, and the material of the hole injection layer includes 2,3,6,7,10,11 - hexacyano - 1,4,5,8,9,12 - hexaazatriphenylene, PEDOT, PEDOT:PSS, derivatives of PEDOT:PSS doped with s - MoO 3 、4,4',4' - tris(N - 3 - methylphenyl - N - phenylamino)triphenylamine, tetracyanoquinodimethane, copper phthalocyanine, nickel oxide, molybdenum oxide, tungsten oxide, vanadium oxide, molybdenum sulfide, tungsten sulfide, and copper oxide, etc. one or more of them; and / or

[0034] The functional layer includes a hole transport layer, and the materials of the hole transport layer include 4,4'-N,N'-dicarbazolyl-biphenyl, poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine], N,N'-diphenyl-N,N'-bis(1-naphthyl)-1,1'-biphenyl-4,4”-diamine, N,N'-diphenyl-N,N'-bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine, poly(N,N'-bis(4-butylphenyl)-N,N'-bis(phenyl)benzidine), N,N'-bis(3-methylphenyl)-N,N'-bis(phenyl)-spiro, N,N'-bis(4-(N,N'-diphenyl-amino)phenyl)-N,N'-diphenylbenzidine, 4,4',4'-tris(N-carbazolyl)-triphenylamine, 4,4',4'-tris(N-3-methylphenyl-N-phenylamino)triphenylamine, poly[(9,9'-dioctylfluorene-2,7-diyl)-co-(4,4'-(N-(4-sec-butylphenyl)diphenylamine))], poly(N-vinylcarbazole) and its derivatives, N,N'-bis(1-naphthyl)-N,N'-diphenyl-1,1'-biphenyl-4-4'-diamine, spiro-NPB, poly(phenylene vinylene), poly[2-methoxy-5-(2-ethylhexoxy)-1,4-phenylene vinylene], poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylene vinylene], 2,2',7,7'-tetrakis[N,N-bis(4-methoxyphenyl)amino]-9,9'-spirobifluorene, 4,4'-cyclohexylbis[N,N-bis(4-methylphenyl)aniline], 1,3-bis(carbazol-9-yl)benzene, polyaniline, polypyrrole, poly(p-phenylene vinylene), aromatic tertiary amines, polynuclear aromatic tertiary amines, 4,4'-bis(p-carbazolyl)-1,1'-biphenyl compound, N,N,N',N'-tetraarylbenzidine, PEDOT:PSS and its derivatives, polymethacrylate and its derivatives, poly(9,9-octylfluorene) and its derivatives, poly(spirofluorene) and its derivatives, doped graphene, undoped graphene, C60, doped or undoped NiO, doped or undoped MoO 3 、doped or undoped WO 3 、doped or undoped V 2 O 5 、doped or undoped p-type gallium nitride, doped or undoped CrO 3 、doped or undoped CuO, one or more of them; and / or

[0035] The functional layer includes a light-emitting layer, and the material of the light-emitting layer includes one or more of organic light-emitting materials and quantum dot light-emitting materials. The organic light-emitting materials include one or more of 4,4'-bis(N-carbazolyl)-1,1'-biphenyl: tris[2-(p-tolyl)pyridineiridium(III)], 4,4',4''-tris(carbazol-9-yl)triphenylamine: tris[2-(p-tolyl)pyridineiridium, diarylanthracene derivatives, stilbene aromatic derivatives, pyrene derivatives, fluorene derivatives, TBPe fluorescent materials, TTPX fluorescent materials, TBRb fluorescent materials, DBP fluorescent materials, delayed fluorescence materials, TTA materials, thermally activated delayed materials, polymers containing B-N covalent bonds, hybrid local charge transfer excited state materials, exciplex luminescent materials, polyacetylene and its derivatives, poly(p-phenylene) and its derivatives, polythiophene and its derivatives, polyfluorene and its derivatives; The quantum dot light-emitting materials include one or more of single-structure quantum dots, core-shell structure quantum dots and perovskite semiconductor materials. The materials of the single-structure quantum dots, the core materials of the core-shell structure quantum dots and the shell materials of the core-shell structure quantum dots are each independently selected from one or more of group II-VI compounds, group IV-VI compounds, group III-V compounds and group I-III-VI compounds. The shell layer of the core-shell structure quantum dots includes one or more layers;The II-VI group compounds include one or more of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, and HgZnSTe; the IV-VI group compounds include one or more of SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, SnPbSeTe, SnPbSTe; the III-V group compounds include one or more of GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, and InAlPSb; the I-III-VI group compounds include one or more of CuInS; 2 , CuInSe 2 , and AgInS 2 ; the perovskite semiconductor material includes doped or undoped inorganic perovskite semiconductors or organic-inorganic hybrid perovskite semiconductors. The structural general formula of the inorganic perovskite semiconductor is AMX 3 , where A is Cs + ions, M is a divalent metal cation, including Pb 2 + , Sn 2+ , Cu 2+ , Ni 2+ , Cd 2+ , Cr 2+ , Mn 2+ , Co 2+, Fe 2+ , Ge 2+ , Yb 2+ , Eu 2+ or more than one of them, X is a halogen anion, including Cl - , Br - , I - or more than one of them; the structural general formula of the organic-inorganic hybrid perovskite semiconductor is BMX 3 , where B is an organic amine cation, including CH 3 (CH 2 ) n-2 NH 3 + or [NH 3 (CH 2 ) n NH 3 2+ , where n≥2, M is a divalent metal cation, including Pb 2+ , Sn 2+ , Cu 2+ , Ni 2+ , Cd 2+ , Cr 2+ , Mn 2+ , Co 2+ , Fe 2+ , Ge 2+ , Yb 2+ , Eu 2+ or more than one of them, X is a halogen anion, including Cl - , Br - , I - or more than one of them; and / or

[0036] The functional layer includes an electron transport layer, and the material of the electron transport layer includes one or more of an inorganic electron transport material and an organic electron transport material. The inorganic electron transport material includes one or more of a metal oxide, a doped metal oxide, a IIB-VIA group semiconductor material, a IIIA-VA group semiconductor material, and a IB-IIIA-VIA group semiconductor material. The metal oxide includes ZnO, TiO 2 , SnO 2 , ZrO 2 , Ta 2 O 5 or more than one of them; the metal oxide in the doped metal oxide includes ZnO, TiO 2 , SnO 2 , ZrO 2 , Ta 2 O 5 , Al 2 O​3 One or more of the above, wherein the dopants in the doped metal oxide include one or several of Al, Mg, Li, Mn, Y, La, Cu, Ni, Zr, Ce, In, Ga, Sn; the IIB-VIA group semiconductor material includes one or more of ZnS, ZnSe, CdS; the IIIA-VA group semiconductor material includes one or more of InP, GaP; the IB-IIIA-VIA group semiconductor material includes one or more of CuInS, CuGaS; the organic electron transport material includes one or more of quinoxaline compounds, imidazole compounds, triazine compounds, fluorene-containing compounds, hydroxyquinoline compounds.

[0037] Correspondingly, the embodiment of the present application further provides a display device, including the above optoelectronic device.

[0038] The composite electrode in the present application includes the conductive nanowire layer. The conductive nanowires in the conductive nanowire layer can have a large number of contact points with the first conductive polymer filled in their gaps, thereby increasing the contact area between the conductive nanowires and the first conductive polymer, providing more charge transfer interfaces, and further improving the charge transfer efficiency of the composite electrode. Description of the Drawings

[0039] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the following will briefly introduce the drawings required for the description of the embodiments. Obviously, the drawings in the following description are only some embodiments of the present application. For those skilled in the art, without creative efforts, other drawings can be obtained based on these drawings.

[0040] Figure 1 is a schematic structural diagram of a composite electrode provided by an embodiment of the present application;

[0041] Figure 2 is a schematic structural diagram of another composite electrode provided by an embodiment of the present application;

[0042] Figure 3 is a schematic structural diagram of yet another composite electrode provided by an embodiment of the present application;

[0043] Figure 4 is a schematic structural diagram of yet another composite electrode provided by an embodiment of the present application;

[0044] Figure 5 is a schematic structural diagram of yet another composite electrode provided by an embodiment of the present application;

[0045] Figure 6 is a schematic structural diagram of yet another composite electrode provided by an embodiment of the present application;

[0046] Figure 7 It is a flow chart of a method for preparing a composite electrode provided by an embodiment of the present application;

[0047] Figure 8 It is a flow chart of another method for preparing a composite electrode provided by an embodiment of the present application;

[0048] Figure 9 It is a flow chart of a method for preparing an optoelectronic device provided by an embodiment of the present application;

[0049] Figure 10 It is a schematic structural diagram of an optoelectronic device provided by an embodiment of the present application.

[0050] Reference numerals:

[0051] Composite electrode 101; Conductive nanowire layer 1; Graphene layer 2; Interface modification layer 3; Conductive polymer layer 4; Optoelectronic device 100; Anode 10; Functional layer 20; Hole injection layer 21; Hole transport layer 22; Light-emitting layer 23; Electron transport layer 24; Cathode 30. Detailed implementation manners

[0052] Next, the technical solutions in the embodiments of the present application will be clearly and completely described in conjunction with the accompanying drawings in the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative efforts belong to the scope of protection of the present application. In addition, it should be understood that the specific implementation manners described herein are only used to illustrate and explain the present application, and are not used to limit the present application.

[0053] In the present application, unless otherwise stated, the orientation terms such as "upper" and "lower" usually refer to the upper and lower in the actual use or working state of the device, specifically the drawing direction in the drawings; while "inner" and "outer" refer to the outline of the device. In addition, in the description of the present application, the term "comprising" means "including but not limited to". The terms first, second, third, etc. are only used as labels and do not impose numerical requirements or establish an order.

[0054] In the present application, "and / or" describes the association relationship of associated objects, indicating that three relationships can exist. For example, A and / or B can represent: A exists alone, A and B exist simultaneously, and B exists alone. Where A and B can be singular or plural.

[0055] In this application, "at least one" means one or more, and "a plurality" means two or more. "At least one kind", "at least one item (or one) below" or similar expressions refer to any combination of these items, including any combination of single item (or one) or plural items (or ones). For example, "at least one item (or one) among a, b, or c", or "at least one item (or one) among a, b, and c" can both represent: a, b, c, a - b (i.e., a and b), a - c, b - c, or a - b - c, where a, b, and c can be single or multiple respectively.

[0056] In this application, when forming another layer "on" a certain layer, the so - called "on" is a broad concept, which can mean that the formed another layer is adjacent to a certain layer, or it can mean that there are other spacer structure layers between another layer and a certain layer. For example, when forming a second electrode "on" the first carrier functional layer, the so - called "on" can mean that the formed second electrode is adjacent to the first carrier functional layer, or it can mean that there are other spacer structure layers between the second electrode and the first carrier functional layer, such as a light - emitting layer.

[0057] Various embodiments of this application can exist in the form of a range; it should be understood that the description in the form of a range is only for convenience and brevity, and should not be construed as a rigid limitation on the scope of this application; therefore, it should be considered that the range description has specifically disclosed all possible sub - ranges and single values within that range. For example, it should be considered that the range description from 1 to 6 has specifically disclosed sub - ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., and single numbers within that range, such as 1, 2, 3, 4, 5, and 6, which applies regardless of the range. Additionally, whenever a numerical range is indicated herein, it means including any cited number (fraction or integer) within the indicated range.

[0058] The technical solution of this application is as follows:

[0059] In a first aspect, please refer to Figures 1 to 3 , an embodiment of this application provides a composite electrode 101, which includes a conductive nanowire layer 1 and a graphene layer 2 stacked in sequence.

[0060] The conductive nanowire layer 1 includes conductive nanowires and a first conductive polymer, and there are gaps between adjacent conductive nanowires, and the first conductive polymer is disposed in the gaps between the conductive nanowires.

[0061] The conductive nanowires are arranged in an array. In other words, the conductive nanowire layer 1 includes conductive nanowires arranged in an array.

[0062] In the composite electrode 101 described in the present application, the conductive nanowire layer 1 is included, and the conductive nanowire layer 1 includes the conductive nanowires. On the one hand, the conductive nanowires have a high specific surface area and conductivity, enabling charges to be rapidly transported inside them, thus having a high charge transport efficiency. On the other hand, the conductive nanowires can provide a direct charge transport path, and the spacing between the nanowires is small, which can form a continuous conductive network, allowing charges to be directly transported from one nanowire to another without passing through a longer transport path or detouring, thereby further enhancing the charge transport efficiency. On yet another hand, grain boundaries and defects can cause scattering and reflection of electrons, resulting in a reduction in charge transport efficiency, while the conductive nanowires have fewer grain boundaries and defects, thus having a high charge transport efficiency.

[0063] The material of the conductive nanowires may include a first conductive metal oxide. The first conductive metal oxide includes, but is not limited to, one or more of zinc oxide (ZnO), calcium oxide (CaO), gallium oxide (Ga 2 O 3 ), indium oxide (In 2 O 3 ), tin oxide (SnO 2 ), lead oxide (PbO 2 ), and cadmium oxide (CdO).

[0064] In some embodiments, the first conductive metal oxide further includes a first doping element, and the first doping element includes, but is not limited to, one or more of scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), copper (Cu), iron (Fe), cobalt (Co), lithium (Li), and potassium (K). The first doping element can change the electronic structure and crystal structure of the first conductive metal oxide, improving the conductive performance and optical performance of the first conductive metal oxide.

[0065] Please further refer to Figures 1 to 3 , it can be understood that the conductive nanowires can be perpendicular to (please refer to Figure 1 ), intersect with (please refer to Figure 2 ), or be parallel to (please refer to Figure 3 ) the graphene layer 2 in their length direction. In at least one preferred embodiment, the conductive nanowires are perpendicular to or intersect with the graphene layer 2 in their length direction. More preferably, the conductive nanowires are perpendicular to the graphene layer 2 in their length direction.

[0066] The average diameter of the conductive nanowires is 1 to 10 nm, for example, 1 nm, 2 nm, 3 nm, 4 nm, 5 nm, 6 nm, 7 nm, 8 nm, 9 nm, 10 nm, etc. Within the range of the average diameter, on the one hand, due to the relatively large surface area of the conductive nanowires, the injection efficiency of carriers can be improved; on the other hand, the range of carrier injection in the conductive nanowires can be made more concentrated, and the injection uniformity is better, avoiding the performance differences of the device including the composite electrode 101 caused by uneven carrier injection; on the further hand, the loss of electrons and holes during the transport process can be reduced, further improving the carrier transport efficiency.

[0067] The average length of the conductive nanowires is 10 to 100 nm, for example, 10 nm, 15 nm, 20 nm, 25 nm, 30 nm, 35 nm, 40 nm, 45 nm, 50 nm, 55 nm, 60 nm, 65 nm, 70 nm, 75 nm, 80 nm, 85 nm, 90 nm, 95 nm, 100 nm, etc. Within the range of the average length, on the one hand, it helps to reduce the charge injection resistance, thereby accelerating the charge injection speed and enhancing the conductivity of the composite electrode 101; on the other hand, the composite electrode 101 can have better transparency, and when using the composite electrode 101 as the electrode on the light-emitting side of an optoelectronic device, the light-emitting efficiency of the optoelectronic device can be improved.

[0068] The spacing between the array-arranged conductive nanowires is 1 to 80 nm, for example, 1 nm, 5 nm, 10 nm, 15 nm, 20 nm, 25 nm, 30 nm, 35 nm, 40 nm, 45 nm, 50 nm, 55 nm, 60 nm, 65 nm, 70 nm, 75 nm, 80 nm, etc. Within the range of the spacing, the composite electrode 101 can have better charge transport efficiency.

[0069] The thickness of the conductive nanowire layer 1 is 30 to 100 nm, for example, 30 nm, 35 nm, 40 nm, 45 nm, 50 nm, 55 nm, 60 nm, 65 nm, 70 nm, 75 nm, 80 nm, 85 nm, 90 nm, 95 nm, 100 nm, etc. Within the range of the thickness, the composite electrode 101 can have both better conductivity and better transparency.

[0070] The first conductive polymer includes, but is not limited to, one or more of poly(3,4-ethylenedioxythiophene) poly(styrene sulfonate) (PEDOT:PSS), polythiophene (PT), polyacrylonitrile (PAN), polybenzimidazole (PBI), and polyacetylene (PA). When energized, the first conductive polymer can have a high carrier concentration, mobility, and conductivity, and can provide more conductive channels for charges, thereby enhancing the conductivity of the composite electrode 101.

[0071] Please refer to Figure 4 , the composite electrode 101 further includes an interface modification layer 3, and the interface modification layer 3 is located between the conductive nanowire layer 1 and the graphene layer 2.

[0072] The interface modification layer 3 includes an interface modification material, and the interface modification material includes, but is not limited to, one or more of conductive metal oxide particles and carbon nanotubes. The material of the conductive metal oxide particles includes a second conductive metal oxide, and the second conductive metal oxide includes, but is not limited to, TiO 2 , SnO 2 , ITO (indium tin oxide), FTO (fluorine-doped tin oxide), IZO (indium zinc oxide), AgO, etc.

[0073] In some embodiments, the second conductive metal oxide may also be doped with a second doping element, and the second doping element includes, but is not limited to, one or more of scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), copper (Cu), iron (Fe), cobalt (Co), lithium (Li), potassium (K). The second doping element can change the electronic structure and crystal structure of the second conductive metal oxide, and improve the conductive performance and optical performance of the second conductive metal oxide.

[0074] The composite electrode 101 described in this application further includes the interface modification layer 3. On the one hand, the material of the interface modification layer 3 can fill the gaps and defects between the conductive nanowire layer 1 and the graphene layer 2, and there is good interface matching between the material of the interface modification layer 3 and the conductive nanowires in the conductive nanowire layer 1 as well as with the graphene in the graphene layer 2. The interface contact area is high and the interface contact resistance is small, which can effectively reduce the scattering and loss of charges at the interface, thereby improving the charge transport efficiency of the composite electrode 101. On the other hand, the material of the interface modification layer 3 has good conductivity and transparency, which can provide more conductive channels and better electron transport paths, facilitating the transport of charges between different layers, thereby further enhancing the charge transport efficiency of the composite electrode 101. On the other hand, when the composite electrode 101 is used in a device, the material of the interface modification layer 3 has good chemical stability and durability. If the interface modification layer 3 is located outside compared to the conductive nanowire layer 1 (i.e., the interface modification layer 3 is closer to the external environment), it can prevent oxygen or moisture in the environment from entering the conductive nanowire layer 1, thereby enhancing the antioxidant, moisture resistance, and durability of the composite electrode 101. In addition, there are a large number of contact points between the conductive nanowires in the conductive nanowire layer 1 and the first conductive polymer as well as the interface modification layer 3, thereby increasing the contact area between the conductive nanowires and the first conductive polymer as well as the interface modification layer 3, providing more charge transport interfaces, and further enhancing the charge transport efficiency of the composite electrode 101.

[0075] It can be understood that the material of the conductive nanowires can be the same as or different from the material of the interface modification layer 3. When the material of the conductive nanowires is the same as the material of the interface modification layer 3, consistent material properties and interface characteristics can be maintained, which is beneficial for electron transport and interface matching. The specific surface area of the conductive nanowires is relatively small compared to the specific surface area of the material of the interface modification layer 3, and the transport paths of electrons and holes are relatively long, which is beneficial for improving the transport efficiency of carriers. While the surface area of the material of the interface modification layer 3 is relatively large, and electrons and holes are prone to recombination at the defects or surface modifications on its surface. Therefore, charge injection can be regulated.

[0076] The thickness of the interface modification layer 3 is 5 - 15 nm. For example, 5 nm, 8 nm, 10 nm, 12 nm, 14 nm, 15 nm, etc. Within this thickness range, the absorption and scattering of light can be reduced, which helps to improve transparency. It can fill the gaps and defects between the conductive nanowire layer 1 and the graphene layer 2, thereby forming a tighter interface structure and enhancing the bonding force between different layers.

[0077] The material of the graphene layer 2 includes graphene, which has high transparency, optical properties, and electrical conductivity, and can effectively improve the transparency, optical properties, and electrical conductivity of the composite electrode 101. In addition, graphene can provide better photoelectric conversion efficiency, thereby further improving the optical properties of the composite electrode 101.

[0078] In some embodiments, the thickness of the graphene layer 2 is 10 - 50 nm. For example, 10, 15, 20, 25, 30, 35, 40, 45, 50, etc. Within this thickness range, the composite electrode 101 can have good transparency and electrical conductivity.

[0079] Please refer to Figures 5 to 6 , in some embodiments, the composite electrode 101 further includes a conductive polymer layer 4, and the conductive polymer layer 4 is located between the conductive nanowire layer 1 and the interface modification layer 3, or the conductive polymer layer 4 is combined on the surface of the conductive nanowire layer 1 away from the interface modification layer 3.

[0080] The conductive polymer layer 4 includes a second conductive polymer. The combination of the conductive polymer layer 4 on the surface of the conductive nanowire layer 1 can effectively cover the conductive nanowire layer 1, thus facilitating the formation of a flat surface, helping to reduce resistance and interface reflection, and thus contributing to improving the charge transfer efficiency of the composite electrode 101. In addition, there can be a large number of contact points between the conductive nanowires in the conductive nanowire layer 1 and the first conductive polymer and the second conductive polymer in the conductive polymer layer 4, thereby increasing the contact area between the conductive nanowires and the first and second conductive polymers, providing more charge transfer interfaces, and further enhancing the charge transfer efficiency of the composite electrode 101.

[0081] The second conductive polymer includes, but is not limited to, one or more of poly(3,4 - ethylenedioxythiophene) poly(styrene sulfonate) (PEDOT:PSS), polythiophene (PT), polyacrylonitrile (PAN), polybenzimidazole (PBI), and polyacetylene (PA). The second conductive polymer can have a high carrier concentration, mobility, and electrical conductivity under energization, and can provide more conductive channels for charges, thereby enhancing the electrical conductivity of the composite electrode 101.

[0082] It can be understood that the first conductive polymer and the second conductive polymer can be the same or different. In at least one embodiment, the first conductive polymer and the second conductive polymer are the same.

[0083] The thickness of the conductive polymer layer 4 ranges from 5 to 20 nm, for example, 5 nm, 8 nm, 10 nm, 12 nm, 15 nm, 16 nm, 18 nm, 20 nm, etc. Within this thickness range, the conductive nanowire layer 1 can be effectively covered, which is beneficial to obtaining a composite electrode 101 with a flat surface, and further beneficial to improving the performance such as the stability and conductivity of the composite electrode 101.

[0084] In a second aspect, please refer to Figure 1 and Figure 7 , embodiments of the present application further provide a method for preparing a composite electrode, including the following steps:

[0085] Step S11: Provide a substrate;

[0086] Step S12: Deposit a first conductive metal oxide on the substrate to form conductive nanowires arranged in an array, and fill a first conductive polymer into the gaps between the conductive nanowires to obtain the conductive nanowire layer 1;

[0087] Step S13: Form a graphene layer 2 on the conductive nanowire layer 1 to obtain the composite electrode 101.

[0088] Please refer to Figure 4 , in some embodiments, step S13 includes: sequentially forming a stacked interfacial modification layer 3 and graphene layer 2 on the conductive nanowire layer 1 to obtain the composite electrode 101.

[0089] Please refer to Figure 5 , in some embodiments, step S13 includes: sequentially forming a stacked conductive polymer layer 4, interfacial modification layer 3 and graphene layer 2 on the conductive nanowire layer 1 to obtain the composite electrode 101.

[0090] In a third aspect, please refer to Figure 1 and Figure 8 , embodiments of the present application further provide another method for preparing a composite electrode, including the following steps:

[0091] Step S21: Provide a substrate;

[0092] Step S22: Form a graphene layer 2 on the substrate;

[0093] Step S23: Deposit a first conductive metal oxide on the graphene layer 2 to form conductive nanowires arranged in an array, and fill a first conductive polymer into the gaps between the conductive nanowires to obtain the conductive nanowire layer 1, and obtain the composite electrode 101.

[0094] Please refer to Figure 4, in some embodiments, step S22 includes: sequentially forming a stacked graphene layer 2 and an interface modification layer 3 on the substrate. At this time, in step S23, a first conductive metal oxide is deposited on the interface modification layer 3.

[0095] Please refer to Figure 6 , in some embodiments, after obtaining the conductive nanowire layer 1, it further includes: forming a conductive polymer layer 4 on the conductive nanowire layer 1.

[0096] In the two preparation methods:

[0097] The substrate can be a substrate known for preparing electrodes.

[0098] In some embodiments, the substrate is a rigid substrate or a flexible substrate, and for example, it can include one or more of, but is not limited to, glass, silicon wafer, polycarbonate, polymethyl methacrylate, polyethylene terephthalate, polyethylene naphthalate, polyamide, and polyethersulfone.

[0099] In some other embodiments, the substrate can be a half-device of an optoelectronic device for which a composite electrode is to be prepared, such as a half-device of an optoelectronic device including a stacked bottom electrode and a functional layer, etc.

[0100] The first conductive metal oxide and the conductive nanowires are as described above, and will not be elaborated here.

[0101] In some embodiments, the method of depositing the first conductive metal oxide on the substrate to form a conductive nanowire array can be a nanowire solution preparation method or a vapor deposition method.

[0102] As an example, the nanowire solution preparation method can be: dispersing the first conductive metal oxide and a first surfactant in a first solvent to obtain a first conductive metal oxide dispersion, setting the first conductive metal oxide dispersion on a first substrate, and then performing high-temperature heat treatment to grow metal ions on the substrate to form a conductive nanowire array.

[0103] It can be understood that the first substrate can be the substrate described above, or a substrate including the graphene layer 2, or a substrate including the stacked graphene layer 2 and the interface modification layer 3.

[0104] The first solvent includes one or more of, but is not limited to, water and alcohol solvents, and the alcohol solvents include one or more of, but are not limited to, methanol, ethanol, and isopropanol.

[0105] The first surfactant is a surfactant known to be used in the solution method for preparing nanowires, and may include, for example, but not limited to, one or more of ethylene glycol monobutyl ether (EGDE), sodium dodecyl sulfate (SDS), cetyltrimethylammonium bromide (CTAB), polystyrene-b-polyacrylic acid (PS-b-PAA), polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), and hexadecylphenol polyoxyethylene ether (Triton X-100).

[0106] In the first conductive metal oxide dispersion, the concentration range of the first conductive metal oxide is 0.1 to 1 mol / L. For example, 0.1 mol / L, 0.2 mol / L, 0.3 mol / L, 0.4 mol / L, 0.5 mol / L, 0.6 mol / L, 0.7 mol / L, 0.8 mol / L, 0.9 mol / L, 1.0 mol / L, etc. Within this concentration range, the first conductive metal oxide can be uniformly dispersed, which is beneficial to preparing a conductive nanowire array with better conductivity and stability.

[0107] In the first conductive metal oxide dispersion, the temperature range of the high-temperature treatment is 70 to 300 °C. For example, 70 °C, 80 °C, 90 °C, 100 °C, 200 °C, 300 °C, etc., and the time range is 10 to 60 min. For example, 10 min, 15 min, 20 min, 25 min, 30 min, 35 min, 40 min, 45 min, 50 min, 55 min, 60 min. Within this temperature and time range, it is beneficial to preparing a conductive nanowire array with better conductivity and stability.

[0108] The first conductive polymer is as described above and will not be elaborated here.

[0109] The method of filling the first conductive polymer into the gaps of the conductive nanowire array can be a chemical method or a physical method. Among them, the chemical methods include chemical vapor deposition, successive ionic layer adsorption and reaction, anodic oxidation, electrodeposition, and coprecipitation. The physical methods include the physical coating method and the solution method described above. Among them, the solution method can be spin coating, printing, inkjet printing, doctor blading, printing, dip coating, immersion, spraying, roll coating, casting, slot die coating, and bar coating, etc.

[0110] In at least some embodiments, the method of filling the first conductive polymer into the gaps of the conductive nanowire array includes: dissolving the first conductive polymer in a second solvent to obtain a first conductive polymer solution, and spin coating the first conductive polymer solution on the conductive nanowire array to make the first conductive polymer solution penetrate and fill the gaps of the conductive nanowire array.

[0111] The second solvent includes, but is not limited to, water and the alcohol solvents described above.

[0112] In the first conductive polymer solution, the concentration range of the first conductive polymer is 0.1 - 1 mol / L. For example, 0.1 mol / L, 0.2 mol / L, 0.3 mol / L, 0.4 mol / L, 0.5 mol / L, 0.6 mol / L, 0.7 mol / L, 0.8 mol / L, 0.9 mol / L, 1 mol / L, etc. Within this concentration range, it is beneficial for the first conductive polymer to form a good filling in the gaps of the conductive nanowire array.

[0113] In some embodiments, after filling the first conductive polymer in the gaps of the conductive nanowire array, a first drying is further included.

[0114] The first drying can be a method known for drying wet films. For example, it can include one or more of vacuum drying, reduced-pressure drying, freeze-drying, and baking.

[0115] In at least one embodiment, the first drying is baking, wherein the baking temperature is 60 - 100 °C and the time is 10 - 30 min.

[0116] In some embodiments, the method for forming the graphene layer 2 can be the chemical method or physical method described above.

[0117] In at least some embodiments, the method for forming the graphene layer 2 includes: dispersing graphene in a third solvent to obtain a graphene dispersion, and spin-coating the graphene dispersion on a second substrate.

[0118] It can be understood that the second substrate can be the substrate described above, or a substrate formed with the conductive nanowire layer 1, or a substrate formed with the stacked conductive nanowire layer 1 and the interface modification layer 3, or a substrate formed with the stacked conductive nanowire layer 1, the conductive polymer layer 4, and the interface modification layer 3.

[0119] The third solvent includes, but is not limited to, water and the alcohol solvents described above.

[0120] In the graphene dispersion, the concentration range of the graphene is 0.1 - 1 mol / L. For example, 0.1 mol / L, 0.2 mol / L, 0.3 mol / L, 0.4 mol / L, 0.5 mol / L, 0.6 mol / L, 0.7 mol / L, 0.8 mol / L, 0.9 mol / L, 1 mol / L, etc. Within this range, it is beneficial to prepare a graphene layer 2 with a uniform surface and a uniform thickness, thereby improving the conductivity and transparency of the composite electrode 101.

[0121] In some embodiments, after spin-coating the graphene dispersion on the second substrate, the following steps are further included: second drying.

[0122] The second drying can be a method known for drying wet films, and for example, it can include one or more of vacuum drying, reduced-pressure drying, freeze-drying, and baking.

[0123] In at least one embodiment, the second drying is baking, where the baking temperature is 60 - 100 °C and the time is 10 - 30 min. In this way, the graphene can be effectively dried, and the obtained graphene layer 2 can have a good film-forming effect.

[0124] In some embodiments, the method for forming the interface modification layer 3 includes: disposing the interface modification material on the third substrate to form the interface modification layer 3.

[0125] It can be understood that the method for disposing the interface modification material on the third substrate can be the physical method or the chemical method described above.

[0126] In at least some embodiments, the method for disposing the interface modification material on the third substrate can be the chemical method or the physical method described above.

[0127] It can be understood that the third substrate can be a substrate including the graphene layer 2, or a substrate including the conductive nanowire layer 1, or a substrate including the conductive nanowire layer 1 and the conductive polymer layer 4.

[0128] In at least some embodiments, the method for disposing the interface modification material on the third substrate includes: dissolving the interface modification material and the second surfactant in a fourth solvent to obtain an interface modification material solution, and spin-coating the interface modification material solution on the third substrate.

[0129] The fourth solvent includes but is not limited to water and the alcohol solvents described above.

[0130] The second surfactant includes but is not limited to one or more of polyethylene glycol (PEG), sodium octylbenzenesulfonate (SDBS), and cetyltrimethylammonium bromide (CTAB). The second surfactant can form a micelle structure in the solution to help achieve uniform dispersion and enhance the adhesion of the coating.

[0131] The interface modification material is as described above and will not be elaborated here.

[0132] In the interfacial modification material solution, the concentration range of the interfacial modification material is 0.01 - 0.1 mol / L. For example, 0.01 mol / L, 0.02 mol / L, 0.03 mol / L, 0.04 mol / L, 0.05 mol / L, 0.06 mol / L, 0.07 mol / L, 0.08 mol / L, 0.09 mol / L, 0.1 mol / L, etc. Within this range, it is beneficial to obtain an interfacial modification layer 3 with good film-forming properties.

[0133] In the interfacial modification material solution, the concentration range of the second surfactant is 0.01 - 0.1 mol / L. For example, 0.01 mol / L, 0.02 mol / L, 0.03 mol / L, 0.04 mol / L, 0.05 mol / L, 0.06 mol / L, 0.07 mol / L, 0.08 mol / L, 0.09 mol / L, 0.1 mol / L, etc. Within this range, the interfacial modification material can be evenly dispersed in the fifth solvent, and it is also beneficial to obtain an interfacial modification layer 3 with good film-forming properties.

[0134] In some embodiments, after spin-coating the interfacial modification material solution on the third substrate, a third drying is further included.

[0135] The third drying can be a method known for drying wet films. For example, it can include, but is not limited to, one or more of vacuum drying, reduced-pressure drying, freeze-drying, and baking.

[0136] In at least one embodiment, the third drying is baking, where the baking temperature is 60 - 120 °C and the time is 10 - 30 min. In this way, the interfacial modification material can be effectively dried, and the obtained interfacial modification layer 3 can have a good film-forming effect.

[0137] In some embodiments, the method for forming the conductive polymer layer 4 can be the chemical method or the physical method described above.

[0138] In at least some embodiments, the method for forming the conductive polymer layer 4 includes: dissolving the second conductive polymer in the fifth solvent to obtain a second conductive polymer solution, and spin-coating the second conductive polymer solution on the fourth substrate.

[0139] It can be understood that the fourth substrate can be a substrate including the conductive nanowire layer 1, or a substrate including the stacked graphene layer 2 and the conductive nanowire layer 1, or a substrate including the stacked graphene layer 2, the interfacial modification layer 3, and the conductive nanowire layer 1.

[0140] The fifth solvent includes, but is not limited to, water and the alcohol solvents described above.

[0141] The second conductive polymer is as described above and will not be elaborated here.

[0142] In the second conductive polymer solution, the concentration range of the second conductive polymer is 0.1 - 1 mol / L. For example, 0.1 mol / L, 0.2 mol / L, 0.3 mol / L, 0.4 mol / L, 0.5 mol / L, 0.6 mol / L, 0.7 mol / L, 0.8 mol / L, 0.9 mol / L, 1.0 mol / L, etc. Within this concentration range, it is beneficial for the composite electrode 101 to have a flatter film layer.

[0143] In some embodiments, after the second conductive polymer is disposed on the fourth substrate, a fourth drying is further included.

[0144] The fourth drying can be a method known for drying wet films. For example, it can include, but is not limited to, one or more of vacuum drying, reduced-pressure drying, freeze-drying, and baking.

[0145] In at least one embodiment, the fourth drying is baking, where the baking temperature is 60 - 100 °C and the time is 10 - 30 min.

[0146] In some embodiments, the method for forming the conductive polymer layer 4 is as follows: When filling the first conductive polymer in the gaps of the conductive nanowire array, the deposition time is prolonged or the deposition amount is increased. After the gaps between the conductive nanowire arrays are filled, there is still excess first conductive polymer to form a thin film on the conductive nanowire layer 1, thereby obtaining the conductive polymer layer 4.

[0147] Fourthly, please refer to Figures 9 to 10 , the embodiments of the present application further provide a method for preparing an optoelectronic device, including the following steps:

[0148] Step S31: Provide a substrate and prepare a first electrode on the substrate;

[0149] Step S32: Prepare a functional layer 20 on the first electrode;

[0150] Step S33: Prepare a second electrode on the surface of the functional layer away from the first electrode to obtain the optoelectronic device 100.

[0151] Wherein, the first electrode is the composite electrode 101, and / or the second electrode is the composite electrode 101. In other words, at least one of the first electrode and the second electrode is prepared by the preparation method of the composite electrode described above.

[0152] It can be understood that when both the first electrode and the second electrode are the composite electrode 101 of the present application, the materials of the first electrode and the second electrode can be the same or different.

[0153] When one of the first electrode and the second electrode is not the composite electrode 101 described in this application, the electrode that is not the composite electrode 101 described in this application may include a doped metal oxide electrode, a composite electrode, a graphene electrode, a carbon nanotube electrode, a metal elemental electrode or an alloy electrode. The material of the doped metal oxide electrode includes one or more of indium-doped tin oxide, fluorine-doped tin oxide, antimony-doped tin oxide, aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, magnesium-doped zinc oxide, aluminum-doped magnesium oxide, cadmium-doped zinc oxide. The composite electrode includes AZO / Ag / AZO, AZO / Al / AZO, ITO / Ag / ITO, ITO / Al / ITO, ZnO / Ag / ZnO, ZnO / Al / ZnO, TiO 2 / Ag / TiO 2 、TiO 2 / Al / TiO 2 、ZnS / Ag / ZnS, ZnS / Al / ZnS, Ca / Al, LiF / Ca, LiF / Al, BaF 2 / Al, CsF / Al, CaCO 3 / Al or BaF 2 / Ca / Al. The material of the metal elemental electrode includes one or more of Ag, Ni, Pt, Au, Ir, Cu, Mo, Al, Ca, Mg and Ba. The alloy electrode includes an Au:Mg alloy electrode or an Ag:Mg alloy electrode.

[0154] It can be understood that the first electrode is the anode 10 and the second electrode is the cathode 30; or the first electrode is the cathode 30 and the second electrode is the anode 10.

[0155] The functional layer 20 includes one or more of a hole injection layer 21, a hole transport layer 22, a light-emitting layer 23 and an electron transport layer 24.

[0156] It can be understood that the methods for forming the hole injection layer 21, the hole transport layer 22, the light-emitting layer 23, and the electron transport layer 24 can be realized by conventional techniques in the art, such as the physical method or the chemical method described above.

[0157] The material of the hole injection layer 21 may also be a material known in the art for the hole injection layer, and may be selected from, but not limited to, 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (HAT-CN), PEDOT, PEDOT:PSS, PEDOT:PSS doped with derivatives of s-MoO 3 (PEDOT:PSS:s-MoO 3) one or more of 4,4',4'-tris(N-(3-methylphenyl)-N-phenylamino)triphenylamine (m-MTDATA), tetracyanoquinodimethane (F4-TCQN), copper phthalocyanine, nickel oxide, molybdenum oxide, tungsten oxide, vanadium oxide, molybdenum sulfide, tungsten sulfide, and copper oxide.

[0158] The material of the hole transport layer 22 can be a material known in the art for hole transport layers. For example, it can be selected from but not limited to 4,4'-N,N'-dicarbazolyl-biphenyl (CBP), poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA), N,N'-diphenyl-N,N'-bis(1-naphthyl)-1,1'-biphenyl-4,4”-diamine (α-NPD), N,N'-diphenyl-N,N'-bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine (TPD), poly(N,N' bis(4-butylphenyl)-N,N'-bis(phenyl)benzidine) (Poly-TPD), N,N'-bis(3-methylphenyl)-N,N'-bis(phenyl)-spiro(spiro-TPD), N,N'-bis(4-(N,N'-diphenyl-amino)phenyl)-N,N'-diphenylbenzidine (DNTPD), 4,4',4'-tris(N-carbazolyl)-triphenylamine (TCTA), 4,4',4'-tris(N-3-methylphenyl-N-phenylamino)triphenylamine (m-MTDATA), poly[(9,9'-dioctylfluorene-2,7-diyl)-co-(4,4'-(N-(4-sec-butylphenyl)diphenylamine))] (TFB), poly(N-vinylcarbazole) (PVK) and its derivatives, N,N'-bis(1-naphthyl)-N,N'-diphenyl-1,1'-biphenyl-4-4'-diamine (NPB), spiro-NPB, poly(phenylene vinylene) (PPV), poly[2-methoxy-5-(2-ethylhexoxy)-1,4-phenylene vinylene] (MEH-PPV), poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylene vinylene] (MOMO-PPV), 2,2',7,7'-tetra[N,N-bis(4-methoxyphenyl)amino]-9,9'-spirobifluorene (spiro-omeTAD), 4,4'-cyclohexylbis[N,N-bis(4-methylphenyl)aniline] (TAPC), 1,3-bis(carbazol-9-yl)benzene (MCP), polyaniline, polypyrrole, poly(p-)phenylene vinylene, aromatic tertiary amines, polynuclear aromatic tertiary amines, 4,4'-bis(p-carbazolyl)-1,1'-biphenyl compounds, N,N,N',N'-tetraarylbenzidine, PEDOT:PSS and its derivatives, polymethacrylate and its derivatives, poly(9,9-octylfluorene) and its derivatives, poly(spirofluorene) and its derivatives, doped graphene, undoped graphene, C60, doped or undoped NiO, doped or undoped MoO 3 、doped or undoped WO 3 、doped or undoped V 2 O 5 、doped or undoped p-type gallium nitride, doped or undoped CrO 3One or more of doped or undoped CuO.

[0159] In some embodiments, in the doped metal oxide particles, the mass fraction of the doping element in the doped metal oxide particles is 1-20%, for example, 1-10%, 5-15%, 8-18%, 10-20%, etc. Within the range of the doping amount, the stability and electron transport performance of the electron transport layer 24 can be effectively improved.

[0160] The material of the light-emitting layer 23 may include, but is not limited to, one or more of organic light-emitting materials and quantum dot light-emitting materials.

[0161] The organic light-emitting material may include, but is not limited to, CBP:Ir(mppy) 3 (4,4'-Bis(N-carbazolyl)-1,1'-biphenyl: tris[2-(p-tolyl)pyridine iridium(III)), TCTX:Ir(mmpy)(4,4',4”-tris(carbazol-9-yl)triphenylamine: tris[2-(p-tolyl)pyridine iridium), diaryl anthracene derivatives, stilbene aromatic derivatives, pyrene derivatives, fluorene derivatives, TBPe fluorescent materials, TTPX fluorescent materials, TBRb fluorescent materials, DBP fluorescent materials, delayed fluorescence materials, TTA materials, TADF (thermally activated delayed) materials, polymers containing B-N covalent bonds, HLCT (hybrid local charge transfer excited state) materials, Exciplex (excimer complex) light-emitting materials, polyacetylene and its derivatives, poly(p-phenylene) and its derivatives, polythiophene and its derivatives, polyfluorene and its derivatives, etc.

[0162] The quantum dot light-emitting material may include, but is not limited to, one or more of single-structure quantum dots, core-shell structure quantum dots, and perovskite semiconductor materials.

[0163] The materials of the single-structure quantum dots, the core materials of the core-shell structure quantum dots, and the shell materials of the core-shell structure quantum dots may respectively include, but are not limited to, one or more of II-VI group compounds, IV-VI group compounds, III-V group compounds, and I-III-VI group compounds. The shell of the core-shell structure quantum dots includes one or more layers.

[0164] The II-VI group compounds may include, but are not limited to, one or more of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, and HgZnSTe. The IV-VI group compounds may include, but are not limited to, one or more of SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, SnPbSeTe, and SnPbSTe. The III-V group compounds may include, but are not limited to, one or more of GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, and InAlPSb. The I-III-VI group compounds may include, but are not limited to, one or more of CuInS 2 , CuInSe 2 , and AgInS 2 .

[0165] As an example, the quantum dots with a core-shell structure may include, but are not limited to, one or more of CdSe / CdSeS / CdS, InP / ZnSeS / ZnS, CdZnSe / ZnSe / ZnS, CdSeS / ZnSeS / ZnS, CdSe / ZnS, CdSe / ZnSe / ZnS, ZnSe / ZnS, ZnSeTe / ZnS, CdSe / CdZnSeS / ZnS, and InP / ZnSe / ZnS.

[0166] The perovskite semiconductor material may include, but is not limited to, doped or undoped inorganic perovskite semiconductors, or organic-inorganic hybrid perovskite semiconductors. The general structural formula of the inorganic perovskite semiconductor is AMX 3 , where A is a Cs + ion, M is a divalent metal cation, including Pb 2+ , Sn 2+ , Cu 2+ , Ni 2+ , Cd 2+ , Cr 2+ , Mn 2+ , Co 2+ , Fe 2+ , Ge 2+ , Yb 2+ , Eu 2+ or more of them, and X is a halogen anion, including Cl - , Br - , I - or more of them. The general structural formula of the organic-inorganic hybrid perovskite semiconductor is BMX 3 , where B is an organic amine cation, including CH 3 (CH 2 ) n-2 NH 3 + or [NH 3 (CH 2 ) n NH 3 2+ , where n≥2, M is a divalent metal cation, including Pb 2+ , Sn 2+ , Cu 2+ , Ni 2+ , Cd 2+ , Cr 2+ , Mn 2+ , Co 2+ , Fe 2+ , Ge 2+ , Yb 2+ , Eu 2+ or more of them, and X is a halogen anion, including Cl - , Br - , I - or more of them.

[0167] ​The material of the electron transport layer 24 is a material known in the art for electron transport layers, and can be selected from, for example, but not limited to, one or more of inorganic electron transport materials and organic electron transport materials. The inorganic electron transport materials include, but are not limited to, one or more of metal oxides, doped metal oxides, IIB-VIA group semiconductor materials, IIIA-VA group semiconductor materials, and IB-IIIA-VIA group semiconductor materials. Specifically, the metal oxides are selected from, but not limited to, ZnO, TiO 2 、SnO 2 、ZrO 2 、Ta 2 O 5 and the like; the metal oxides in the doped metal oxides are selected from, but not limited to, ZnO, TiO 2 、SnO 2 、ZrO 2 、Ta 2 O 5 、Al 2 O 3 and the like, and the dopants in the doped metal oxides are selected from, but not limited to, one or several of Al, Mg, Li, Mn, Y, La, Cu, Ni, Zr, Ce, In, Ga, Sn. By way of example, the doped metal oxides can be aluminum-doped zinc oxide (AZO), lithium-doped zinc oxide (LZO), magnesium-doped zinc oxide (MZO), tin-doped zinc oxide, etc.; the IIB-VIA group semiconductor materials are selected from, but not limited to, one or more of ZnS, ZnSe, CdS; the IIIA-VA group semiconductor materials are selected from, but not limited to, one or more of InP, GaP; the IB-IIIA-VIA group semiconductor materials are selected from, but not limited to, one or more of CuInS, CuGaS. The organic electron transport materials include, but are not limited to, one or more of quinoxaline compounds, imidazole compounds, triazine compounds, fluorene-containing compounds, hydroxyquinoline compounds.

[0168] It can be understood that in some embodiments, the optoelectronic device 100 may further include functional layers that are conventionally used in optoelectronic devices and are helpful for improving the performance of optoelectronic devices, such as an electron blocking layer, a hole blocking layer, an electron injection layer, an interface modification layer, etc.

[0169] It can be understood that the materials of the respective layers of the optoelectronic device 100 can be adjusted according to the light emission requirements of the optoelectronic device 100.

[0170] In some embodiments, the optoelectronic device further includes a substrate, and the substrate is disposed on the surface of the first electrode facing away from the light-emitting layer 23.

[0171] The substrate may be a rigid substrate or a flexible substrate. In some embodiments, the material of the substrate may include, but is not limited to, one or more of glass, silicon wafer, polycarbonate, polymethyl methacrylate, polyethylene terephthalate, polyethylene naphthalate, polyamide, and polyethersulfone.

[0172] It can be understood that the optoelectronic device 100 may be a normal optoelectronic device or an inverted optoelectronic device. The optoelectronic device 100 may be a quantum dot optoelectronic device or an organic optoelectronic device.

[0173] It can be understood that when the optoelectronic device 100 further includes functional layers that are commonly used in optoelectronic devices and are helpful for improving the performance of the optoelectronic device, such as an electron blocking layer, a hole blocking layer, an electron injection layer, an interface modification layer, etc., the preparation method of the optoelectronic device 100 may further include the step of preparing the above functional layers by using conventional techniques in the art.

[0174] Fifth aspect, please refer to Figure 10 , the embodiments of the present application further provide an optoelectronic device 100 prepared by the preparation method described above. The optoelectronic device 100 includes a stacked anode 10, a functional layer 20, and a cathode 30, wherein at least one of the anode 10 and the cathode 30 is the composite electrode 101 described above.

[0175] In some embodiments, when the anode 10 is the composite electrode 101, the conductive nanowire layer 1 of the composite electrode 101 is bonded to the functional layer 20, or the conductive polymer layer 4 of the composite electrode 101 is bonded to the functional layer 20.

[0176] In some embodiments, when the cathode 30 is the composite electrode 101, the conductive nanowire layer 1 of the composite electrode 101 is bonded to the functional layer 20, or the conductive polymer layer 4 of the composite electrode 101 is bonded to the functional layer 20.

[0177] The functional layer 20 is as described above and will not be elaborated here.

[0178] Sixth aspect, the present application also relates to a display device, and the display device includes the optoelectronic device 100.

[0179] The display device may be any electronic product with a display function. The electronic product includes, but is not limited to, a smart phone, a tablet computer, a notebook computer, a digital camera, a digital video camera, a smart wearable device, a smart weighing electronic scale, a vehicle-mounted display, a television, or an e-book reader. Among them, the smart wearable device may be, for example, a smart bracelet, a smart watch, a virtual reality (VR) helmet, etc.

[0180] The present application will be specifically described below through specific embodiments. The following embodiments are only partial embodiments of the present application and do not limit the present application.

[0181] Embodiment 1

[0182] Dissolve 1 g of zinc oxide powder in 15 ml of dimethyl sulfoxide, add 0.5 g of ethylene glycol monobutyl ether (EGDE) as a surfactant to form a zinc oxide solution, then continuously drop the zinc oxide solution onto the substrate and heat-treat it at 80 °C for 30 minutes to grow conductive nanowire arrays on the substrate;

[0183] Dissolve PEDOT:PSS in water to form a conductive polymer solution with a concentration of 10 mg / mL. Spin-coat the conductive polymer solution on the conductive nanowire layer 1, where the spin-coating speed is 3000 rpm / s and the time is 30 s, to obtain a conductive nanowire layer 1 with a thickness of 50 nm and a conductive polymer layer 4 with a thickness of 15 nm bonded to the surface of the conductive nanowire layer 1;

[0184] Add 0.1 g of TiO 2 powder to 15 ml of dimethyl sulfoxide, add 1 ml of the surfactant polyethylene glycol (PEG), mix well to form an interfacial modification material solution, spin-coat the interfacial modification material solution on the conductive polymer layer 4, and dry it. Among them, the spin-coating speed is 3000 rpm / s, the spin-coating time is 30 s, the drying temperature is 100 °C, and the drying time is 10 minutes to obtain an interfacial modification layer 3 with a thickness of 10 nm;

[0185] Spin-coat a graphene dispersion with a concentration of 5 mg / mL on the interfacial modification layer 3, where the spin-coating speed is 1000 rpm / s and the spin-coating time is 30 s, to form a graphene layer 2 with a thickness of 40 nm, and obtain a composite electrode 101.

[0186] Embodiment 2

[0187] Heat indium oxide powder in an inert gas Ar, where the mass ratio of indium oxide powder to the inert gas is 1:2, to form indium oxide vapor and grow conductive nanowire arrays on the substrate;

[0188] Dissolve PT in dimethyl sulfoxide to form a conductive polymer solution with a concentration of 10 mg / mL. Spray the conductive polymer solution on the conductive nanowire array at a spraying speed of 2 mL / min to obtain a conductive nanowire layer 1 with a thickness of 50 nm and a conductive polymer layer 4 with a thickness of 15 nm bonded to the surface of the conductive nanowire layer 1;

[0189] Add 0.1 g of SnO 2The powder is added to 15 ml of dimethyl sulfoxide, and 1 ml of surfactant sodium octylbenzenesulfonate is added and mixed well to form an interfacial modification material solution. The interfacial modification material solution is sprayed onto the conductive polymer layer 4 at a spraying speed of 2 mL / min and dried. Among them, the spin coating speed is 3000 rpm / s, the spin coating time is 30 s, the drying temperature is 120 °C, and the drying time is 15 minutes to obtain an interfacial modification layer 3 with a thickness of 10 nm;

[0190] The graphene dispersion liquid with a concentration of 5 mg / mL is sprayed onto the interfacial modification layer 3 at a spraying speed of 2 mL / min to form a graphene layer 2 with a thickness of 40 nm, and a composite electrode 101 is obtained.

[0191] Example 3

[0192] Dissolve 1 g of SnO 2 powder in 10 ml of dimethyl sulfoxide, and add 0.5 g of ethylene glycol monobutyl ether (EGDE) as a surfactant to form SnO 2 solution. Then, the SnO 2 solution is continuously dropped onto the substrate and heat-treated at 100 °C for 30 minutes to grow a conductive nanowire array of SnO 2 on the substrate;

[0193] Dissolve PBI in ethanol to form a conductive polymer solution with a concentration of 10 mg / mL. The conductive polymer solution is brushed onto the conductive nanowire layer 1 at a speed of 2 mL / min to obtain a conductive nanowire layer 1 with a thickness of 50 nm and a conductive polymer layer 4 with a thickness of 15 nm bonded to the surface of the conductive nanowire layer 1;

[0194] Add 0.1 g of fluorine-doped tin dioxide powder to 15 ml of dimethyl sulfoxide, add 1 ml of surfactant CTAB, and mix well to form an interfacial modification material solution. The interfacial modification material solution is brushed onto the conductive polymer layer 4 at a speed of 2 mL / min and dried. Among them, the drying temperature is 80 °C and the drying time is 20 minutes to obtain an interfacial modification layer 3 with a thickness of 10 nm;

[0195] The graphene dispersion liquid with a concentration of 5 mg / mL is spin-coated onto the interfacial modification layer 3. Among them, the spin coating speed is 1000 rpm / s and the spin coating time is 30 s to form a graphene layer 2 with a thickness of 40 nm, and a composite electrode 101 is obtained.

[0196] Example 4

[0197] Add 0.5 g of the surfactant ethylene glycol monobutyl ether (EGDE) to 10 ml of a standard calcium oxide solution (Wengjiang Reagent, model: PB02805) with a concentration of 1.5 mol / L to form a CaO mixed solution. Then, continuously drop the CaO mixed solution onto the substrate and heat-treat it at a high temperature of 200 °C for 30 minutes to grow conductive nanowire arrays of CaO on the substrate.

[0198] Dissolve PA in toluene, add 1 ml of the surfactant polyethylene glycol (PEG), and mix well to form an interfacial modification material solution. Brush the interfacial modification material solution onto the conductive polymer layer 4 at a speed of 2 mL / min and dry it. The drying temperature is 60 °C and the drying time is 30 minutes to obtain an interfacial modification layer 3 with a thickness of 10 nm.

[0199] Spin-coat a graphene dispersion solution with a concentration of 5 mg / mL on the interfacial modification layer 3. The spin-coating speed is 1000 rpm / s and the spin-coating time is 30 s to form a graphene layer 2 with a thickness of 40 nm, obtaining a composite electrode 101.

[0200] Example 5

[0201] This example is basically the same as Example 1, except that the high-temperature heat treatment temperature in this example is 70 °C.

[0202] Example 6

[0203] This example is basically the same as Example 1, except that the high-temperature heat treatment temperature in this example is 90 °C.

[0204] Example 7

[0205] This example is basically the same as Example 1, except that the thickness of the conductive nanowire layer 1 in this example is 30 nm.

[0206] Example 8

[0207] This example is basically the same as Example 1, except that the thickness of the conductive nanowire layer 1 in this example is 100 nm.

[0208] Example 9

[0209] This example is basically the same as Example 1, except that the thickness of the conductive polymer layer 4 in this example is 5 nm.

[0210] Example 10

[0211] This example is basically the same as Example 1, except that the thickness of the conductive polymer layer 4 in this example is 20 nm.

[0212] Example 11

[0213] This embodiment is basically the same as Embodiment 1, except that the thickness of the interface modification layer 3 in this embodiment is 5 nm.

[0214] Embodiment 12

[0215] This embodiment is basically the same as Embodiment 1, except that the thickness of the interface modification layer 3 in this embodiment is 15 nm.

[0216] Embodiment 13

[0217] This embodiment is basically the same as Embodiment 1, except that the thickness of the graphene layer 2 in this embodiment is 10 nm.

[0218] Embodiment 14

[0219] This embodiment is basically the same as Embodiment 1, except that the thickness of the graphene layer 2 in this embodiment is 50 nm.

[0220] Embodiment 15

[0221] This embodiment is basically the same as Embodiment 1, except that when preparing the interface modification layer 3 in this embodiment, carbon nanotubes are used to replace TiO in Embodiment 1 2 .

[0222] Embodiment 16

[0223] This embodiment is basically the same as Embodiment 1, except that the composite electrode 101 in this embodiment only includes a conductive nanowire layer 1, a conductive polymer layer 4, and a graphene layer 2.

[0224] Embodiment 17

[0225] Spin-coat a graphene dispersion solution with a concentration of 5 mg / mL on the substrate, where the spin-coating speed is 1000 rpm / s and the spin-coating time is 30 s to form a graphene layer 2 with a thickness of 40 nm;

[0226] Add 0.1 g of TiO 2 powder to 15 ml of dimethyl sulfoxide, add 1 ml of the surfactant polyethylene glycol (PEG), mix well to form an interface modification material solution, spin-coat the interface modification material solution on the graphene layer 2, and dry it. Among them, the spin-coating speed is 3000 rpm / s, the spin-coating time is 30 s, the drying temperature is 100 °C, and the drying time is 10 minutes to obtain an interface modification layer 3 with a thickness of 10 nm;

[0227] Dissolve 1 g of zinc oxide powder in 15 ml of dimethyl sulfoxide, add 0.5 g of ethylene glycol monobutyl ether (EGDE) as a surfactant to form a zinc oxide solution, then dropwise coat the zinc oxide solution on the interface modification layer 3, and heat-treat it at 80 °C for 30 minutes to grow conductive nanowire arrays of zinc oxide on the substrate;

[0228] Dissolve PEDOT:PSS in water to form a conductive polymer solution with a concentration of 10 mg / mL. Spin-coat the conductive polymer solution on the conductive nanowire layer 1, where the spin-coating speed is 3000 rpm / s and the time is 30 s, to obtain a conductive nanowire layer 1 with a thickness of 50 nm and a conductive polymer layer 4 with a thickness of 15 nm bonded to the surface of the conductive nanowire layer 1, thus obtaining the composite electrode 101.

[0229] Comparative Example 1

[0230] This comparative example is basically the same as Example 1, except that the composite electrode 101 of this comparative example only includes the conductive nanowire layer 1.

[0231] Comparative Example 2

[0232] This comparative example is basically the same as Example 1, except that the composite electrode 101 of this comparative example only includes the conductive polymer layer 4.

[0233] Comparative Example 3

[0234] This comparative example is basically the same as Example 1, except that the composite electrode 101 of this comparative example only includes the interface modification layer 3.

[0235] Comparative Example 4

[0236] This comparative example is basically the same as Example 1, except that the composite electrode 101 of this comparative example only includes the graphene layer 2.

[0237] Comparative Example 5

[0238] This comparative example is basically the same as Example 1, except that the composite electrode 101 of this comparative example only includes the conductive nanowire layer 1 and the conductive polymer layer 4.

[0239] Comparative Example 6

[0240] This comparative example is basically the same as Example 1, except that the composite electrode 101 of this comparative example only includes the conductive nanowire layer 1, the conductive polymer layer 4, and the interface modification layer 3.

[0241] Conductivity, stability, light transmittance, and water and oxygen corrosion resistance tests were respectively carried out on the composite electrodes of Examples 1 to 17 and Comparative Examples 1 to 6, and the test results are shown in Table 1.

[0242] The conductivity was tested by the four-probe resistance measurement method. The current and voltage values on the composite electrode were measured, and the resistance value of the composite electrode was obtained by calculation. The smaller the resistance value, the better the conductivity of the composite electrode;

[0243] The test method for stability was as follows: The change rate of the resistance of the composite electrode after being energized for 5 h at a current of 2 mA was tested;

[0244] The test method for light transmittance was as follows: The spectrophotometer method was used. The light beam emitted by the light source passed through the material sample, and then the light intensity transmitted through the sample was measured by a photodetector and compared with the light intensity without the sample. The calculation formula for the transmittance was: Transmittance (%) = (transmitted light intensity / light intensity without sample) × 100%. According to the measurement results of the transmittance, the light transmittance performance of the material could be evaluated;

[0245] The test method for water and oxygen corrosion resistance was: the salt spray corrosion test method. The test conditions were a salt spray concentration of 5% NaCl, a temperature of 35 °C, and a relative humidity of 95%. The time when the corrosion phenomenon occurred was recorded.

[0246] Table 1:

[0247]

[0248]

[0249] As can be seen from Table 1:

[0250] Compared with the composite electrodes of Comparative Examples 1-6, the composite electrodes of Examples 1-17 have higher electrical conductivity, stability, light transmittance and resistance to water and oxygen corrosion. The reason may be that the conductive nanowires in the conductive nanowire layer of the composite electrodes of Examples 1-17 have a high charge transfer efficiency; and the second conductive polymer filled in the gaps of the conductive nanowire array can increase the contact area between the conductive nanowires, the first conductive polymer and the second conductive polymer, providing more charge transfer interfaces, and further improving the charge transfer efficiency of the composite electrode; furthermore, the interface modification layer of the composite electrode can improve the interface matching, with a high interface contact area and a small interface contact resistance, which can effectively reduce the scattering and loss of charges at the interface, thereby improving the charge transfer efficiency of the composite electrode; on the other hand, the material of the interface modification layer has good electrical conductivity and transparency, which can provide more conductive channels and better electron transfer paths, facilitating the transfer of charges between different layers, and further improving the charge transfer efficiency of the composite electrode; on the one hand, when the composite electrode is used in a device, the material of the interface modification layer has good chemical stability and durability. If the interface modification layer is located outside the conductive nanowire layer (i.e., the interface modification layer is closer to the external environment), it can prevent oxygen or moisture in the environment from entering the conductive nanowire layer, thereby enhancing the antioxidant, moisture resistance and durability of the composite electrode.

[0251] Device Example 1

[0252] A conductive glass substrate with an ITO anode 10 having a thickness of 100 nm is provided. The ITO conductive glass is cleaned with a cleaner to preliminarily remove the stains on the surface, and then ultrasonically cleaned in deionized water, acetone, absolute ethanol and deionized water for 20 min respectively to remove the impurities on the surface. Finally, it is dried with high-purity nitrogen.

[0253] In a glove box, the PEDOT:PSS material is spin-coated on the first electrode, where the spin-coating speed is 4000 rpm, the time is 30 s, and it is annealed at 150 °C for 15 min to obtain a hole injection layer 21 with a thickness of 40 nm.

[0254] The TFB material is spin-coated on the hole injection layer 21, where the spin-coating speed is 3000 rpm, the time is 30 s, and it is annealed at 150 °C for 30 min to obtain a hole transport layer 22 with a thickness of 30 nm.

[0255] CdZnSe quantum dots are spin-coated on the hole transport layer 22, where the spin-coating speed is 1500 rpm, the time is 30 s, and it is annealed at 100 °C for 5 min to obtain a light-emitting layer 23 with a thickness of 30 nm.

[0256] Spin-coat an ethanol solution of ZnO on the light-emitting layer 23, where the spin-coating speed is 4000 rpm, the time is 30 s, and anneal at 100 °C for 5 min to obtain an electron transport layer 24 with a thickness of 35 nm;

[0257] Use the method of Example 1 to prepare a composite electrode 101 on the electron transport layer 24 to obtain a cathode 30;

[0258] Encapsulate in an environment where both the oxygen content and the water content are lower than 0.1 ppm to obtain an optoelectronic device 100.

[0259] Device Examples 2-16

[0260] Device Examples 2-16 are basically the same as Device Example 1, except that in Device Examples 2-16, the method of Examples 2-16 is used to prepare a composite electrode 101 on the electron transport layer 24 to obtain a cathode 30.

[0261] Device Example 17

[0262] Device Example 17 is basically the same as Device Example 1, except that in Device Example 17, the method of Example 17 is used to prepare a composite electrode 101 on a glass substrate to obtain an anode 10, and the preparation method of the cathode 30 in Device Example 17 is: evaporate Ag on the electron transport layer 24 to obtain a cathode with a thickness of 80 nm.

[0263] Device Example 18

[0264] Device Example 18 is basically the same as Device Example 1, except that in Device Example 18, the method of Example 16 is used to prepare a composite electrode 101 on a glass substrate to obtain an anode 10.

[0265] Device Example 19

[0266] Provide a conductive glass substrate with an Ag cathode 30 having a thickness of 80 nm. Clean the ITO conductive glass with a cleaner to initially remove the stains on the surface, and then ultrasonically clean it in deionized water, acetone, absolute ethanol, and deionized water for 20 min in sequence to remove the impurities on the surface. Finally, dry it with high-purity nitrogen;

[0267] Spin-coat an ethanol solution of ZnO on the first electrode, where the spin-coating speed is 4000 rpm, the time is 30 s, and anneal at 100 °C for 5 min to obtain an electron transport layer 24 with a thickness of 35 nm;

[0268] Spin-coat CdZnSe quantum dots on the electron transport layer 24, where the spin-coating speed is 1500 rpm, the time is 30 s, and anneal at 100 °C for 5 min to obtain a light-emitting layer 23 with a thickness of 30 nm;

[0269] Spin-coat the TFB material on the light-emitting layer 23, where the spin-coating speed is 3000 rpm, the time is 30 s, and anneal at 150 °C for 30 min to obtain a hole-transporting layer 22 with a thickness of 30 nm;

[0270] Spin-coat the PEDOT:PSS material on the hole-transporting layer 22, where the spin-coating speed is 4000 rpm, the time is 30 s, and anneal at 150 °C for 15 min to obtain a hole-injecting layer 21 with a thickness of 40 nm;

[0271] Use the method of Example 1 to prepare the composite electrode 101 on the hole-injecting layer 21 to obtain an anode 10 with a thickness of 80 nm;

[0272] Encapsulate in an environment where both the oxygen content and the water content are lower than 0.1 ppm to obtain the optoelectronic device 100.

[0273] Device Example 20

[0274] Device Example 20 is basically the same as Device Example 19, except that in Device Example 20, the method of Example 16 is used to prepare the composite electrode 101 on the glass substrate to obtain the anode 10, and the preparation method of the anode 10 in Device Example 20 is: evaporate ITO on the hole-injecting layer 21 to obtain an anode 10 with a thickness of 80 nm.

[0275] Device Example 21

[0276] Device Example 21 is basically the same as Device Example 19, except that in Device Example 21, the method of Example 16 is used to prepare the composite electrode 101 on the glass substrate to obtain the anode 10.

[0277] Device Comparative Examples 1-6

[0278] Device Comparative Examples 1-6 are basically the same as Device Example 1, except that in Device Comparative Examples 1-6, the methods of Comparative Examples 1-6 are used to prepare the composite electrode 101 on the electron-transporting layer 24 to obtain the second electrode (cathode).

[0279] Perform the maximum brightness L max , external quantum efficiency EQE, and lifetime T95@1000 nit tests on the optoelectronic devices of Device Examples 1-21 and Device Comparative Examples 1-6. The test results are shown in Table 2.

[0280] Among them, the maximum brightness L maxThe test method for the external quantum efficiency EQE is as follows: Using the Fosida FPD optical property measurement equipment, an efficiency test system built by controlling the QE PRO spectrometer, Keithley 2400, and Keithley 6485 through LabView, parameters such as voltage, current, brightness, and emission spectrum are measured, and the maximum brightness L is recorded. max and the external quantum efficiency EQE of the device is obtained through calculation;

[0281] The test method for the lifetime T95@1000nit is as follows: In CDA gas, under constant current or voltage drive, the time it takes for the brightness of the device to decay to a certain proportion of the maximum brightness is measured. The time when the brightness decays to 95% of the maximum brightness is defined as T95, and this lifetime is the measured lifetime. To shorten the lifetime test cycle, the device lifetime test is usually carried out by accelerating the device aging at high brightness, and the lifetime at low brightness is obtained by fitting through the decay fitting formula. For example, the lifetime at 1000nits is denoted as T95@1000nits, and the calculation formula is:

[0282]

[0283] where T95 L is the lifetime at low brightness, generally taking the lifetime at 1000nits, T95 H is the lifetime at high brightness, that is, the measured lifetime, L H is the maximum brightness to which the device is accelerated, L L is generally 1000nits, A is the acceleration factor, taking 1.7. Among them, the constant current is 2mA.

[0284] Table 2:

[0285]

[0286]

[0287] It can be seen from Table 1 that:

[0288] Compared with the optoelectronic devices of Comparative Examples 1-6 of the device, the optoelectronic devices of Examples 1-21 of the device have higher maximum brightness, higher luminous efficiency, and longer lifetime. It can be seen that using the composite electrode 101 of the present application as the cathode or anode of the optoelectronic device can effectively improve the maximum brightness, higher luminous efficiency, and longer lifetime of the optoelectronic device. The reason may be that the composite electrode 101 of the present application has properties such as high charge transport efficiency and stability.

[0289] The above has introduced in detail the technical solutions provided by the embodiments of the present application. Specific examples are used herein to elaborate on the principle and implementation manner of the present application. The description of the above embodiments is only used to help understand the method and its core idea of the present application; at the same time, for those skilled in the art, according to the idea of the present application, there will be changes in the specific implementation manner and application scope. In summary, the content of this specification should not be construed as a limitation to the present application.

Claims

1. A composite electrode, characterized in that, it comprises a stacked conductive nanowire layer and a graphene layer, and the conductive nanowire layer includes conductive nanowires and a first conductive polymer disposed in the gaps between the conductive nanowires.

2. The composite electrode according to claim 1, characterized in that, the conductive nanowires are arranged in an array; and / or the material of the conductive nanowires includes a first conductive metal oxide, and the first conductive metal oxide includes one or more of zinc oxide, calcium oxide, gallium oxide, indium oxide, tin oxide, lead oxide, and cadmium oxide.

3. The composite electrode according to claim 2, characterized in that, the first conductive metal oxide further includes a first doping element, and the first doping element includes one or more of thorium, scandium, lanthanum, cerium, copper, iron, cobalt, lithium, and potassium.

4. The composite electrode according to claim 1, characterized in that, the first conductive polymer includes one or more of polycarbazole, polythiophene, polyacrylonitrile, polybenzimidazole, and polyacetylene.

5. The composite electrode according to claim 2, characterized in that, the conductive nanowires are perpendicular to, intersect with, or parallel to the graphene layer in their length direction; and / or the average diameter of the conductive nanowires is 1 - 10 nm; and / or the average length of the conductive nanowires is 10 - 100 nm; and / or the spacing between the conductive nanowires is 1 - 80 nm; and / or the thickness of the conductive nanowire layer is 30 - 100 nm; and / or the thickness of the graphene layer is 10 - 50 nm.

6. The composite electrode according to claim 1, characterized in that, The composite electrode further includes an interfacial modification layer, which is located between the conductive nanowire layer and the graphene layer. The interfacial modification layer includes one or more of conductive metal oxide particles and carbon nanotubes. The material of the conductive metal oxide particles includes a second conductive metal oxide, and the second conductive metal oxide includes TiO 2 , SnO 2 , ITO, FTO, IZO, AgO, or one or more thereof.

7. The composite electrode according to claim 6, characterized in that, the second conductive metal oxide is further doped with a second doping element, and the second doping element includes one or more of thorium, scandium, lanthanum, cerium, copper, iron, cobalt, lithium, and potassium; and / or the thickness of the interface modification layer is 5 - 15 nm.

8. The composite electrode according to claim 6, characterized in that, the composite electrode further includes a conductive polymer layer, the conductive polymer layer is located between the conductive nanowire layer and the interface modification layer, or the conductive polymer layer is disposed on the surface of the conductive nanowire layer away from the interface modification layer.

9. The composite electrode according to claim 8, characterized in that, the conductive polymer layer includes a second conductive polymer, and the second conductive polymer includes one or more of polycarbazole, polythiophene, polyacrylonitrile, polybenzimidazole, and polyacetylene; and / or the thickness of the conductive polymer layer is 5 - 20 nm.

10. An optoelectronic device, comprising a stacked anode, a functional layer, and a cathode, characterized in that, at least one of the anode and the cathode is a composite electrode, the composite electrode includes a stacked conductive nanowire layer and a graphene layer, the conductive nanowire layer includes conductive nanowires and a first conductive polymer filled in the gaps between the conductive nanowires, and the conductive nanowire layer is close to the functional layer.

11. The optoelectronic device according to claim 10, characterized in that, the conductive nanowires are arranged in an array; and / or The material of the conductive nanowire includes a first conductive metal oxide, and the first conductive metal oxide includes one or more of zinc oxide, calcium oxide, gallium oxide, indium oxide, tin oxide, lead oxide, and cadmium oxide; and / or The first conductive polymer includes one or more of polycarbazole, polythiophene, polyacrylonitrile, polybenzimidazole, and polyacetylene; and / or The conductive nanowire is perpendicular to, intersects with, or is parallel to the graphene layer.

12. The optoelectronic device according to claim 10, characterized in that The composite electrode further includes an interfacial modification layer, which is located between the conductive nanowire layer and the graphene layer. The interfacial modification layer includes one or more of conductive metal oxide particles and carbon nanotubes. The material of the conductive metal oxide particles includes a second conductive metal oxide, and the second conductive metal oxide includes TiO 2 , SnO 2 , ITO, FTO, IZO, AgO, or one or more thereof.

13. The optoelectronic device according to claim 12, characterized in that The composite electrode further includes a conductive polymer layer, the conductive polymer layer is located between the conductive nanowire layer and the interface modification layer, and the conductive nanowire layer is bonded to the functional layer; or, The conductive polymer layer is disposed on the surface of the conductive nanowire layer away from the interface modification layer, and the conductive polymer layer is bonded to the functional layer.

14. The optoelectronic device according to claim 10, characterized in that The functional layer includes a hole injection layer, and the material of the hole injection layer includes one or more of 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene, PEDOT, PEDOT:PSS, PEDOT:PSS doped with derivatives of s-MoO 3 , 4,4',4'-tris(N-3-methylphenyl-N-phenylamino)triphenylamine, tetracyanoquinodimethane, copper phthalocyanine, nickel oxide, molybdenum oxide, tungsten oxide, vanadium oxide, molybdenum sulfide, tungsten sulfide, and copper oxide; and / or The functional layer includes a hole transport layer, and the materials of the hole transport layer include 4,4'-N,N'-dicarbazolyl-biphenyl, poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine], N,N'-diphenyl-N,N'-bis(1-naphthyl)-1,1'-biphenyl-4,4”-diamine, N,N'-diphenyl-N,N'-bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine, poly(N,N'-bis(4-butylphenyl)-N,N'-bis(phenyl)benzidine), N,N'-bis(3-methylphenyl)-N,N'-bis(phenyl)-spiro, N,N'-bis(4-(N,N'-diphenyl-amino)phenyl)-N,N'-diphenylbenzidine, 4,4',4'-tris(N-carbazolyl)-triphenylamine, 4,4',4'-tris(N-3-methylphenyl-N-phenylamino)triphenylamine, poly[(9,9'-dioctylfluorene-2,7-diyl)-co-(4,4'-(N-(4-sec-butylphenyl)diphenylamine))], poly(N-vinylcarbazole) and its derivatives, N,N'-bis(1-naphthyl)-N,N'-diphenyl-1,1'-biphenyl-4-4'-diamine, spiro-NPB, poly(phenylene vinylene), poly[2-methoxy-5-(2-ethylhexoxy)-1,4-phenylene vinylene], poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylene vinylene], 2,2',7,7'-tetrakis[N,N-bis(4-methoxyphenyl)amino]-9,9'-spirobifluorene, 4,4'-cyclohexylbis[N,N-bis(4-methylphenyl)aniline], 1,3-bis(carbazol-9-yl)benzene, polyaniline, polypyrrole, poly(p-phenylene vinylene), aromatic tertiary amines, polynuclear aromatic tertiary amines, 4,4'-bis(p-carbazolyl)-1,1'-biphenyl compounds, N,N,N',N'-tetraarylbenzidine, PEDOT:PSS and its derivatives, polymethacrylate and its derivatives, poly(9,9-octylfluorene) and its derivatives, poly(spirofluorene) and its derivatives, doped graphene, undoped graphene, C60, doped or undoped NiO, doped or undoped MoO 3 , doped or undoped WO 3 , doped or undoped V 2 O 5 , doped or undoped p-type gallium nitride, doped or undoped CrO 3 , doped or undoped CuO, one or more of them; and / or The functional layer includes a light-emitting layer, and the material of the light-emitting layer includes one or more of an organic light-emitting material and a quantum dot light-emitting material. The organic light-emitting material includes one or more of 4,4'-bis(N-carbazolyl)-1,1'-biphenyl: tris[2-(p-tolyl)pyridineiridium(III)], 4,4',4''-tris(carbazol-9-yl)triphenylamine: tris[2-(p-tolyl)pyridineiridium, diarylanthracene derivatives, stilbene aromatic derivatives, pyrene derivatives, fluorene derivatives, TBPe fluorescent material, TTPX fluorescent material, TBRb fluorescent material, DBP fluorescent material, delayed fluorescence material, TTA material, thermally activated delayed material, a polymer containing a B-N covalent bond, a hybrid local charge transfer excited state material, an exciplex luminescent material, polyacetylene and its derivatives, poly(p-phenylene) and its derivatives, polythiophene and its derivatives, polyfluorene and its derivatives; The quantum dot light-emitting material includes one or more of a single-structure quantum dot, a core-shell structure quantum dot, and a perovskite semiconductor material. The materials of the single-structure quantum dot, the core material of the core-shell structure quantum dot, and the shell material of the core-shell structure quantum dot are each independently selected from one or more of II-VI group compounds, IV-VI group compounds, III-V group compounds, and I-III-VI group compounds. The shell layer of the core-shell structure quantum dot includes one or more layers;The II-VI compounds include one or more of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, and HgZnSTe; the IV-VI compounds include one or more of SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, SnPbSeTe, SnPbSTe; the III-V compounds include one or more of GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, and InAlPSb; the I-III-VI compounds include one or more of CuInS; 2 , CuInSe 2 and AgInS 2 ; the perovskite semiconductor material includes doped or undoped inorganic perovskite semiconductors or organic-inorganic hybrid perovskite semiconductors. The structural general formula of the inorganic perovskite semiconductor is AMX 3 , where A is a Cs + ion, M is a divalent metal cation, including Pb 2+ , Sn 2+ , Cu 2+ , Ni 2+ , Cd 2 + , Cr 2+ , Mn 2+ , Co 2+ , Fe 2+ , Ge 2+ , Yb 2+ , Eu 2+ One or more of the following, X is a halogen anion, including Cl - , Br - , I - One or more of the following; the structural general formula of the organic-inorganic hybrid perovskite semiconductor is BMX 3 , where B is an organic amine cation, including CH 3 (CH 2 ) n-2 NH 3 + or [NH 3 (CH 2 ) n NH 3 2+ , where n≥2, M is a divalent metal cation, including Pb 2+ , Sn 2+ , Cu 2+ , Ni 2+ , Cd 2+ , Cr 2+ , Mn 2+ , Co 2+ , Fe 2+ , Ge 2+ , Yb 2+ , Eu 2+ One or more of the following, X is a halogen anion, including Cl - , Br - , I - One or more of the following; and / or​ The functional layer includes an electron transport layer, and the material of the electron transport layer includes one or more of inorganic electron transport materials and organic electron transport materials. The inorganic electron transport materials include one or more of metal oxides, doped metal oxides, IIB-VIA group semiconductor materials, IIIA-VA group semiconductor materials, and IB-IIIA-VIA group semiconductor materials. The metal oxides include one or more of ZnO, TiO 2 , SnO 2 , ZrO 2 , Ta 2 O 5 ; The metal oxides in the doped metal oxides include one or more of ZnO, TiO 2 , SnO 2 , ZrO 2 , Ta 2 O 5 , Al 2 O 3 ; The dopants in the doped metal oxides include one or several of Al, Mg, Li, Mn, Y, La, Cu, Ni, Zr, Ce, In, Ga, Sn; The IIB-VIA group semiconductor materials include one or more of ZnS, ZnSe, CdS; The IIIA-VA group semiconductor materials include one or more of InP, GaP; The IB-IIIA-VIA group semiconductor materials include one or more of CuInS, CuGaS; The organic electron transport materials include one or more of quinoxaline compounds, imidazole compounds, triazine compounds, fluorene-containing compounds, hydroxyquinoline compounds.

15. A display device, characterized in that it includes the optoelectronic device according to any one of claims 10 to 14.

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