Composite material, preparation method of film, film, photoelectric device and display equipment

Abstract

The invention provides a composite material, a preparation method of a film, the film, a photoelectric device and display equipment, the composite material comprises a first compound and a second compound, the first compound comprises quantum dots with the surfaces connected with ligands, and the second compound comprises a gel; the ligand is connected with the gel agent. By connecting the ligands on the surfaces of the quantum dots with the gels, the distance between the quantum dots is increased, the electrostatic adsorption force between the quantum dots is reduced, the quantum dots are not prone to agglomeration, and therefore the stability of the quantum dots is improved.

Description

Technical Field

[0001] The present application relates to the technical field of optoelectronic devices, and particularly relates to a composite material, a preparation method of a thin film, the thin film, an optoelectronic device, and a display device. Background Art

[0002] Quantum dots are semiconductor nanostructures that confine excitons in three spatial directions. This confinement can be attributed to electrostatic potential (generated by external electrodes, doping, strain, impurities), the interface between two different semiconductor materials (e.g., in self-assembled quantum dots), the surface of the semiconductor (e.g., semiconductor nanocrystals), or a combination of the above three.

[0003] Quantum dots are prone to agglomeration and precipitation during storage, resulting in the unusability of the material and the need to improve stability. Summary of the Invention

[0004] Based on this, embodiments of the present application provide a composite material, a preparation method of a thin film, the thin film, an optoelectronic device, and a display device.

[0005] In a first aspect, embodiments of the present application provide a composite material, which includes a first compound and a second compound. The first compound includes quantum dots with ligands connected to the surface, and the second compound includes a gelling agent; the ligand is connected to the gelling agent.

[0006] In a second aspect, embodiments of the present application provide a preparation method of a thin film, including the following steps:

[0007] Providing a first mixture including a first compound and a second mixture including a second compound, where the first compound is quantum dots with ligands connected to the surface, and the second compound is a gelling agent;

[0008] Depositing the first mixture and the second mixture, and performing heat treatment after deposition to obtain the thin film.

[0009] In a third aspect, embodiments of the present application provide a thin film, which includes the above composite material or is prepared by the above preparation method of the thin film.

[0010] In a fourth aspect, embodiments of the present application provide an optoelectronic device including:

[0011] An anode and a cathode disposed opposite to each other;

[0012] An excitation layer disposed between the first functional layer and the second functional layer;

[0013] Wherein, the excitation layer includes the above composite material or a thin film prepared by the above preparation method of the thin film.

[0014] Fifth aspect, embodiments of the present application provide a display device, including a thin film prepared by the thin film preparation method as described above, or an optoelectronic device as described above.

[0015] Advantageous effects of embodiments of the present application:

[0016] In the embodiments of the present application, by connecting the ligands on the surface of the quantum dots with the gelling agent, the distance between the quantum dots is increased, the electrostatic adsorption force between the quantum dots is reduced, and the quantum dots are not easily agglomerated, thereby improving the stability of the quantum dots. Description of the Drawings

[0017] 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 also be obtained based on these drawings.

[0018] Figure 1 It is a TEM image of Test Example 1 provided by an embodiment of the present application.

[0019] Figure 2 It is a TEM image of Test Example 2 provided by an embodiment of the present application.

[0020] Figure 3 It is a TEM image of Test Example 3 provided by an embodiment of the present application.

[0021] Figure 4 It is a TEM image of Test Example 4 provided by an embodiment of the present application.

[0022] Figure 5 It is a TEM image of Test Example 5 provided by an embodiment of the present application.

[0023] Figure 6 It is a TEM image of Test Example 6 provided by an embodiment of the present application.

[0024] Figure 7 It is a TEM image of Test Example 7 provided by an embodiment of the present application.

[0025] Figure 8 It is a TEM image of Test Example 8 provided by an embodiment of the present application.

[0026] Figure 9 It is a TEM image of Test Example 9 provided by an embodiment of the present application.

[0027] Figure 10 It is a schematic diagram of the layer structure of the upright device provided by an embodiment of the present application;

[0028] Figure 11It is a schematic diagram of the layer structure of the inverted device provided by the embodiment of the present application; Description of the Drawings:

[0030] 1. Anode; 2. Hole transport layer; 3. Excitation layer; 4. Electron transport layer; 5. Cathode. Detailed Embodiments

[0031] Next, the technical solutions in the embodiments of the present application will be clearly and completely described in conjunction with the 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 embodiments described herein are only used to illustrate and explain the present application, and are not used to limit the present application.

[0032] 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; and "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.

[0033] In the present application, "and / or" describes the association relationship of associated objects and indicates 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.

[0034] In the present application, "at least one" means one or more, and "multiple" means two or more. "At least one kind", "at least one item (piece) below" or similar expressions refer to any combination of these items, including any combination of single item (piece) or plural items (pieces). For example, "at least one item (piece) among a, b, or c", or, "at least one item (piece) among a, b, and c" can both represent: a, b, c, a - b (that is, a and b), a - c, b - c, or a - b - c, where a, b, and c can be single or multiple respectively.

[0035] 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 the certain layer, or there are other spacer structure layers between the another layer and the certain layer. For example, when forming a second electrode "on" a first carrier functional layer, the so-called "on" can mean that the formed second electrode is adjacent to the first carrier functional layer, or there are other spacer structure layers between the second electrode and the first carrier functional layer, such as an excitation layer.

[0036] The various embodiments of this application may 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 described range description has specifically disclosed all possible sub-ranges and the individual 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 the individual 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.

[0037] The technical solution of this application is as follows:

[0038] The first aspect

[0039] A composite material provided by an embodiment of this application includes a first compound and a second compound. The first compound includes quantum dots with ligands connected to their surfaces, and the second compound includes a gelling agent; the ligand is connected to the gelling agent.

[0040] In some embodiments, the ligand is connected to the gelling agent through an amide bond.

[0041] By connecting the ligand on the surface of the quantum dots and the gelling agent, the distance between the quantum dots is increased, the electrostatic adsorption force between the quantum dots is reduced, making it difficult for the quantum dots to aggregate, thereby improving the stability of the quantum dots and extending the storage time of the quantum dots.

[0042] In some embodiments, the ligand is selected from aliphatic carboxylic acid ligands with 1 - 30 carbon atoms, aromatic carboxylic acid ligands with 6 - 30 ring atoms, aromatic heterocyclic carboxylic acid ligands with 5 - 30 ring atoms, or aliphatic heterocyclic carboxylic acid ligands with 3 - 30 carbon atoms.

[0043] In some embodiments, the gelling agent is selected from those with a conductivity of 10 2 -10 3A conductive gel of S / m. This enables the composite material to maintain a relatively high conductivity, enhances the ability of quantum dots to transfer charges, improves the charge transfer efficiency, makes it easier for electrons to jump from one quantum dot to another, and reduces the transmission energy consumption.

[0044] In some other embodiments, the fatty carboxylic acid ligands include but are not limited to: caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, lignoceric acid, cerotic acid, oleic acid, linoleic acid, arachidonic acid, eicosapentaenoic acid, erucic acid, and docosahexaenoic acid, one or more of them. The aromatic carboxylic acid ligands include but are not limited to: benzoic acid, salicylic acid, caffeic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, one or more of them. The aromatic heterocyclic carboxylic acid ligands include but are not limited to: tetrahydrofuran-2,5-dicarboxylic acid, (S)-tetrahydrofuran-2-carboxylic acid, indoleacetic acid, indolepropionic acid, indolebutyric acid, 4-pyrimidinecarboxylic acid, picolinic acid, 2,3-pyridinedicarboxylic acid, 2-pyrimidineacetic acid, one or more of them. The aliphatic heterocyclic carboxylic acid ligands include but are not limited to: 2-oxirane carboxylic acid, cyclopentanethiolacetic acid, and oxolinic acid, one or more of them.

[0045] In some embodiments, the ligand is selected from fatty carboxylic acid ligands having 1 to 8 carbon atoms.

[0046] In some embodiments, the ligand is selected from one or more of mercaptoacetic acid, mercaptopropionic acid, mercaptobutyric acid, and mercaptooleic acid; and / or

[0047] In some embodiments, the gelling agent has an amino group.

[0048] In some embodiments, the gelling agent is selected from one or more of N,N'-bis(octadecyl)-L-glutamic acid diamide, N,N'-bis(octadecyl)-d-amino glutamic acid diamide, L-glutamic acid amide-15N, N(2)-L-alanyl-L-glutamine, polyacrylamide / polyethyleneimine composite gel, polystyrene / chitosan composite gel, and polyaniline gel. The gelling agent has a three-dimensional network structure and can encapsulate quantum dots, playing a role in protecting and dispersing the quantum dots.In some embodiments, the quantum dots 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 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; 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, and 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 materials include doped or undoped inorganic perovskite semiconductors or organic-inorganic hybrid perovskite semiconductors. The structural general formula of the inorganic perovskite semiconductors is AMX 3 , where A is Cs +The 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 them, X is a halogen anion, including Cl - , Br - , I - One or more 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+ One or more of them, X is a halogen anion, including Cl - , Br - , I - One or more of them.

[0049] In some embodiments, the mass ratio of the second compound to the first compound is 1:(10 - 20).

[0050] Second aspect

[0051] The embodiments of the present application also provide a method for preparing a thin film, including the following steps:

[0052] Providing a first mixture including a first compound and a second mixture including a second compound, the first compound is a quantum dot with a ligand connected to the surface, and the second compound is a gelling agent;​

[0053] Deposit the first mixture and the second mixture, and perform heat treatment after the deposition to obtain a thin film.

[0054] In some embodiments, the ligand contains a carboxyl group, and the gelling agent contains an amino group; and / or

[0055] In the step of depositing the first mixture and the second mixture, the mass ratio of the second compound to the first compound is 1:(10 - 20); and / or

[0056] The first mixture is obtained by mixing a first compound with a first solvent, and the concentration of the first mixture is 10 - 20 mg / ml; and / or

[0057] The second mixture is obtained by mixing a second compound with a second solvent, and the concentration of the second mixture is 1 - 2 mg / ml; both the first solvent and the second solvent are polar solvents and have a boiling point of 80 - 120 °C.

[0058] The heat treatment causes an amino - carboxylic acid condensation reaction between the first mixture and the second mixture. Abandon the high - boiling - point solvents used in the related art and use low - boiling - point solvents to reduce the liquid surface tension and prevent the coffee - ring effect. The ratio of the second mixture to the first mixture is adjusted according to the ratio of the second compound to the first compound of 1:(10 - 20) and the concentrations of the first mixture and the second mixture.

[0059] In some embodiments, the first solvent is selected from one or more of alkanes, aromatic hydrocarbons, halogenated hydrocarbons, alcohol compounds, ether compounds, furan compounds, pyridine compounds, and amide compounds; and / or

[0060] The second solvent is selected from one or more of alkanes, aromatic hydrocarbons, halogenated hydrocarbons, alcohol compounds, ether compounds, furan compounds, pyridine compounds, and amide compounds.

[0061] The alkanes include, but are not limited to, one or more of nonane, decane, terpanes, butylcyclohexane, n - octane, n - hexane, n - heptane, n - nonane, n - decane, cyclohexane, and cyclopentane; the aromatic hydrocarbons include, but are not limited to, one or more of diethylbenzene, triphenyl, propylbenzene, isopropylbenzene, and butylbenzene; the halogenated hydrocarbons include, but are not limited to, one or more of chloroform and carbon tetrachloride; the alcohol compounds include, but are not limited to, one or more of methanol, ethanol, propanol, butanol, and ethylene glycol; the ether compounds include, but are not limited to, one or more of ethylene glycol monomethyl ether; the furan compounds include, but are not limited to, one or more of tetrahydrofuran and 2 - methylfuran; the pyridine compounds include, but are not limited to, pyridine; the amide compounds include, but are not limited to, N,N - dimethylformamide; the sulfone compounds include, but are not limited to, dimethyl sulfoxide.

[0062] In some embodiments, the first solvent is selected from one of propanol, isopropanol, butanol, n-butanol, isobutanol, hexanol, isopropanol, benzene, cyclohexane, and n-heptane; and / or

[0063] the second solvent is selected from one of propanol, isopropanol, butanol, n-butanol, isobutanol, hexanol, isopropanol, benzene, cyclohexane, and n-heptane; and / or

[0064] the pH value of the first solvent is 7; and / or

[0065] the pH value of the second solvent is 7.

[0066] When the pH value of the first solvent and / or the second solvent is 7, the surface charge states of the quantum dots and the gelling agent can remain relatively stable, and the surface charge will greatly affect the stability and activity of the quantum dots and the gelling agent. Therefore, a pH value of 7 can reduce the oxidation of the quantum dots and the gelling agent and maintain their stability and activity.

[0067] In some embodiments, the heat treatment temperature is 80 - 110 °C; and / or

[0068] the heat treatment time is 30 - 60 min.

[0069] The heat treatment causes an amino-carboxyl condensation reaction between the first mixture and the second mixture. The specific heat treatment temperature is selected according to the boiling points of the first solvent and the second solvent.

[0070] In the temperature range of 80 - 110 °C, the collision frequency between reaction molecules can be increased, thereby accelerating the rate of the amino-carboxyl condensation reaction, because increasing the temperature increases the probability of effective reactions; it can also promote the reaction to proceed in a direction more favorable for the formation of the target product, thereby increasing the yield of the target product.

[0071] In some embodiments, the step of depositing the first mixture and the second mixture specifically includes:

[0072] depositing the first mixture and then depositing the second mixture on the first mixture; or

[0073] depositing the second mixture and then depositing the first mixture on the first mixture; or

[0074] mixing the first mixture and the second mixture at 60 - 80 °C and then depositing.

[0075] Mixing the first mixture and the second mixture at 60 - 80 °C and then depositing can ensure that the first mixture and the second mixture are always in a solution state, avoid forming a gel state that affects deposition, and at the same time avoid the temperature reaching the reaction temperature of the first mixture and the second mixture.

[0076] In some embodiments, the ligand and the gelling agent in the thin film are connected by an amide bond after the heat treatment; and / or

[0077] The ligand is selected from fatty carboxylic acid ligands with 1-30 carbon atoms, aromatic carboxylic acid ligands with 6-30 ring atoms, aromatic heterocyclic carboxylic acid ligands with 5-30 ring atoms, or aliphatic heterocyclic carboxylic acid ligands with 3-30 carbon atoms; and / or

[0078] The gelling agent is selected from conductive gels with a conductivity of 10 2 -10 3 S / m; and / or

[0079] The ligand is selected from one or more of mercaptoacetic acid, mercaptopropionic acid, mercaptobutyric acid, and mercaptooleic acid; and / or

[0080] The gelling agent is selected from one or more of N,N'-bis(octadecyl)-L-glutamic acid diamide, N,N'-bis(octadecyl)-d-aminoglutamic acid diamide, L-glutamic acid amide-15N, N(2)-L-alanyl-L-glutamine, polyacrylamide / polyethyleneimine composite gel, polystyrene / chitosan composite gel, and polyaniline gel.

[0081] In a third aspect

[0082] An embodiment of the present application provides a thin film prepared by the above thin film preparation method.

[0083] In some embodiments, the thin film is gel-like.

[0084] In a fourth aspect

[0085] An embodiment of the present application provides an optoelectronic device, comprising:

[0086] An anode and a cathode disposed opposite to each other;

[0087] An excitation layer disposed between the first functional layer and the second functional layer;

[0088] Among them, the excitation layer includes the composite material as described above or the composite material prepared by the composite material preparation method as described above. In the related art, the high-boiling-point solvent has the advantage of fast volatilization rate and reducing the blockage of the printing nozzle. Usually, the solution obtained by mixing quantum dots with the high-boiling-point solvent is used as the excitation layer solution. However, this high-boiling-point solvent is prone to the coffee ring phenomenon, resulting in uneven film formation of the excitation layer, thereby affecting the device performance. And when the excitation layer solution still has fluidity, it needs to be immediately transferred to other processes. In this embodiment, by making the gelator and the quantum dots undergo an amino-carboxyl condensation reaction, the distance between the quantum dots is increased, and the low-boiling-point solvent used can reduce the liquid surface tension and improve the coffee ring phenomenon; at the same time, a quantum dot material with gel properties is formed. After cooling, the fluidity disappears, and the film layer is stable during the transfer process, jointly making the formed film layer have a lower roughness and better uniformity, and further making the current density difference at each part of the excitation layer small, improving the device performance.

[0089] In some embodiments, the anode and the cathode each independently 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, and the alloy electrode includes an Au:Mg alloy electrode or an Ag:Mg alloy electrode; and / or

[0090] The first functional layer and the second functional layer are disposed between the anode and the cathode; the materials of the first functional 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-ethylhexyloxy)-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 amine, polynuclear aromatic tertiary amine, 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, 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene, PEDOT, PEDOT:PSS, PEDOT:PSS doped with s-MoO 3 derivatives, 4,4',4'-tris(N-3-methylphenyl-N-phenylamino)triphenylamine, tetracyanoquinodimethane, doped graphene, undoped graphene, C60, copper phthalocyanine, second doped metal oxide particles, second undoped metal oxide particles, metal sulfide and metal nitride, one or more of them; and / or

[0091] The material of the second functional layer includes one or more of inorganic electronic functional materials and organic electronic functional materials. The inorganic electronic functional materials include one or more of first doped metal oxide particles, first undoped metal oxide particles, IIB-VIA group semiconductor materials, IIIA-VA group semiconductor materials, and IB-IIIA-VIA group semiconductor materials. The organic electronic functional materials include one or more of quinoxaline compounds, imidazole compounds, triazine compounds, fluorene-containing compounds, hydroxyquinoline compounds, and fullerene derivatives.

[0092] Fifthly, an embodiment of the present application provides a method for manufacturing an optoelectronic device, including the following steps:

[0093] S1 Deposit a hole injection layer material on the anode to obtain a hole injection layer;

[0094] S2 Deposit a hole transport layer on the hole injection layer to obtain a hole transport layer;

[0095] S3 Deposit a first mixture and a second mixture on the hole transport layer, heat-treat the deposited first mixture and second mixture at 80-110 °C for 30-60 min, and then cool to obtain an excitation layer;

[0096] S4 Deposit an electron transport layer material on the excitation layer to obtain an electron transport layer;

[0097] S5 Deposit an electron injection layer material on the electron transport layer to obtain an electron injection layer;

[0098] S6 Evaporate the material of the cathode onto the electron injection layer to obtain a cathode;

[0099] S7 Package.

[0100] An upright optoelectronic device is obtained. In this embodiment, the cooling temperature is the temperature when a gel-like thin film is formed.

[0101] In some embodiments, step S3 is specifically: deposit the first mixture on the hole transport layer, deposit the second mixture on the first mixture, heat-treat the deposited first mixture and second mixture at 80-110 °C for 30-60 min, and then cool to 25 °C to obtain an excitation layer.

[0102] In some other embodiments, step S3 may also be: deposit the second mixture on the hole transport layer, deposit the first mixture on the second mixture, heat-treat the deposited first mixture and second mixture at 80-110 °C for 30-60 min, and then cool to 25 °C to obtain an excitation layer;

[0103] In some embodiments, step S3 may also be: at 60 - 80°C, mix the first mixture and the second mixture and then deposit the mixture on the hole transport layer, heat-treat at 80 - 110°C for 30 - 60 min, and cool to 25°C to obtain the excitation layer.

[0104] In some embodiments, the method for preparing the optoelectronic device may also be:

[0105] S1 Deposit the electron injection layer material on the upper cathode to obtain the electron injection layer;

[0106] S2 Deposit the electron transport layer material on the hole injection layer to obtain the electron transport layer;

[0107] S3 Deposit the first mixture and the second mixture on the electron transport layer, heat-treat the deposited first mixture and second mixture at 80 - 110°C for 30 - 60 min, and cool to obtain the excitation layer;

[0108] S4 Deposit the hole injection layer material on the hole transport layer to obtain the hole injection layer;

[0109] S5 Evaporate the anode material onto the hole injection layer to obtain the anode.

[0110] S6 Package.

[0111] An inverted optoelectronic device is obtained. In this embodiment, forming a gel-like thin film is used as the cooling standard.

[0112] In some embodiments, step S3 may be: deposit the first mixture on the electron transport layer, deposit the second mixture on the first mixture, heat-treat the deposited first mixture and second mixture at 80 - 110°C for 30 - 60 min, and cool to 25°C to obtain the excitation layer;

[0113] Or it may be: deposit the second mixture on the electron transport layer, deposit the first mixture on the second mixture, heat-treat the deposited first mixture and second mixture at 80 - 110°C for 30 - 60 min, and cool to 25°C to obtain the excitation layer;

[0114] Or it may also be: at 60 - 80°C, mix the first mixture and the second mixture and then deposit the mixture on the electron transport layer, heat-treat at 80 - 110°C for 30 - 60 min, and cool to 25°C to obtain the excitation layer.

[0115] The deposition method can be realized by using the well-known technical means in the art, specifically:

[0116] The excitation layer can be formed by chemical vapor deposition, sequential ionic layer adsorption and reaction, anodic oxidation, coprecipitation, and solution processing. Among them, chemical methods include, for example, chemical vapor deposition, sequential ionic layer adsorption and reaction, anodic oxidation, electrolytic deposition, and coprecipitation.

[0117] The hole transport layer can be formed by physical coating methods. Physical coating methods include, for example, thermal evaporation coating, electron beam evaporation coating, magnetron sputtering, multi-arc ion coating, physical vapor deposition, atomic layer deposition, and pulsed laser deposition. Solution processing methods include, for example, spin coating, printing, inkjet printing, doctor blading, printing, dip coating, immersion, spraying, roll coating, casting, slot die coating, and bar coating.

[0118] The electron transport layer can be formed by chemical vapor deposition, sequential ionic layer adsorption and reaction, anodic oxidation, coprecipitation, and solution processing.

[0119] When the hole injection layer and the electron injection layer are organic molecular compounds, all of the above-listed methods can be used. When they are inorganic molecular compounds, solution processing methods can be used.

[0120] Specific processing methods and conditions can refer to common methods in the art and will not be elaborated here.

[0121] Sixth aspect

[0122] The embodiments of the present application provide a display device, including the composite material prepared by the composite material preparation method as described above, or the optoelectronic device as described above. The display device can 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 scale, a vehicle-mounted display, a television, or an e-book reader. Among them, the smart wearable device can be, for example, a smart bracelet, a smart watch, a virtual reality (VR) helmet, etc.

[0123] The following specifically describes the present application through specific embodiments. The following embodiments are only partial embodiments of the present application and do not limit the present application.

[0124] Taking the CdSe / CdZnS quantum dot material as an example, a synthesis method of a quantum dot material with ligands connected to the surface includes the following steps:

[0125] S1. Mix a cadmium source, a zinc source, and a ligand additive, and add a selenium source and a sulfur source at 180°C to 320°C.

[0126] S2. At 240 to 320°C, add a selenium source to the reaction system of S1 again to form a transition layer on the core of the quantum dots.

[0127] S3. At 240 - 320 °C, add a sulfur source to the reaction system of S2 again, and react to obtain quantum dots.

[0128] Among them, the cadmium source includes but is not limited to at least one of cadmium powder, cadmium oxide, cadmium chloride, cadmium oxalate, cadmium acetate, cadmium carbonate, cadmium stearate, cadmium acetylacetonate, cadmium myristate; the zinc source includes but is not limited to at least one of zinc powder, zinc oxide, zinc chloride, zinc oxalate, zinc acetate, zinc carbonate, zinc stearate, zinc acetylacetonate, zinc myristate, zinc undecylenate; the selenium source includes but is not limited to at least one of inorganic selenium, organophosphorus complexes of selenium, organic selenium compounds, organic selenol compounds. Specifically, the selenium source includes but is not limited to at least one of selenium powder, a 15 - ene solution of selenium, selenium dioxide, trioctylphosphine selenide, tributylphosphine selenide, selenol, diselenide, selenoether, selenoester, selenoamide, selenazole; the sulfur source includes but is not limited to at least one of inorganic sulfur, organophosphorus complexes of sulfur, organic sulfur compounds, organic thiol compounds.

[0129] Specifically, the sulfur source includes but is not limited to at least one of sulfur powder, a 15 - ene solution of sulfur, a n - octylamine solution of sulfur, trioctylphosphine sulfur, tributylphosphine sulfur, 1 - octanethiol.

[0130] The feeding amount of the ligand additive is 1 - 10 times the total feeding amount of the cadmium source and the zinc source in step S1. The feeding amount of the zinc source in step S1 is 18 - 20 times that of the cadmium source, and the total feeding amount of the selenium source and the sulfur source in step S1 is 1 - 8 times the feeding amount of the cadmium source;

[0131] The feeding amount of the selenium source in step S2 is 0.5 - 2 times the feeding amount of the cadmium source in step S1; the feeding amount of the sulfur source in step S3 is 6 - 10 times the feeding amount of the cadmium source in step S1;

[0132] The organic solvent is at least one of alkanes, alkenes, halogenated hydrocarbons, aromatic hydrocarbons, ethers, amines, ketones, esters with 10 - 22 carbon atoms. Specifically, the organic solvent is at least one of tetradecene, pentadecene, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, paraffin oil.

[0133] Ligand additives: mercaptoacetic acid, mercaptopropionic acid, mercaptobutyric acid, mercaptooleic acid.

[0134] Quantum Dot Synthesis Example 1

[0135] This synthesis example provides a method for synthesizing CdSe / CdZnS quantum dot materials coated with mercaptoacetic acid ligands on the surface, specifically including the following steps:

[0136] Mix 0.4 mmol of cadmium oxide, 8 mmol of zinc acetate, 8 mmol of mercaptoacetic acid and 200 ml of 1-octadecene. Heat to 300 °C under an inert gas atmosphere, inject 0.4 mmol of trioctylphosphine selenide and 0.2 mmol of trioctylphosphine sulfide, and carry out the reaction. After the reaction is completed, cool to 280 °C, add 0.22 mmol of trioctylphosphine selenide, and continue the reaction. Finally, add 3 mmol of trioctylphosphine sulfide and continue the reaction. Precipitate and purify the obtained product with n-heptane and ethanol to obtain CdSe / CdZnS quantum dot material coated with mercaptoacetic acid on the surface.

[0137] Quantum Dot Synthesis Example 2

[0138] This synthesis example provides a method for synthesizing CdSe / CdZnS quantum dot material coated with mercaptopropionic acid ligand on the surface. The difference from Quantum Dot Synthesis Example 1 is that mercaptoacetic acid is replaced by mercaptopropionic acid. CdSe / CdZnS quantum dot material coated with mercaptoacetic acid on the surface is obtained.

[0139] Quantum Dot Synthesis Example 3

[0140] This synthesis example provides a method for synthesizing CdSe / CdZnS quantum dot material coated with mercaptobutyric acid ligand on the surface. The difference from Quantum Dot Synthesis Example 1 is that mercaptoacetic acid is replaced by mercaptopropionic acid. CdSe / CdZnS quantum dot material coated with mercaptoacetic acid on the surface is obtained.

[0141] Quantum Dot Synthesis Example 4

[0142] This synthesis example provides a method for synthesizing CdSe / CdZnS quantum dot material coated with mercaptopropionic acid ligand on the surface. The difference from Quantum Dot Synthesis Example 1 is that mercaptoacetic acid is replaced by mercaptopropionic acid. CdSe / CdZnS quantum dot material coated with mercaptoacetic acid on the surface is obtained.

[0143] Gelling Agent Synthesis Example 1

[0144] This synthesis example provides a method for synthesizing polystyrene / chitosan composite gel, which specifically includes the following steps:

[0145] 1. Dissolve 1 g of chitosan powder in 200 ml of water to prepare a chitosan aqueous solution;

[0146] 2. Add 1 g of polystyrene particles to the chitosan aqueous solution and mix evenly;

[0147] 3. Heat the mixture to 120 - 150 °C, heat for 20 min to melt the polystyrene, then mix with the chitosan aqueous solution and cool to 25 °C to obtain polystyrene / chitosan composite gel.

[0148] Gelling Agent Synthesis Example 2

[0149] This synthesis example provides a method for synthesizing polyacrylamide / polyethyleneimine composite gel, which specifically includes the following steps:

[0150] Add 0.5 g of polyacrylamide (PAM) to 100 ml of water and stir well to dissolve it; add 0.1 g of polyethyleneimine (PEI) to 100 ml of water and stir well to dissolve it. Slowly stir and mix the two solutions prepared above at 60 °C to avoid the generation of bubbles. Continuously stir for 1 h until a uniform polyacrylamide / polyethyleneimine composite gel is obtained.

[0151] Gelator Synthesis Example 3

[0152] This synthesis example provides a method for synthesizing N,N'-bis(octadecyl)-L-glutamic acid diamide (), which specifically includes the following steps:

[0153] 1. Mix L-glutamic acid and N,N'-dihydrocarbamate in a molar ratio of 1:1.1 and dissolve them in dimethyl sulfoxamide (DMF), and stir and react for 30 minutes;

[0154] 2. Add the condensing agent N-hydroxysuccinimide (HBTU) and the catalyst dimethylaminoimidazole (DMAP), and continue to stir and react for 2 hours;

[0155] 3. Add octadecyl bromide and continue to stir and react for 12 hours;

[0156] 4. Transfer the reaction solution to a separatory funnel, add a hydrochloric acid solution with the same volume as the reaction solution, and separate the organic phase;

[0157] 5. Wash the organic phase with chloroform, then wash the organic phase with saturated sodium chloride solution, and finally remove the solvent with a rotary evaporator to obtain N,N'-bis(octadecyl)-L-glutamic acid diamide ().

[0158] The above entire synthesis process needs to be carried out under an inert atmosphere to avoid the influence of oxygen and moisture on the reaction.

[0159] Among them, the molar ratio of L-glutamic acid and N,N'-dihydrocarbamate can be adjusted as needed, generally taking 1:1.1 or 1:1.2. The amounts of HBTU and DMAP added are generally about 10% of the total amount of L-glutamic acid and N,N'-dihydrocarbamate. The amount of octadecyl bromide is 2-3 times the amount of L-glutamic acid.

[0160] Gelator Synthesis Example 4

[0161] This synthesis example provides a method for synthesizing N,N'-bis(octadecyl)-D-glutamic acid diamide (), which specifically includes the following steps:

[0162] 1. Mix D-glutamic acid and N,N'-dihydrocarbamate in a molar ratio of 1:1.1 and dissolve them in dimethyl sulfoxide (DMF), and stir the reaction for 30 minutes;

[0163] 2. Add the condensing agent N-hydroxysuccinimide (HBTU) and the catalyst dimethylaminopyridine (DMAP), and continue to stir the reaction for 2 hours;

[0164] 3. Add octadecyl bromide and continue to stir the reaction for 12 hours;

[0165] 4. Transfer the reaction solution to a separatory funnel, add 100 ml of hydrochloric acid solution with the same volume as the reaction solution, and separate the organic phase;

[0166] 5. Wash the organic phase with chloroform, then wash the organic phase with saturated sodium chloride solution, and finally remove the solvent with a rotary evaporator to obtain the product.

[0167] The above entire synthesis process needs to be carried out under an inert atmosphere to avoid the influence of oxygen and moisture on the reaction.

[0168] The molar ratio of D-glutamic acid and N,N'-dihydrocarbamate can be adjusted as needed, generally taking 1:1.1 or 1:1.2. The amounts of HBTU and DMAP added are generally about 10% of the total amount of D-glutamic acid and N,N'-dihydrocarbamate. The amount of octadecyl bromide can be adjusted as needed, generally taking 2-3 times the amount of D-glutamic acid.

[0169] Use a conductivity tester to test the conductivity of the liquid at the same concentration or the film layer at the same thickness. The conductivities of the gel agents prepared in the above Gel Agent Synthesis Examples 1-4 are as follows:

[0170]

[0171] Composite Material Example 1

[0172] This example provides a composite material and a preparation method thereof.

[0173] The preparation method of the composite material includes the following steps:

[0174] S1. Mix the first compound and the first solvent. The first compound is a CdSe / CdZnS quantum dot material coated with a mercaptoacetic acid ligand, and the first solvent is isopropanol to obtain a 10 mg / mL first mixture;

[0175] S2. Mix the second compound and the second solvent. The second compound is N,N'-bis(octadecyl)-L-glutamic acid diamide, and the second solvent is isopropanol to obtain a 1 mg / mL second mixture;

[0176] S3. Deposit the first mixture and deposit the second mixture on the first mixture, where the mass ratio of the second compound to the first compound is 1:10. After deposition, heat at 90 °C for 30 min to obtain a composite material, and then cool to 25 °C to obtain a gel-like film.

[0177] Composite Material Example 2

[0178] This example provides a composite material and a preparation method thereof.

[0179] Compared with the preparation method of the composite material in Composite Material Example 1, the difference in the preparation method of the composite material in this example is that the first compound is a CdSe / CdZnS quantum dot material coated with mercaptopropionic acid on the surface.

[0180] Composite Material Example 3

[0181] This example provides a composite material and a preparation method thereof.

[0182] Compared with the preparation method of the composite material in Composite Material Example 1, the difference in the preparation method of the composite material in this example is that the first compound is a CdSe / CdZnS quantum dot material coated with mercaptobutyric acid on the surface.

[0183] Composite Material Example 4

[0184] This example provides a composite material and a preparation method thereof.

[0185] Compared with the preparation method of the composite material in Composite Material Example 1, the difference in the preparation method of the composite material in this example is that the first compound is a CdSe / CdZnS quantum dot material coated with mercaptooleic acid on the surface.

[0186] Composite Material Example 5

[0187] This example provides a composite material and a preparation method thereof.

[0188] Compared with the preparation method of the composite material in Composite Material Example 1, the difference in the preparation method of the composite material in this example is that both the first solvent and the second solvent are toluene, and the second compound is N,N'-dioctadecyl-d-aminoglutaramide.

[0189] Composite Material Example 6

[0190] This example provides a composite material and a preparation method thereof.

[0191] Compared with the composite material preparation method in Composite Material Example 1, the difference in the composite material preparation method in this example is that: both the first solvent and the second solvent are cyclohexane, and the second compound is L-glutamic acid amide-15N.

[0192] Composite Material Example 7

[0193] This example provides a composite material and a preparation method thereof.

[0194] Compared with the composite material preparation method in Composite Material Example 1, the difference in the composite material preparation method in this example is that: both the first solvent and the second solvent are n-heptane, and the second compound is N(2)-L-alanyl-L-glutamine.

[0195] Composite Material Example 8

[0196] This example provides a composite material and a preparation method thereof.

[0197] Compared with the composite material preparation method in Composite Material Example 1, the difference in the composite material preparation method in this example is that: both the first solvent and the second solvent are butanol, and step S3 is replaced with "deposit the first mixture and the second mixture, wherein the mass ratio of the second compound to the first compound is 1:10, heat at 90 °C for 30 min, and then cool to 25 °C to obtain a thin film".

[0198] Composite Material Example 9

[0199] This example provides a composite material and a preparation method thereof.

[0200] Compared with the composite material preparation method in Composite Material Example 8, the difference in the composite material preparation method in this example is that: the first compound is a CdSe / CdZnS quantum dot material surface-coated with mercaptopropionic acid.

[0201] Composite Material Example 10

[0202] This example provides a composite material and a preparation method thereof.

[0203] Compared with the composite material preparation method in Composite Material Example 8, the difference in the composite material preparation method in this example is that: the first compound is a CdSe / CdZnS quantum dot material surface-coated with mercaptobutyric acid.

[0204] Composite Material Example 11

[0205] This example provides a composite material and a preparation method thereof.

[0206] Compared with the composite material preparation method in Composite Material Example 8, the difference in the composite material preparation method in this example is that: the first compound is a CdSe / CdZnS quantum dot material coated with mercapto oleic acid on the surface.

[0207] Composite Material Example 12

[0208] This example provides a composite material and a preparation method thereof.

[0209] Compared with the composite material preparation method in Composite Material Example 1, the difference in the composite material preparation method in this example is that: both the first solvent and the second solvent are toluene, and the second compound is a polyacrylamide / polyethyleneimine composite gel.

[0210] Composite Material Example 13

[0211] This example provides a composite material and a preparation method thereof.

[0212] Compared with the composite material preparation method in Composite Material Example 1, the difference in the composite material preparation method in this example is that: both the first solvent and the second solvent are cyclohexane, and the second compound is a polystyrene / chitosan composite gel.

[0213] Composite Material Example 14

[0214] This example provides a composite material and a preparation method thereof.

[0215] Compared with the composite material preparation method in Composite Material Example 1, the difference in the composite material preparation method in this example is that: both the first solvent and the second solvent are n-heptane, and the second compound is a polyaniline gel.

[0216] Composite Material Example 15

[0217] This example provides a composite material and a preparation method thereof.

[0218] Compared with the composite material preparation method in Composite Material Example 6, the difference in the composite material preparation method in this example is that: both the first solvent and the second solvent are butanol.

[0219] Quantum Dot Material Comparative Example 1

[0220] In this comparative example, a CdSe / CdZnS quantum dot material is used. CdZnS is dissolved in cyclooctane to prepare a quantum dot solution, and after depositing the quantum dot solution and drying, a film is prepared.

[0221] Composite Material Performance

[0222] Use TEM scanning electron microscopy to observe the microstructure and test the particle size of the composite materials obtained in the following table:

[0223]

[0224] Test Examples 1 - 8 and Test Comparative Example 1 of the TEM images after 30 days of placement: See successively Figures 1 - 9 。

[0225] It can be seen from the TEM images that there are obviously regular spacings between the quantum dots in Test Examples 1 - 8, which indicates that the quantum dot material does not show agglomeration after long-term placement. In the TEM image of Test Comparative Example 1, the particle size differences are large and obvious agglomeration of the quantum dots occurs. Compared with Test Comparative Example 1, Test Examples 1 - 8 all have a longer storage time. This is mainly because after the carboxyl - amino condensation reaction between the gelling agent and the quantum dots, the surface of the quantum dots has a longer chain structure, thus increasing the distance between the quantum dots, hindering the electrostatic adsorption between the quantum dots, and further making it difficult for the quantum dots to agglomerate.

[0226] Film properties

[0227] The following method is used to detect the properties of the films obtained from Composite Material Examples 1 - 15 above:

[0228] Test method for Ra roughness: Place the probe of the surface roughness meter on the surface to be measured, start the instrument for measurement. Conduct multiple measurements within a certain range, and then calculate the average value of all measurement values, which is the average Ra roughness value.

[0229] Test method for film uniformity: Place the probe of the film thickness tester on the surface of the film to be measured, start the instrument for measurement. Conduct multiple measurements within a certain range, and then calculate the average value of all measurement values, which is the film thickness. Then move the probe on the film surface for multi-point measurement, and then calculate the standard deviation of the measurement values, which is the index of film uniformity.

[0230] The specific performance data are shown in Table 1:

[0231] Table 1

[0232] Ra roughness Film uniformity (%) Film Example 1 5.2 73.5 Film Example 2 5.5 75.2 Film Example 3 5.8 76.9 Film Example 4 6.1 78.6 Film Example 5 6.4 72.1 Film Example 6 5.7 73.8 Film Example 7 6.0 75.5 Film Example 8 6.3 77.2 Film Example 9 7.2 78.9 Film Example 10 7.0 71.3 Film Example 11 7.0 73.0 Film Example 12 6.1 74.7 Film Example 13 6.6 76.4 Film Example 14 6.9 78.1 Film Example 15 7.5 72.2 Film Comparative Example 1 10.2 60.2

[0233] As can be seen from Table 1: Compared with Film Comparative Example 1, Film Examples 1-15 obtained a film with a gel-like state by reacting the quantum dot surface ligand with the gelling agent, having a lower fluidity. And, since the first solvent and the second solvent used are low-boiling solvents with a relatively fast evaporation rate, it is possible to shorten the drying time after the deposition of the first mixture and the second mixture; at the same time, the low-boiling solvent has the effect of reducing the surface tension of the first mixture and the second mixture, thereby improving the coffee ring phenomenon, making the film have a smaller roughness and a higher film uniformity. While the high-boiling solvent cyclooctane used in Film Comparative Example 1 has a slow evaporation rate and is prone to generating a coffee ring.

[0234] Positive device Example 1

[0235] Refer to Figure 10 , this example provides an optoelectronic device and a preparation method thereof. The optoelectronic device includes an anode 1, a hole transport layer 2, an excitation layer 3, an electron transport layer 4, and a cathode 5 arranged in sequence.

[0236] The preparation method of the optoelectronic device includes the following steps:

[0237] S1. Provide a substrate with an ITO anode having a thickness of 80 nm, ultrasonically clean the substrate plated with ITO with acetone and ethanol for 15 min, then wash it again with deionized water, then dry it on a hot plate at 150 °C for 10 min, and finally perform ultraviolet light irradiation for 20 min to improve the ITO work function and surface energy;

[0238] S2. Spin-coat a TFB-chlorobenzene solution with a concentration of 6.5 mg / mL on the anode at a spin-coating speed of 3000 rpm for 30 s, and anneal it at 120 °C for 20 min to obtain a hole transport layer with a thickness of 20 nm;

[0239] S3:

[0240] S3.1. Dissolve the CdSe / CdZnS quantum dot material coated with mercaptoacetic acid ligand on the surface in an isopropanol solvent to obtain a quantum dot solution with a concentration of 10 mg / mL;

[0241] S3.2. Add N,N'-bis(octadecyl)-L-glutamic acid diamide to an isopropanol solvent to obtain a gelling agent solution with a concentration of 1 mg / mL;

[0242] S3.3. Spin-coat the quantum dot solution obtained in step S3.1 on the hole transport layer, and spin-coat the gelling agent solution obtained in step S3.2 on the quantum dot solution. Among them, the mass ratio of the gelling agent to the quantum dot is 1:10, heat it at 90 °C for 30 min, and then cool it to 25 °C to obtain an excitation layer;

[0243] S4. Spin-coat a ZnO-ethanol solution with a concentration of 20 mg / mL on the excitation layer at a spin-coating speed of 4000 rpm for 30 s, and anneal at 80 °C for 10 min to obtain an electron transport layer with a thickness of 70 nm;

[0244] S5. Evaporate Al material at a speed of 1 Å / s for 100 s on the electron transport layer to obtain a cathode with a thickness of 100 nm.

[0245] Package to obtain an optoelectronic device.

[0246] Positive device Example 2

[0247] This example provides an optoelectronic device and a preparation method thereof.

[0248] Compared with the preparation method of the optoelectronic device in Positive device Example 1, the difference in the preparation method of the optoelectronic device in this example is that step S3.1 is replaced with: "Dissolve the CdSe / CdZnS quantum dot material coated with mercaptopropionic acid ligands in an isopropanol solvent to obtain a quantum dot solution with a concentration of 10 mg / mL".

[0249] Positive device Example 3

[0250] This example provides an optoelectronic device and a preparation method thereof.

[0251] Compared with the preparation method of the optoelectronic device in Positive device Example 1, the difference in the preparation method of the optoelectronic device in this example is that step S3.1 is replaced with: "Dissolve the CdSe / CdZnS quantum dot material coated with mercaptobutyric acid ligands in an isopropanol solvent to obtain a quantum dot solution with a concentration of 10 mg / mL".

[0252] Positive device Example 4

[0253] This example provides an optoelectronic device and a preparation method thereof.

[0254] Compared with the preparation method of the optoelectronic device in Positive device Example 1, the difference in the preparation method of the optoelectronic device in this example is that step S3.1 is replaced with: "Dissolve the CdSe / CdZnS quantum dot material coated with mercaptooleic acid ligands in an isopropanol solvent to obtain a quantum dot solution with a concentration of 10 mg / mL".

[0255] Positive device Example 5

[0256] This example provides an optoelectronic device and a preparation method thereof.

[0257] Compared with the preparation method of the optoelectronic device in Positive device Example 1, the difference in the preparation method of the optoelectronic device in this example is that:

[0258] Replace step S3.1 with: "Dissolve the CdSe / CdZnS quantum dot material coated with mercaptoacetic acid ligands on the surface in toluene solvent to obtain a 10 mg / mL quantum dot solution."

[0259] Replace step S3.2 with: "Add N,N'-dioctadecyl-d-aminoglutaramide to toluene solvent to obtain a 1 mg / mL gelling agent solution."

[0260] Positive device Example 6

[0261] This example provides an optoelectronic device and a preparation method thereof.

[0262] Compared with the preparation method of the optoelectronic device in Positive device Example 1, the difference in the preparation method of the optoelectronic device in this example is that:

[0263] Replace step S3.1 with: "Dissolve the CdSe / CdZnS quantum dot material coated with mercaptoacetic acid ligands on the surface in cyclohexane solvent to obtain a 10 mg / mL quantum dot solution."

[0264] Replace step S3.2 with: "Add L-glutamine-15N to cyclohexane solvent to obtain a 1 mg / mL gelling agent solution."

[0265] Positive device Example 7

[0266] This example provides an optoelectronic device and a preparation method thereof.

[0267] Compared with the preparation method of the optoelectronic device in Positive device Example 1, the difference in the preparation method of the optoelectronic device in this example is that:

[0268] Replace step S3.1 with: "Dissolve the CdSe / CdZnS quantum dot material coated with mercaptoacetic acid ligands on the surface in n-heptane solvent to obtain a 10 mg / mL quantum dot solution."

[0269] Replace step S3.2 with: "Add N(2)-L-alanyl-L-glutamine to n-heptane solvent to obtain a 1 mg / mL gelling agent solution."

[0270] Positive device Example 8

[0271] This example provides an optoelectronic device and a preparation method thereof.

[0272] Compared with the preparation method of the optoelectronic device in the forward device Example 1, the difference in the preparation method of the optoelectronic device in this example is that step S3.1 is replaced with: "Dissolve the CdSe / CdZnS quantum dot material coated with mercaptoacetic acid ligands on the surface in a butanol solvent to obtain a quantum dot solution with a concentration of 10 mg / mL.";

[0273] Step S3.2 is replaced with: "Add N,N'-bis(octadecyl)-L-glutamic acid diamide to a butanol solvent to obtain a gelator solution with a concentration of 1 mg / mL.";

[0274] Step S3.3 is replaced with: "Spin-coat the quantum dot solution obtained in step S3.1 on the hole transport layer, where the mass ratio of the gelator to the quantum dots is 1:10. Spin-coat the gelator solution obtained in step S3.2 on the quantum dot solution, heat at 90 °C for 30 min, and then cool to 25 °C to obtain the excitation layer.";

[0275] Forward Device Example 9

[0276] This example provides an optoelectronic device and a preparation method thereof.

[0277] Compared with the preparation method of the optoelectronic device in the forward device Example 8, the difference in the preparation method of the optoelectronic device in this example is that step S3.1 is replaced with: "Dissolve the CdSe / CdZnS quantum dot material coated with mercaptopropionic acid ligands on the surface in a butanol solvent to obtain a quantum dot solution with a concentration of 10 mg / mL.";

[0278] Forward Device Example 10

[0279] This example provides an optoelectronic device and a preparation method thereof.

[0280] Compared with the preparation method of the optoelectronic device in the forward device Example 8, the difference in the preparation method of the optoelectronic device in this example is that step S3.1 is replaced with: "Dissolve the CdSe / CdZnS quantum dot material coated with mercaptobutyric acid ligands on the surface in a butanol solvent to obtain a quantum dot solution with a concentration of 10 mg / mL.";

[0281] Forward Device Example 11

[0282] This example provides an optoelectronic device and a preparation method thereof.

[0283] Compared with the preparation method of the optoelectronic device in the forward device Example 8, the difference in the preparation method of the optoelectronic device in this example is that step S3.1 is replaced with: "Dissolve the CdSe / CdZnS quantum dot material coated with mercaptooleic acid ligands on the surface in a butanol solvent to obtain a quantum dot solution with a concentration of 10 mg / mL.";

[0284] Front-mounted device Example 12

[0285] This example provides an optoelectronic device and a preparation method thereof.

[0286] Compared with the preparation method of the optoelectronic device in Example 1 of the front-mounted device, the difference in the preparation method of the optoelectronic device in this example is that:

[0287] Replace step S3.1 with: "Dissolve the CdSe / CdZnS quantum dot material coated with mercaptoacetic acid ligand in toluene solvent to obtain a 10 mg / mL quantum dot solution";

[0288] Replace step S3.2 with: "Add polyacrylamide / polyethyleneimine composite gel into toluene solvent to obtain a 1 mg / mL gelling agent solution".

[0289] Front-mounted device Example 13

[0290] This example provides an optoelectronic device and a preparation method thereof.

[0291] Compared with the preparation method of the optoelectronic device in Example 1 of the front-mounted device, the difference in the preparation method of the optoelectronic device in this example is that:

[0292] Replace step S3.1 with: "Dissolve the CdSe / CdZnS quantum dot material coated with mercaptoacetic acid ligand in cyclohexane solvent to obtain a 10 mg / mL quantum dot solution";

[0293] Replace step S3.2 with: "Add polystyrene / chitosan composite gel into cyclohexane solvent to obtain a 1 mg / mL gelling agent solution".

[0294] Front-mounted device Example 14

[0295] This example provides an optoelectronic device and a preparation method thereof.

[0296] Compared with the preparation method of the optoelectronic device in Example 1 of the front-mounted device, the difference in the preparation method of the optoelectronic device in this example is that:

[0297] Replace step S3.1 with: "Dissolve the CdSe / CdZnS quantum dot material coated with mercaptoacetic acid ligand in n-heptane solvent to obtain a 10 mg / mL quantum dot solution";

[0298] Replace step S3.2 with: "Add polyaniline gel into n-heptane solvent to obtain a 1 mg / mL gelling agent solution".

[0299] Front-mounted device Example 15

[0300] This embodiment provides an optoelectronic device and a method for preparing the same.

[0301] Compared with the method for preparing the optoelectronic device in the first embodiment of the normal device, the difference in the method for preparing the optoelectronic device in this embodiment lies in:

[0302] Replace step S3.1 with: "Dissolve the CdSe / CdZnS quantum dot material coated with mercaptoacetic acid ligands on the surface in butanol solvent to obtain a quantum dot solution with a concentration of 10 mg / mL";

[0303] Replace step S3.2 with: "Add L-glutamic acid amide-15N to butanol solvent to obtain a gelling agent solution with a concentration of 1 mg / mL".

[0304] Inverted device Example 1

[0305] Refer to Figure 11 , this embodiment provides an optoelectronic device and a method for preparing the same. The optoelectronic device includes a cathode 5, an electron transport layer 4, an excitation layer 3, a hole transport layer 2, and an anode 1 arranged in sequence.

[0306] The method for preparing the optoelectronic device includes the following steps:

[0307] S1. Provide a substrate with an ITO cathode having a thickness of 70 nm, ultrasonically clean the substrate plated with Al with acetone and ethanol for 15 min, then wash it again with deionized water, then dry it on a hot plate at 150 °C for 10 min, and finally perform ultraviolet light irradiation for 20 min to improve the work function and surface energy of the ITO;

[0308] S2. Spin-coat a ZnO-ethanol solution with a concentration of 20 mg / mL on the cathode at a spin-coating speed of 4000 rpm for 30 s, and anneal it at 80 °C for 10 min to obtain an electron transport layer with a thickness of 70 nm;

[0309] S3.

[0310] S3.1. Dissolve the CdSe / CdZnS quantum dot material coated with mercaptoacetic acid ligands on the surface in isopropanol solvent to obtain a quantum dot solution with a concentration of 10 mg / mL;

[0311] S3.2. Add N,N'-bis(octadecyl)-L-glutamic acid diamide to isopropanol solvent to obtain a gelling agent solution with a concentration of 1 mg / mL;

[0312] S3.3. Spin-coat the quantum dot solution obtained in step S3.1 on the hole transport layer, and spin-coat the gelling agent solution obtained in step S3.2 on the quantum dot solution, where the mass ratio of the gelling agent to the quantum dot is 1:10, heat it at 90 °C for 30 min, and then cool it to 25 °C to obtain an excitation layer;

[0313] S4. Spin-coat a TFB-chlorobenzene solution with a concentration of 6.5 mg / mL on the excitation layer at a spin-coating speed of 3000 rpm for 30 s, and anneal at 120 °C for 20 min to obtain a hole transport layer with a thickness of 20 nm.

[0314] S5. Evaporate Al material at a speed of 1 Å / s for 100 s on the hole transport layer to obtain an anode with a thickness of 100 nm.

[0315] Package to obtain an optoelectronic device.

[0316] Inverted device Example 2

[0317] This example provides an optoelectronic device and a preparation method thereof.

[0318] Compared with the preparation method of the optoelectronic device in Inverted device Example 1, the difference in the preparation method of the optoelectronic device in this example is that:

[0319] Replace step S3.1 with: "Dissolve the CdSe / CdZnS quantum dot material coated with mercaptopropionic acid ligands in toluene solvent to obtain a quantum dot solution with a concentration of 10 mg / mL";

[0320] Replace step S3.2 with: "Add N,N'-bis(octadecyl)-L-glutamic acid diamide to toluene solvent to obtain a gelator solution with a concentration of 1 mg / mL;".

[0321] Inverted device Example 3

[0322] This example provides an optoelectronic device and a preparation method thereof.

[0323] Compared with the preparation method of the optoelectronic device in Inverted device Example 1, the difference in the preparation method of the optoelectronic device in this example is that:

[0324] Replace step S3.1 with: "Dissolve the CdSe / CdZnS quantum dot material coated with mercaptobutyric acid ligands in cyclohexane solvent to obtain a quantum dot solution with a concentration of 10 mg / mL".

[0325] Replace step S3.2 with: "Add N,N'-bis(octadecyl)-L-glutamic acid diamide to cyclohexane solvent to obtain a gelator solution with a concentration of 1 mg / mL;".

[0326] Inverted device Example 4

[0327] This example provides an optoelectronic device and a preparation method thereof.

[0328] Compared with the preparation method of the optoelectronic device in the forward device Example 1, the difference in the preparation method of the optoelectronic device in this example is as follows:

[0329] Replace step S3.1 with: "Dissolve the CdSe / CdZnS quantum dot material coated with mercaptooleic acid ligands on the surface in n - heptane solvent to obtain a 10 mg / mL quantum dot solution";

[0330] Replace step S3.2 with: "Add N,N'-bis(octadecyl)-L-glutamic acid diamide to n - heptane solvent to obtain a 1 mg / mL gelling agent solution;".

[0331] In the above forward device examples and inverted device examples, some of the gelling agents are the gelling agents obtained from Synthesis Examples 1 - 4, and the CAS numbers of other gelling agents are:

[0332] The CAS number of L - glutamate - amide - 15N is: 59681 - 32 - 2;

[0333] The CAS number of N(2)-L-alanyl-L-glutamine is: 39537 - 23 - 0;

[0334] The CAS number of polyaniline gel is: 5612 - 44 - 2;

[0335] Forward device Comparative Example 1

[0336] This example provides an optoelectronic device and its preparation method.

[0337] Compared with the preparation method of the optoelectronic device in the forward device Example 1, the difference in the preparation method of the optoelectronic device in this example is: Replace step S3 with: "Spin - coat CdZnS blue - light quantum dot - cyclooctane with a concentration of 10 mg / mL on the hole - transporting layer at a spin - coating speed of 1500 rpm for 30 s, and anneal at 100 °C for 5 min to obtain an excitation layer".

[0338] Inverted device Comparative Example 1

[0339] This example provides an optoelectronic device and its preparation method.

[0340] Compared with the preparation method of the optoelectronic device in the inverted device Example 1, the difference in the preparation method of the optoelectronic device in this example is: Replace step S3 with: "Spin - coat CdZnS blue - light quantum dot - cyclooctane with a concentration of 10 mg / mL on the electron - transporting layer at a spin - coating speed of 1500 rpm for 30 s, and anneal at 100 °C for 5 min to obtain an excitation layer".

[0341] Device performance

[0342] The device performance is tested using the following methods:

[0343] Test method for CE luminous efficiency: Connect the above device to a current-voltage tester to measure its current and voltage. Connect the above device to a spectrometer to measure its luminous spectrum. Calculate the CE luminous efficiency based on the measurement results, which is the ratio of the electron injection rate to the photon emission rate.

[0344] The specific performance data are shown in Table 2:

[0345] Table 2

[0346]

[0347]

[0348] It can be seen from Table 2 that compared with Comparative Examples 1 and 2, both the upright device and the inverted device have significantly improved luminous efficiency. The main reason is that after the ligands on the surface of the quantum dot material and the gelling agent undergo electrostatic self-assembly, a quantum dot material with gel properties is formed, which makes the film have lower fluidity. Therefore, it is not easy to change the film morphology during subsequent processing and movement, and it does not affect the uniformity of the film layer. It is not easy to have uneven current distribution due to uneven film layers. Therefore, it can reduce the difference in carrier transmission rate in the quantum dot film layer and improve the luminous efficiency of the device.

[0349] The embodiments of the present application are introduced in detail above. Specific examples are used in this article to illustrate the principles and implementation methods of the present application. The description of the above embodiments is only used to help understand the method and core idea of ​​the present application. At the same time, for technical personnel in this field, according to the idea of ​​the present application, 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 application.

Claims

1. A composite material, characterized in that, the composite material comprises a first compound and a second compound, the first compound comprises quantum dots with ligands connected to the surface, and the second compound comprises a gelling agent; the ligand is connected to the gelling agent.

2. The composite material according to claim 1, characterized in that, the ligand is connected to the gelling agent through an amide bond; and / or the ligand is selected from fatty carboxylic acid ligands with 1-30 carbon atoms, aromatic carboxylic acid ligands with 6-30 ring atoms, aromatic heterocyclic carboxylic acid ligands with 5-30 ring atoms or aliphatic heterocyclic carboxylic acid ligands with 3-30 carbon atoms; and / or The gelling agent is selected from conductive gels with a conductivity of 10 2 -10 3 S / m.

3. The composite material according to claim 2, characterized in that, the ligand is selected from fatty carboxylic acid ligands with 1-8 carbon atoms.

4. The composite material according to claim 3, characterized in that, the ligand is selected from one or more of mercaptoacetic acid, mercaptopropionic acid, mercaptobutyric acid and mercaptooleic acid; and / or the gelling agent is selected from one or more of N,N'-bis(octadecyl)-L-glutamic acid diamide, N,N'-dioctadecyl-d-aminoglutamic acid diamide, L-glutamic acid amide-15N, N(2)-L-alanyl-L-glutamine, polyacrylamide / polyethyleneimine composite gel, polystyrene / chitosan composite gel and polyaniline gel.

5. The composite material according to claim 1, characterized in that, The quantum dots 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 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 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, and 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 materials include doped or undoped inorganic perovskite semiconductor or organic-inorganic hybrid perovskite semiconductor. 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+ One or more of them, X is a halogen anion, including Cl - , Br - , I - One or more 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+ One or more of them, X is a halogen anion, including Cl - , Br - , I - One or more of them.​ 6. The composite material according to claim 1, characterized in that, the mass ratio of the second compound to the first compound is 1:(10-20).

7. A method for preparing a thin film, characterized in that, it comprises the following steps: providing a first mixture comprising a first compound and a second mixture comprising a second compound, the first compound being quantum dots with ligands connected to the surface, and the second compound being a gelling agent; depositing the first mixture and the second mixture, and performing heat treatment after deposition to obtain a thin film.

8. The method for preparing a thin film according to claim 7, characterized in that, the ligand contains a carboxyl group and the gelling agent contains an amino group; and / or in the step of depositing the first mixture and the second mixture, the mass ratio of the second compound to the first compound is 1:(10-20); and / or the first mixture comprises the first compound and a first solvent, and the concentration of the first mixture is 10-20 mg / ml; and / or the second mixture comprises the second compound and a second solvent, and the concentration of the second mixture is 1-2 mg / ml; the first solvent and the second solvent are both polar solvents and have a boiling point of 80-120 °C.

9. The method for preparing a thin film according to claim 8, characterized in that, the first solvent is selected from one or more of alkanes, aromatic hydrocarbons, halogenated hydrocarbons, alcohol compounds, ether compounds, furan compounds, pyridine compounds and amide compounds; and / or The second solvent is selected from one or more of alkanes, aromatic hydrocarbons, halogenated hydrocarbons, alcohol compounds, ether compounds, furan compounds, pyridine compounds, and amide compounds.

10. The method for preparing the thin film according to claim 9, wherein, the first solvent is selected from one of propanol, isopropanol, butanol, n-butanol, isobutanol, hexanol, isopropanol, benzene, cyclohexane, and n-heptane; and / or the second solvent is selected from one of propanol, isopropanol, butanol, n-butanol, isobutanol, hexanol, isopropanol, benzene, cyclohexane, and n-heptane.

11. The method for preparing the thin film according to claim 7, wherein, the heat treatment temperature is 80 - 110 °C; and / or the heat treatment time is 30 - 60 min.

12. The method for preparing the thin film according to claim 7, wherein, the step of depositing the first mixture and the second mixture specifically includes: depositing the first mixture and then depositing the second mixture on the first mixture; or depositing the second mixture and then depositing the first mixture on the second mixture; or mixing the first mixture and the second mixture at 60 - 80 °C and then depositing.

13. The method for preparing the thin film according to claim 7, wherein, in the thin film, the ligand and the gelling agent are connected by an amide bond after the heat treatment; and / or the ligand is selected from aliphatic carboxylic acid ligands with 1 - 30 carbon atoms, aromatic carboxylic acid ligands with 6 - 30 ring atoms, aromatic heterocyclic carboxylic acid ligands with 5 - 30 ring atoms, or aliphatic heterocyclic carboxylic acid ligands with 3 - 30 carbon atoms; and / or The gelling agent is selected from conductive gels with a conductivity of 10 2 -10 3 S / m; and / or the ligand is selected from one or more of mercaptoacetic acid, mercaptopropionic acid, mercaptobutyric acid, and mercaptooleic acid; and / or the gelling agent is selected from one or more of N,N'-bis(octadecyl)-L-glutamic acid diamide, N,N'-dioctadecyl-d-amino glutamic acid diamide, L-glutamic acid amide-15N, N(2)-L-alanyl-L-glutamine, polyacrylamide / polyethyleneimine composite gel, polystyrene / chitosan composite gel, and polyaniline gel.

14. A thin film, wherein, it includes the composite material according to any one of claims 1 - 6, or is prepared by the method for preparing the thin film according to any one of claims 7 - 13.

15. The thin film according to claim 14, wherein, the thin film is gel-like.

16. An optoelectronic device, wherein, it includes: an anode and a cathode disposed opposite to each other; an excitation layer disposed between the first functional layer and the second functional layer; wherein, the excitation layer includes the composite material according to any one of claims 1 - 6 or the thin film prepared by the method for preparing the thin film according to any one of claims 7 - 13.

17. The optoelectronic device according to claim 16, wherein: The anode and the cathode each independently 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, and 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; and / or It further includes a first functional layer and a second functional layer, which are disposed between the anode and the cathode; the materials of the first functional 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-ethylhexyloxy)-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, 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene, PEDOT, PEDOT:PSS, PEDOT:PSS doped with s-MoO 3 derivatives, 4,4',4'-tris(N-3-methylphenyl-N-phenylamino)triphenylamine, tetracyanoquinodimethane, doped graphene, undoped graphene, C60, copper phthalocyanine, the second doped metal oxide particles, the second undoped metal oxide particles, the metal sulfide and the metal nitride, one or more of them; and / or The material of the second functional layer includes one or more of inorganic electronic functional materials and organic electronic functional materials. The inorganic electronic functional materials include one or more of the first doped metal oxide particles, the first undoped metal oxide particles, the IIB-VIA group semiconductor materials, the IIIA-VA group semiconductor materials, and the IB-IIIA-VIA group semiconductor materials. The organic electronic functional materials include one or more of quinoxaline compounds, imidazole compounds, triazine compounds, fluorene-containing compounds, hydroxyquinoline compounds, and fullerene derivatives.

18. A display device, characterized in that it includes the thin film as described in claim 14 or 15, or the optoelectronic device as described in claim 16 or 17.

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