Composite electrode and preparation method thereof, photoelectric device and display device

Abstract

The invention provides a composite electrode, a preparation method, a photoelectric device and a flexible display device, and relates to the technical field of photoelectric devices. The composite electrode comprises liquid metal. According to the application, the liquid metal is arranged on the composite electrode, even if the composite electrode generates cracks under the condition of continuous bending, the cracks can be filled and repaired by the liquid metal, so that the performance stability of the composite electrode is improved.

Description

Technical Field

[0001] The present application relates to the technical field of optoelectronic devices, and in particular to a composite electrode and a preparation method thereof, an optoelectronic device and a display device. Background Art

[0002] Existing electrodes have poor flexibility and are prone to cracks when they are constantly bent, causing their performance to drop sharply. Summary of the invention

[0003] The present invention provides a composite electrode, a preparation method, a photoelectric device and a flexible display device to solve the problem that the current electrode has unstable performance under the condition of continuous bending.

[0004] In one aspect, the present application provides a composite electrode comprising liquid metal.

[0005] In some embodiments of the present application, the composite electrode includes an electrode layer and a liquid metal layer which are stacked.

[0006] In some embodiments of the present application, the composite electrode further includes a sealing layer, and the sealing layer is used to seal the liquid metal layer.

[0007] In some embodiments of the present application, the liquid metal is selected from metals or alloys that are liquid at room temperature.

[0008] In some embodiments of the present application, the liquid metal is selected from one or more of sodium-potassium alloy, gallium-indium eutectic alloy, and gallium.

[0009] In some embodiments of the present application, the sealing layer is in a micron glass ball array structure;

[0010] And / or, the material forming the sealing layer includes silicone resin, antioxidant and additive, and the mass ratio is silicone resin: antioxidant: additive = 100: (1-2): (1-5);

[0011] And / or, the material forming the sealing layer includes epoxy resin.

[0012] In some embodiments of the present application, a plurality of grooves are provided on one side of the electrode layer, and the liquid metal layer is at least partially disposed in the grooves;

[0013] And / or, the thickness of the electrode layer is between 15 nm and 25 nm;

[0014] And / or, the electrode layer is selected from a doped metal oxide particle electrode, a composite electrode of metal and metal oxide, a graphene electrode, a carbon nanotube electrode, a metal electrode or an alloy electrode; the material of the doped metal oxide particle electrode is selected from 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 and aluminum-doped magnesium oxide; the composite electrode of metal and metal oxide is selected from one or more of AZO / Ag / AZO, AZO / Al / AZO, ITO / Ag / ITO, ITO / Al / ITO, ZnO / Ag / ZnO, ZnO / Al / ZnO, TiO2 / Ag / TiO2, TiO2 / Al / TiO2, ZnS / Ag / ZnS, ZnS / Al / ZnS; the material of the metal electrode is selected from one or more of Ag, Al, Cu, Mo, Au, Pt, Si, Ca, Mg and Ba.

[0015] A second aspect of the present application provides a method for preparing a composite electrode, the preparation method comprising:

[0016] providing a substrate;

[0017] An electrode layer is prepared on one side of the substrate, wherein a plurality of grooves are provided on a side of the electrode layer away from the substrate;

[0018] applying liquid metal in the groove to form a liquid metal layer; or,

[0019] A substrate with a groove is provided, liquid metal is applied in the groove to form a liquid metal layer; and an electrode layer is prepared on the liquid metal layer.

[0020] A third aspect of the present application provides a photoelectric device, which includes a first electrode, a functional layer and a second electrode stacked in sequence; wherein at least one of the first electrode and the second electrode includes the composite electrode described in any one of claims 1 to 6 or is prepared by the method for preparing the composite electrode described in claim 7.

[0021] In some embodiments of the present application, the optoelectronic device further includes an encapsulation layer, and the encapsulation layer is disposed on a side of the first electrode or the second electrode away from the functional layer.

[0022] In some embodiments of the present application,

[0023] The functional layer comprises a light-emitting layer, wherein the material of the light-emitting layer is independently selected from one or more quantum dot light-emitting materials, wherein the quantum dot light-emitting material is selected from one or more single-structure quantum dots, core-shell quantum dots and perovskite semiconductor materials, wherein the material of the single-structure quantum dots, the core material of the core-shell quantum dots and the shell material of the core-shell quantum dots are selected from at least one of II-VI compounds, IV-VI compounds, III-V compounds and I-III-VI compounds, wherein the II-VI compounds are selected from 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, and the IV-VI group compound is selected from SnS, SnSe, SnTe, PbS, Pb At least one of SnSe, PbTe, SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, SnPbSeTe, SnPbSTe, and the III-V group compound is selected from GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs At least one of InNSb, InPAs, InPSb, GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs and InAlPSb, the I-III-VI group compound is selected from at least one of CuInS2, CuInSe2 and AgInS2, and the perovskite semiconductor material is selected from doped or undoped inorganic perovskite semiconductors, or organic-inorganic hybrid perovskite semiconductors. The inorganic perovskite semiconductor has a general structural formula of AMX3, wherein A is Cs + ion, M is a divalent metal cation selected from Pb 2+Sn 2+ , Cu 2+ 、Ni 2+ 、Cd 2+ Cr 2+ , Mn 2+ 、Co 2+ , Fe 2+ ,Ge 2+ , Yb 2+ 、Eu 2+ At least one of, X is a halogen anion selected from Cl - Br - ,I - The general structural formula of the organic-inorganic hybrid perovskite semiconductor is BMX3, wherein B is an organic amine cation selected from CH3(CH2) n-2 NH3 + or [NH3(CH 2) nNH3] 2+ , where n≥2, M is a divalent metal cation selected from Pb 2+ Sn 2+ , Cu 2+ 、Ni 2 + 、Cd 2+ Cr 2+ , Mn 2+ 、Co 2+ , Fe 2+ ,Ge 2+ , Yb 2+ 、Eu 2+ At least one of, X is a halogen anion selected from Cl - Br - ,I - At least one of; and / or,

[0024] The functional layer comprises an electron transport layer, the material of the electron transport layer is selected from at least one of metal oxides, doped metal oxides, 2-6 group semiconductor materials, 3-5 group semiconductor materials and 1-3-6 group semiconductor materials, the metal oxide is selected from at least one of ZnO, BaO, TiO2 and SnO2; the metal oxide in the doped metal oxide is selected from at least one of ZnO, TiO2 and SnO2, the doping element is selected from at least one of Al, Mg, Li, In and Ga, the 2-6 group semiconductor material is selected from at least one of ZnS, ZnSe and CdS; the 3-5 group semiconductor material is selected from at least one of InP and GaP; the 1-3-6 group semiconductor material is selected from at least one of CuInS and CuGaS; and / or,

[0025] The functional layer includes a hole transport layer, and the materials of the hole transport layer are independently selected from 4,4'-N,N'-dicarbazolyl-biphenyl, 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, N,N'-bis(3-methylphenyl)-N,N'-bis(phenyl)-spiro, N,N'-di(4-(N,N'-diphenyl)-1,1'-biphenyl-4,4"-diamine, N,N'-diphenyl-N,N'-bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine, -diphenyl-amino)phenyl)-N,N'-diphenylbenzidine, 4,4',4'-tri(N-carbazolyl)-triphenylamine, 4,4',4'-tri(N-3-methylphenyl-N-phenylamino)triphenylamine, poly[(9,9'-dioctylfluorene-2,7-diyl)-co-(4,4'-(N-(4-sec-butylphenyl)diphenylamine))], poly(4-butylphenyl-diphenylamine), polyaniline, polypyrrole, poly(p-phenylenevinylene), poly(phenylenevinylene), Poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene vinylene] and poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylene vinylene], copper phthalocyanine, aromatic tertiary amines, polynuclear aromatic tertiary amines, 4,4'-bis(p-carbazolyl)-1,1'-biphenyl compounds, N,N,N',N'-tetraaryl benzidine, PEDOT:PSS and its derivatives, poly(N-vinyl carbazole) and its derivatives, polymethacrylate and its derivatives At least one of biological materials, poly (9,9-octylfluorene) and its derivatives, poly (spirofluorene) and its derivatives, N, N'-di (naphthalene-1-yl) -N, N'-diphenylbenzidine, spiro NPB, doped graphene, undoped graphene, C60, doped or undoped NiO, doped or undoped MoO3, doped or undoped WO3, doped or undoped V2O5, doped or undoped P-type gallium nitride, doped or undoped CrO3, doped or undoped CuO; and / or,

[0026] The functional layer includes a hole injection layer, and the material of the hole injection layer is independently selected from at least one of 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene, PEDOT, PEDOT:PSS, a derivative of PEDOT:PSS doped with s-MoO3, 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.

[0027] A fourth aspect of the present application provides a display device, comprising the optoelectronic device.

[0028] The present application provides a composite electrode. By adding liquid metal into the composite electrode, even if cracks are generated in the composite electrode of the present application under continuous bending, the liquid metal can fill and repair the cracks, thereby improving the performance stability of the composite electrode. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings required for use in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative work.

[0030] Figure 1 A structural block diagram of a first embodiment of a composite electrode of the present application;

[0031] Figure 2 A cross-sectional view of a second embodiment of a composite electrode of the present application;

[0032] Figure 3 A cross-sectional view of a third embodiment of a composite electrode of the present application;

[0033] Figure 4 A structural block diagram of an optoelectronic device according to an embodiment of the present application;

[0034] Figure 5 A schematic structural diagram of an embodiment of a photoelectric device in the present application.

[0035] Reference numerals: 100, optoelectronic device; 110, encapsulation layer; 120, liquid metal layer; 130, electrode layer; 140, functional layer; 150, second electrode. DETAILED DESCRIPTION

[0036] The following will be combined with the drawings in the embodiments of the present application to clearly and completely describe the technical solutions in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative work are within the scope of protection of the present invention.

[0037] In this application, the word "exemplary" is used to mean "serving as an example, illustration, or illustration." Any embodiment described in this application as "exemplary" is not necessarily to be construed as being preferred or advantageous over other embodiments. The following description is given to enable any person skilled in the art to implement and use the invention. In the following description, details are listed for the purpose of explanation. It should be understood that a person of ordinary skill in the art can recognize that the invention can be implemented without using these specific details. In other instances, well-known structures and processes are not elaborated in detail to avoid obscuring the description of the invention with unnecessary details. Therefore, the present invention is not intended to be limited to the embodiments shown, but is consistent with the widest scope consistent with the principles and features disclosed in this application.

[0038] In addition, the terms "first" and "second" are used for descriptive purposes only and should not be understood as indicating or implying relative importance or implicitly indicating the number of the indicated technical features. Therefore, the features defined as "first" and "second" may explicitly or implicitly include one or more of the features. In the description of the present invention, the meaning of "plurality" is two or more, unless otherwise clearly and specifically defined.

[0039] The embodiment of the present application provides a photoelectric device. The photoelectric device in the present application has higher current efficiency and brightness, and longer service life.

[0040] See also Figure 4 The photoelectric device comprises a second electrode 150, a functional layer 140 and a first electrode which are stacked in sequence. The first electrode is a composite electrode. The composite electrode comprises liquid metal. In some embodiments of the present application, please refer to Figure 2 and Figure 3 The composite electrode includes a stacked electrode 130 and a liquid metal layer 120, wherein the liquid metal layer includes the liquid metal. For example, see Figure 1 The electrode layer 130 may be a silver electrode (Ag), and the liquid metal layer 120 may be a gallium-indium eutectic alloy layer stacked on the silver electrode. Of course, in other embodiments of the present application, the liquid metal layer may also be disposed inside the composite electrode.

[0041] It should be noted that in some other embodiments of the present application, the second electrode may be a composite electrode in the present application. In some other embodiments of the present application, the first electrode and the second electrode may be composite electrodes in the present application.

[0042] See also Figure 3In some embodiments of the present application, the composite electrode includes a stacked electrode layer 130, a liquid metal layer 120, and a sealing layer 110. It should be noted that in other embodiments of the present application, the sealing layer 110 can also be used as a packaging layer of the device. It can be understood that the sealing layer 110 can improve the water and oxygen barrier effect of the optoelectronic device and further improve the service life of the optoelectronic device. Of course, in other embodiments of the present application, a packaging layer can also be further provided on the sealing layer, which is not limited here.

[0043] Specifically, the second electrode 150 and the composite electrode (i.e., the first electrode) are a pair of electrodes of the device. Exemplarily, the second electrode 150 is an anode and the composite electrode is a cathode. It should be noted that the second electrode 150 is an electrode known in the prior art. Exemplarily, the second electrode 150 includes an ITO substrate and a silver reflective layer disposed on the ITO substrate. The electrode layer 130 is a silver electrode.

[0044] In the present application, the optoelectronic device further includes a liquid metal layer located on the electrode layer 130. The liquid metal layer refers to a metal layer that exists in liquid form in the optoelectronic device. For example, a metal or alloy material that is liquid at room temperature (e.g., gallium-indium eutectic alloy) can be applied to the electrode layer 130 to form a liquid metal layer on the electrode layer 130. The preparation process is simple and is conducive to reducing the preparation cost of the device.

[0045] It should be noted that in the prior art, the electrode is prone to cracks after repeated bending, resulting in a decrease in the performance of the electrode, thereby shortening the life of the device. In this embodiment, since a liquid metal layer is provided in the composite electrode, when the device is repeatedly bent, even if cracks are generated in the composite electrode, the liquid metal layer can fill and repair the cracks in time, thereby avoiding a sharp drop in the performance of the composite electrode, improving the performance stability of the composite electrode, and helping to increase the service life of the optoelectronic device. In addition, the liquid metal layer is provided on the electrode layer, which can also form a packaging effect on the electrode layer, which is conducive to improving the water and oxygen barrier effect of the optoelectronic device, and further improving the service life of the optoelectronic device.

[0046] In some embodiments of the present application, a plurality of grooves are provided on one side of the electrode layer 130 away from the functional layer 140, and the liquid metal layer is at least partially arranged in the grooves. Specifically, the plurality of grooves are in an array structure, and the liquid metal layer is arranged in the grooves. It is understandable that, since the liquid metal has good fluidity, a groove is provided on one side of the electrode layer 130, and the liquid metal layer is at least partially arranged in the groove, which can make the liquid metal flow everywhere to a certain extent, and is conducive to improving the process stability of the device preparation. Exemplarily, a composite electrode is formed on a flexible substrate with grooves by evaporating silver material. Since the stacking thickness of the electrode layer on the flexible substrate is relatively uniform, a plurality of grooves will also be formed on the electrode layer. Of course, in other embodiments of the present application, a blocking structure may also be provided around the electrode layer 130, and the blocking structure and the electrode layer 130 are jointly enclosed to form a receiving groove, and the liquid metal layer is arranged in the receiving groove.

[0047] In some embodiments of the present application, the thickness of the electrode layer is between 15nm and 25nm. It should be noted that in order to make the optoelectronic device have more stable performance and better bending performance, the thickness of the electrode layer in the prior art is generally about 100nm. In the present application, a liquid metal layer is provided on one side of the electrode layer, which can greatly reduce the thickness of the electrode layer and further improve the bending performance of the optoelectronic device.

[0048] In some embodiments of the present application, the encapsulation layer includes an epoxy resin encapsulation layer. The liquid metal layer is encapsulated on the composite electrode using an epoxy resin encapsulation layer to prevent the liquid metal from flowing everywhere, and at the same time, it can prevent water and oxygen from penetrating into the optoelectronic device, which is beneficial to improving the service life of the device. Epoxy resin is generally viscous and has low fluidity, which can effectively prevent the epoxy resin from being immersed in the liquid metal layer before hardening. In addition, the hardening speed of the epoxy resin is adjustable, and it can be quickly cured after being heated to a predetermined temperature, further preventing the epoxy resin from being immersed in the liquid metal layer, thereby reducing the probability of encapsulation failure. In other embodiments of the present application, the encapsulation layer can also be an acrylic resin encapsulation layer, a polyethylene encapsulation layer, a polyimide encapsulation layer, etc., which are not further limited here.

[0049] In some embodiments of the present application, the encapsulation layer includes an elastic encapsulation layer. It is understandable that the elastic encapsulation layer has high flexibility, and this structural arrangement is conducive to further improving the bending performance of the optoelectronic device. Of course, in other embodiments of the present application, the optoelectronic device may also include an epoxy resin encapsulation layer and an elastic encapsulation layer at the same time. For example, the elastic encapsulation layer is arranged on the liquid metal layer, and the epoxy resin encapsulation layer is arranged on the elastic encapsulation layer, which is not limited here.

[0050] Furthermore, the elastic encapsulation layer is in a micron glass ball array structure. It is understandable that the micron glass ball array can support the encapsulation effect of the liquid metal layer, which can prevent the encapsulation layer from collapsing during the bending and deformation of the optoelectronic device, thereby avoiding the attenuation of the sealing performance of the encapsulation layer, which is conducive to improving the encapsulation effect of the sealing layer.

[0051] In some embodiments of the present application, silicone resin, antioxidant and additive, silicone resin: antioxidant: additive = 100: (1-2): (1-5), exemplarily, silicone resin includes one or more of polymethylsiloxane, polydimethylsiloxane and polyphenylsiloxane. Specifically, silicone resin is polydimethylsiloxane (PDMS), PDMS: antioxidant: additive = 100: (1-2): (1-5). It can be understood that the oxidation resistance of PDMS is relatively weak. In order to enhance the oxidation resistance, sealing and waterproof properties of the encapsulation layer, adding an antioxidant to PDMS can improve the oxidation resistance and heat resistance of PDMS. The additive can improve the sealing and waterproof properties of PDMS. Exemplarily, the antioxidant can be one or more of phthalates and 2,6-di-tert-butyl-p-cresol. The additive can be one or more of 1,2-stilbene and methyl mercaptan.

[0052] In some embodiments of the present application, the functional layer 140 includes a hole injection layer, a hole transport layer, a quantum dot light emitting layer and an electron transport layer stacked in sequence. The materials of the hole injection layer, the hole transport layer, the quantum dot light emitting layer and the electron transport layer have been specifically described above and will not be repeated here.

[0053] Another aspect of the present application provides a method for preparing a composite electrode, the method comprising:

[0054] S1 provides a substrate.

[0055] Specifically, the substrate may be a transparent substrate, and a plurality of grooves are provided on one side of the substrate.

[0056] S2: preparing an electrode layer on one side of the substrate, wherein a plurality of grooves are provided on a side of the electrode layer away from the substrate.

[0057] Specifically, an electrode layer can be prepared on the side of the substrate with the groove by using an evaporation process. It is understandable that since the substrate itself has a groove structure, a groove structure will inevitably be formed on the electrode layer formed by evaporation on the substrate. It should be noted that the material and preparation method of the electrode layer can refer to the prior art, which does not belong to the main improvement of the present application and will not be further elaborated here.

[0058] S3 applies liquid metal in the groove to form a liquid metal layer.

[0059] Specifically, the liquid metal material is dripped into the groove, and the groove can restrict the flow of the liquid metal.

[0060] In some embodiments of the present application, the preparation method further comprises:

[0061] S4: preparing a sealing layer on the liquid metal layer to obtain the composite electrode photoelectric device, wherein the sealing layer is used to seal the liquid metal layer. In addition, the present application also provides another method for preparing a composite electrode, the preparation method comprising:

[0062] S1 ′ provides a substrate having a groove.

[0063] Specifically, the substrate may be a transparent substrate, and a plurality of grooves are provided on one side of the substrate.

[0064] S2 ′ applies liquid metal in the groove to form a liquid metal layer.

[0065] Specifically, the liquid metal material is dripped into the groove, and the groove can restrict the flow of the liquid metal.

[0066] S3′ prepares an electrode layer on the liquid metal layer.

[0067] Specifically, an evaporation process may be used to prepare an electrode layer on one side of the liquid metal layer of the substrate.

[0068] In some embodiments of the present application, epoxy resin is used as a sealing layer to seal the liquid metal layer. Specifically, the epoxy resin glue is slowly dripped onto the liquid metal layer and immediately heated (for example, heated at 60 degrees), so that the epoxy resin can be quickly cured.

[0069] Of course, in some other embodiments of the present application, a silicone material can also be used as the encapsulation layer. Specifically, a composite material of PDMS, an active stabilizer, and an antioxidant is prepared according to a preset ratio. The prepared composite material is applied to the liquid metal and heated to harden the composite material.

[0070] Composite electrode example 1

[0071] Step 1: providing a substrate, wherein one side of the substrate is provided with a groove;

[0072] Step 2: Vacuum not higher than 3x10 by thermal evaporation -4 Pa, evaporating Ag on the side of the substrate with the groove at a rate of 1 angstrom / second and a thickness of 20 nm to obtain an Ag electrode layer;

[0073] Step 3: applying liquid metal material (gallium-indium eutectic alloy) on the Ag electrode layer to obtain a liquid metal layer;

[0074] Step 4: preparing a sealing layer on the liquid metal layer, wherein the material of the sealing layer is epoxy resin. An electrode experimental sample 1 is obtained.

[0075] Composite electrode example 2

[0076] The difference between the composite electrode example 1 and the composite electrode example 1 is that the liquid metal material is a sodium-potassium alloy. An electrode experimental sample 2 is obtained.

[0077] Composite electrode example 3

[0078] The difference between the composite electrode example 1 and the composite electrode example 1 is that the liquid metal material is gallium. An electrode experimental sample 3 is obtained.

[0079] Composite electrode embodiment 4

[0080] The difference between it and the composite electrode example 1 is that the material of the sealing layer includes PDMS, phthalate and 1,2-diphenylethylene, and the electrode experimental sample 4 is obtained by calculating the mass ratio of PDMS: phthalate: 1,2-diphenylethylene = 100:1.5:2.5.

[0081] Composite electrode example 5

[0082] Step 1: providing a substrate with a groove;

[0083] Step 2: applying liquid metal material (gallium-indium eutectic alloy) into the groove to obtain a liquid metal layer;

[0084] Step 3: Prepare a Ag electrode layer on the liquid metal layer to obtain a composite electrode experimental sample 5.

[0085] Composite electrode comparative example 1

[0086] Step 1: providing a substrate, wherein one side of the substrate is provided with a groove;

[0087] Step 2: Vacuum not higher than 3x10 by thermal evaporation -4 Pa, Ag was evaporated on the side of the substrate with the groove at a rate of 1 angstrom / second and a thickness of 20 nm to obtain an electrode layer. Electrode comparison sample 1 was obtained.

[0088] Composite electrode comparative example 2

[0089] Step 1: providing a substrate, wherein one side of the substrate is provided with a groove;

[0090] Step 2: applying liquid metal material (gallium-indium eutectic alloy) into the groove to obtain a liquid metal layer;

[0091] Step 3: preparing a sealing layer on the liquid metal layer, wherein the material of the sealing layer is epoxy resin, thereby obtaining an electrode comparative sample 2.

[0092] A bending test was performed on electrode experimental samples 1 to 4, electrode comparison sample 1 and electrode comparison sample 2 to test the number of bending times required for the conductivity of all samples to drop to 90% of the initial conductivity. The higher the number, the stronger the bending resistance of the composite electrode.

[0093] Table 1

[0094]

[0095] Device Example 1

[0096] Step 1: Prepare a hole injection layer by spin coating on a substrate (ITO substrate). The material is PEDOT:PSS, the rotation speed is 5000 r / min, the time is 30 seconds, and then heated at 150° C. for 15 minutes to form a hole injection layer.

[0097] Step 2: Spin-coat TFB (8 mg / mL) on the PEDOT:PSS layer at a speed of 3000 r / min for 30 seconds, and then heat at 120°C for 10 minutes to form a hole transport layer.

[0098] Step 3: Spin coating the first hole transport layer to prepare a quantum dot light-emitting layer, the quantum dot material is blue CdZnSe (20 mg / mL), the rotation speed is 2000 r / min, and the time is 30 seconds.

[0099] Step 4: Prepare an electron transport layer by spin coating on the quantum dot light-emitting layer. The material is ZnO (30 mg / mL), the rotation speed is 3000 r / min, and the time is 30 seconds.

[0100] Step 5: Vacuum not higher than 3x10 by thermal evaporation -4 Pa, evaporate Ag at a rate of 1 angstrom / second and a thickness of 20 nm to obtain an Ag electrode layer;

[0101] Step 6: Apply liquid metal material (gallium-indium eutectic alloy) on the Ag electrode layer to obtain a liquid metal layer.

[0102] Step 7: Slowly drip the epoxy resin onto the liquid metal layer and immediately heat it at 60 degrees to quickly solidify the epoxy resin and form a sealing layer.

[0103] Device Example 2

[0104] The difference between this embodiment and Example 1 is that the material used to prepare the sealing layer in step 7 is PDMS.

[0105] Device Example 3

[0106] The difference between this embodiment and Example 1 is that the material used to prepare the liquid metal layer in step 6 is a sodium-potassium alloy.

[0107] Device Example 4

[0108] The difference between this embodiment and Example 1 is that the material used to prepare the liquid metal layer in step 6 is gallium metal.

[0109] Device Example 5

[0110] The difference from Example 1 is that the materials for preparing the sealing layer in step 7 include PDMS, phthalate and 1,2-diphenylethylene, and the mass ratio is PDMS: phthalate: 1,2-diphenylethylene=100:1.5:2.5.

[0111] Device Example 6

[0112] Step 1: providing a substrate, wherein one side of the substrate is provided with a groove;

[0113] Step 2: Apply liquid metal material (gallium-indium eutectic alloy) into the groove of the substrate to obtain a liquid metal layer.

[0114] Step 3: Prepare a Ag electrode layer on the liquid metal layer.

[0115] Step 4: Prepare a hole injection layer by spin coating on the Ag electrode layer. The material is PEDOT:PSS, the rotation speed is 5000 r / min, the time is 30 seconds, and then heated at 150° C. for 15 minutes to form a hole injection layer.

[0116] After step 4, the steps of preparing the hole transport layer, the quantum dot light-emitting layer, the electron transport layer, the Ag electrode layer, the liquid metal layer and the sealing layer are the same as those in Example 1.

[0117] Device Example 7

[0118] The difference between this embodiment and Example 1 is that the material for preparing the quantum dot light-emitting layer in step 3 is red CdZnS.

[0119] Device Example 8

[0120] The difference between this embodiment and Example 7 is that the material used to prepare the sealing layer in step 7 is PDMS.

[0121] Device Example 9

[0122] The difference between this embodiment and Example 7 is that the material used to prepare the liquid metal layer in step 6 is a sodium-potassium alloy.

[0123] Device Example 10

[0124] The difference between this embodiment and Example 7 is that the material used to prepare the liquid metal layer in step 6 is gallium metal.

[0125] Device Example 11

[0126] The difference between this embodiment and Example 7 is that the materials for preparing the sealing layer in step 7 include PDMS, phthalate and 1,2-diphenylethylene, and the mass ratio is PDMS:phthalate:1,2-diphenylethylene=100:1.5:2.5.

[0127] Device Example 12

[0128] Step 1: providing a substrate, wherein one side of the substrate is provided with a groove;

[0129] Step 2: Apply liquid metal material (gallium-indium eutectic alloy) into the groove of the substrate to obtain a liquid metal layer.

[0130] Step 3: Prepare a Ag electrode layer on the liquid metal layer.

[0131] Step 4: Prepare a hole injection layer by spin coating on the Ag electrode layer. The material is PEDOT:PSS, the rotation speed is 5000 r / min, the time is 30 seconds, and then heated at 150° C. for 15 minutes to form a hole injection layer.

[0132] The steps of preparing the hole transport layer, quantum dot light-emitting layer, electron transport layer, Ag electrode layer, liquid metal layer and sealing layer after step 4 are the same as those in Example 7.

[0133] Device Comparison Example 1

[0134] Step 1: Prepare a hole injection layer by spin coating on a substrate (ITO substrate). The material is PEDOT:PSS, the rotation speed is 5000 r / min, the time is 30 seconds, and then heated at 150° C. for 15 minutes to form a hole injection layer.

[0135] Step 2: Spin-coat TFB (8 mg / mL) on the PEDOT:PSS layer at a speed of 3000 r / min for 30 seconds, and then heat at 120°C for 10 minutes to form a hole transport layer.

[0136] Step 3: Spin coating the first hole transport layer to prepare a quantum dot light-emitting layer, the quantum dot material is blue CdZnSe (20 mg / mL), the rotation speed is 2000 r / min, and the time is 30 seconds.

[0137] Step 4: Prepare an electron transport layer by spin coating on the quantum dot light-emitting layer. The material is ZnO (30 mg / mL), the rotation speed is 3000 r / min, and the time is 30 seconds.

[0138] Step 5: Vacuum not higher than 3x10 by thermal evaporation -4 Pa, evaporate Ag at a rate of 1 angstrom / s and a thickness of 20 nm to obtain an electrode.

[0139] Step 6: Prepare a sealing layer on the electrode using PDMS material.

[0140] Device Comparison Example 2

[0141] Step 1: Prepare a hole injection layer by spin coating on a substrate (ITO substrate). The material is PEDOT:PSS, the rotation speed is 5000 r / min, the time is 30 seconds, and then heated at 150° C. for 15 minutes to form a hole injection layer.

[0142] Step 2: Spin-coat TFB (8 mg / mL) on the PEDOT:PSS layer at a speed of 3000 r / min for 30 seconds, and then heat at 120°C for 10 minutes to form a hole transport layer.

[0143] Step 3: Spin coating the first hole transport layer to prepare a quantum dot light-emitting layer, the quantum dot material is blue CdZnSe (20 mg / mL), the rotation speed is 2000 r / min, and the time is 30 seconds.

[0144] Step 4: Prepare an electron transport layer by spin coating on the quantum dot light-emitting layer. The material is ZnO (30 mg / mL), the rotation speed is 3000 r / min, and the time is 30 seconds.

[0145] Step 5: Apply liquid metal material (gallium-indium eutectic alloy) on the electron transport layer to obtain a liquid metal layer.

[0146] Step 6: Prepare a sealing layer on the liquid metal layer using PDMS material.

[0147] Device Comparison Example 3

[0148] The difference between it and Comparative Example 1 is that the quantum dot material is red CdZnS.

[0149] Device Comparison Example 4

[0150] The difference between it and Comparative Example 2 is that the quantum dot material is red CdZnS.

[0151] The photoelectric efficiency and working life of the different sample devices obtained in Examples 1-10 and Comparative Examples 1-4 were tested with a 2mA constant current drive device, and the results are shown in Table 1. T95-1K represents the time taken for the brightness of the device to decay from 100% to 95% at a brightness of 1000nit. This value is calculated from the values ​​of L and T95. EQE represents the external quantum efficiency of the device. Under the premise that the area of ​​the light-emitting area and the driving current are consistent, the higher the EQE, the better the device performance.

[0152] Table 2

[0153]

[0154]

[0155] It can be seen from the experimental data in Table 1 that the liquid metal layer in the composite electrode can significantly improve its conductivity under repeated bending. When the decrease in electrode conductivity is basically the same, the number of bends of the experimental sample 1 is increased by 50% compared with the comparative sample 1, and the bending resistance of the electrode is significantly improved.

[0156] It can be seen from the experimental data in Table 2 that when the device with liquid metal is powered on, the damage to the electrode is also weaker, and the corresponding EQE and life performance are also improved.

[0157] The above is a detailed introduction to a composite electrode and its preparation method, optoelectronic device and display device provided in the embodiments of the present application. Specific examples are used in this article to illustrate the principles and implementation methods of the present invention. The description of the above embodiments is only used to help understand the method of the present invention and its core idea; at the same time, for technical personnel in this field, according to the idea of ​​the present invention, there will be changes in the specific implementation method and application scope. In summary, the content of this specification should not be understood as a limitation on the present invention.

Claims

1. A composite electrode, characterized in that: The composite electrode includes liquid metal.

2. The composite electrode according to claim 1, characterized in that The composite electrode comprises an electrode layer and a liquid metal layer which are stacked; the liquid metal layer comprises the liquid metal.

3. The composite electrode according to claim 2, characterized in that The composite electrode further comprises a sealing layer, which is arranged on a side of the liquid metal layer away from the electrode layer, so as to seal the liquid metal layer.

4. The composite electrode according to claim 1, characterized in that The liquid metal is selected from a metal element or alloy that is liquid at room temperature; and / or, the liquid metal is selected from one or more of a sodium-potassium alloy, a gallium-indium eutectic alloy, and gallium.

5. The composite electrode according to claim 2, characterized in that The sealing layer is in a micron glass ball array structure; And / or, the material forming the sealing layer includes silicone resin, antioxidant and additive, and the mass ratio is silicone resin: antioxidant: additive = 100: (1-2): (1-5); And / or, the material forming the sealing layer includes epoxy resin.

6. The composite electrode according to claim 2, characterized in that A plurality of grooves are provided on one side of the electrode layer, and the liquid metal layer is at least partially disposed in the grooves; And / or, the thickness of the electrode layer is between 15 nm and 25 nm; And / or, the material of the electrode layer is selected from a doped metal oxide particle electrode, a composite electrode of metal and metal oxide, a graphene electrode, a carbon nanotube electrode, a metal electrode or an alloy electrode; the material of the doped metal oxide particle electrode is selected from 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 and aluminum-doped magnesium oxide; the composite electrode of metal and metal oxide is selected from one or more of AZO / Ag / AZO, AZO / Al / AZO, ITO / Ag / ITO, ITO / Al / ITO, ZnO / Ag / ZnO, ZnO / Al / ZnO, TiO2 / Ag / TiO2, TiO2 / Al / TiO2, ZnS / Ag / ZnS, ZnS / Al / ZnS; the material of the metal electrode is selected from one or more of Ag, Al, Cu, Mo, Au, Pt, Si, Ca, Mg and Ba.

7. A method for preparing a composite electrode, characterized in that: The preparation method comprises: providing a substrate; An electrode layer is prepared on one side of the substrate, wherein a plurality of grooves are provided on a side of the electrode layer away from the substrate; applying liquid metal in the groove to form a liquid metal layer; or, providing a substrate having a groove, wherein liquid metal is applied in the groove to form a liquid metal layer; An electrode layer is prepared on the liquid metal layer.

8. A photoelectric device, characterized in that: The photoelectric device comprises a first electrode, a functional layer and a second electrode which are stacked in sequence; wherein at least one of the first electrode and the second electrode comprises the composite electrode according to any one of claims 1 to 6 or is prepared by the method for preparing the composite electrode according to claim 7.

9. The optoelectronic device according to claim 8, characterized in that The optoelectronic device further includes a packaging layer, which is disposed on a side of the first electrode or the second electrode away from the functional layer.

10. The optoelectronic device according to claim 8, characterized in that The functional layer comprises a light-emitting layer, wherein the material of the light-emitting layer is independently selected from one or more quantum dot light-emitting materials, wherein the quantum dot light-emitting material is selected from one or more single-structure quantum dots, core-shell quantum dots and perovskite semiconductor materials, wherein the material of the single-structure quantum dots, the core material of the core-shell quantum dots and the shell material of the core-shell quantum dots are selected from at least one of II-VI compounds, IV-VI compounds, III-V compounds and I-III-VI compounds, wherein the II-VI compounds are selected from 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, and the IV-VI group compound is selected from SnS, SnSe, SnTe, PbS, Pb At least one of SnSe, PbTe, SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, SnPbSeTe, SnPbSTe, and the III-V group compound is selected from GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs At least one of InNSb, InPAs, InPSb, GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs and InAlPSb, the I-III-VI group compound is selected from at least one of CuInS2, CuInSe2 and AgInS2, and the perovskite semiconductor material is selected from doped or undoped inorganic perovskite semiconductors, or organic-inorganic hybrid perovskite semiconductors. The inorganic perovskite semiconductor has a general structural formula of AMX3, wherein A is Cs + ion, M is a divalent metal cation selected from Pb 2+ Sn 2+ , Cu 2+ 、Ni 2+ 、Cd 2+ Cr 2+ , Mn 2+ 、Co 2+ , Fe 2+ ,Ge 2+ , Yb 2+ 、Eu 2+ At least one of, X is a halogen anion selected from Cl - Br - ,I - The general structural formula of the organic-inorganic hybrid perovskite semiconductor is BMX3, wherein B is an organic amine cation selected from CH3(CH2) n-2 NH3 + or [NH3(CH 2) nNH3] 2+ , where n≥2, M is a divalent metal cation selected from Pb 2+ Sn 2+ , Cu 2+ 、Ni 2+ 、Cd 2+ Cr 2+ , Mn 2+ 、Co 2+ , Fe 2+ ,Ge 2+ , Yb 2+ 、Eu 2+ At least one of, X is a halogen anion selected from Cl - Br - ,I - At least one of; and / or, The functional layer comprises an electron transport layer, the material of the electron transport layer is selected from at least one of metal oxides, doped metal oxides, 2-6 group semiconductor materials, 3-5 group semiconductor materials and 1-3-6 group semiconductor materials, the metal oxide is selected from at least one of ZnO, BaO, TiO2 and SnO2; the metal oxide in the doped metal oxide is selected from at least one of ZnO, TiO2 and SnO2, the doping element is selected from at least one of Al, Mg, Li, In and Ga, the 2-6 group semiconductor material is selected from at least one of ZnS, ZnSe and CdS; the 3-5 group semiconductor material is selected from at least one of InP and GaP; the 1-3-6 group semiconductor material is selected from at least one of CuInS and CuGaS; and / or, The functional layer includes a hole transport layer, and the materials of the hole transport layer are independently selected from 4,4'-N,N'-dicarbazolyl-biphenyl, 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, N,N'-bis(3-methylphenyl)-N,N'-bis(phenyl)-spiro, N,N'-di(4-(N,N'-diphenyl)-1,1'-biphenyl-4,4"-diamine, N,N'-diphenyl-N,N'-bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine, -diphenyl-amino)phenyl)-N,N'-diphenylbenzidine, 4,4',4'-tri(N-carbazolyl)-triphenylamine, 4,4',4'-tri(N-3-methylphenyl-N-phenylamino)triphenylamine, poly[(9,9'-dioctylfluorene-2,7-diyl)-co-(4,4'-(N-(4-sec-butylphenyl)diphenylamine))], poly(4-butylphenyl-diphenylamine), polyaniline, polypyrrole, poly(p-phenylenevinylene), poly(phenylenevinylene), Poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene vinylene] and poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylene vinylene], copper phthalocyanine, aromatic tertiary amines, polynuclear aromatic tertiary amines, 4,4'-bis(p-carbazolyl)-1,1'-biphenyl compounds, N,N,N',N'-tetraaryl benzidine, PEDOT:PSS and its derivatives, poly(N-vinyl carbazole) and its derivatives, polymethacrylate and its derivatives At least one of biological materials, poly (9,9-octylfluorene) and its derivatives, poly (spirofluorene) and its derivatives, N, N'-di (naphthalene-1-yl) -N, N'-diphenylbenzidine, spiro NPB, doped graphene, undoped graphene, C60, doped or undoped NiO, doped or undoped MoO3, doped or undoped WO3, doped or undoped V2O5, doped or undoped P-type gallium nitride, doped or undoped CrO3, doped or undoped CuO; and / or, The functional layer includes a hole injection layer, and the material of the hole injection layer is independently selected from at least one of 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene, PEDOT, PEDOT:PSS, a derivative of PEDOT:PSS doped with s-MoO3, 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.

11. A display device, characterized in that: The optoelectronic device comprises the optoelectronic device according to any one of claims 8 to 10.

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