Composite material, thin film, preparation method of thin film and photoelectric device

Abstract

The invention discloses a composite material, a film and a photoelectric device, the composite material comprises a nanoparticle with a core-shell structure, the material of the core of the nanoparticle comprises at least one P-type inorganic compound or at least one N-type inorganic compound, and the material of the shell of the nanoparticle comprises a polymer, the composite material has good performance stability, can be applied to the photoelectric device, is beneficial to improving the device efficiency of the photoelectric device and prolonging the device service life of the photoelectric device, and reduces the electric leakage rate of the photoelectric device.

Description

Technical Field

[0001] This application relates to the field of optoelectronic technology, specifically to a composite material, a thin film, a method for preparing the same, and an optoelectronic device. Background Technology

[0002] Nanoparticles, with their small size, high specific surface area, high reactivity, and unique photoelectric and thermal properties, have been widely used in optoelectronics, catalysis, medicine, and environmental protection. The morphology and size of nanoparticles are important factors influencing their performance and applications.

[0003] Nanoparticles have a large number of defect states and tend to aggregate in solution, resulting in poor film quality in solution-based methods and negatively impacting the performance of devices using nanoparticles. Summary of the Invention

[0004] In view of the shortcomings of the prior art, this application provides a composite material, a thin film, and an optoelectronic device.

[0005] The technical solution of this application is as follows:

[0006] In a first aspect, this application provides a composite material comprising nanoparticles having a core-shell structure, wherein the core of the nanoparticles is made of at least one p-type inorganic compound or at least one n-type inorganic compound, and the shell of the nanoparticles is made of at least one polymer.

[0007] In a second aspect, this application provides a thin film, the material of which includes the composite material as described in the first aspect, and / or the thin film is prepared using the composite material as described in the first aspect.

[0008] Thirdly, this application provides a method for preparing a thin film, comprising the steps of: depositing a dispersion containing nanoparticles, drying the deposited dispersion to form a film, and obtaining a thin film; wherein the nanoparticles are nanoparticles as described in the first aspect.

[0009] Fourthly, this application provides an optoelectronic device, comprising:

[0010] The anode and cathode are arranged opposite each other; and

[0011] Multiple functional layers are disposed between the anode and the cathode;

[0012] Wherein, at least one of the plurality of functional layers comprises a composite material as described in the first aspect, or a thin film as described in the second aspect, or a thin film prepared by the method described in the third aspect, or at least one of the plurality of functional layers is prepared using a composite material as described in the first aspect.

[0013] This application provides a composite material, a thin film, and an optoelectronic device, which have the following technical advantages:

[0014] The composite material provided in this application includes nanoparticles with a core-shell structure. The shell material of the nanoparticles includes at least one polymer. Based on the shell coating the core, the surface defect states of the core can be effectively passivated, thereby improving the problem of easy agglomeration of nanoparticles in solution and making the composite material have good performance stability. Attached Figure Description

[0015] The technical solution and other beneficial effects of this application will become apparent from the following detailed description of specific embodiments in conjunction with the accompanying drawings.

[0016] Figure 1 This application provides a schematic diagram of the structure of an optoelectronic device. Detailed Implementation

[0017] The technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of this application, and not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of this application without creative effort are within the scope of protection of this application.

[0018] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those familiar to those skilled in the art. Furthermore, any methods and materials similar to or equivalent to those described herein may be applied to this invention. The preferred embodiments and materials described herein are for illustrative purposes only and do not limit the scope of this application.

[0019] It should be noted that the order of description of the following embodiments is not intended to limit the preferred order of embodiments. 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 merely for convenience and brevity and should not be construed as a rigid limitation on the scope of the invention; therefore, it should be considered that the range description has specifically disclosed all possible sub-ranges and single numerical values ​​within that range. For example, it should be considered that the range description from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., and single numbers within the range, such as 1, 2, 3, 4, 5, and 6, regardless of the range. Furthermore, whenever a numerical range is indicated herein, it means including any referenced number (fraction or integer) within the indicated range.

[0020] In the description of this application, the term "comprising" means "including but not limited to".

[0021] The term "at least one" refers to one or more items, while "multiple" or "multi-item" refers to two or more items. The terms "at least one," "at least one of the following," or similar expressions refer to any combination of these items, including any combination of single or multiple items. For example, "at least one of a, b, or c" or "at least one of a, b, and c" can be expressed as: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can be single or multiple.

[0022] The term "and / or" encompasses any one of two or more of the listed items, as well as any and all combinations of the listed items. These combinations include any two listed items, any number of listed items, or a combination of all listed items. For example, "A and / or B" includes three parallel solutions: A, B, and A+B. Similarly, the technical solution "A, and / or, B, and / or, C, and / or, D" includes any one of A, B, C, and D (i.e., all connected by "logical OR"), any and all combinations of A, B, C, and D, including combinations of any two or three of A, B, C, and D, and combinations of all four of A, B, C, and D (i.e., all connected by "logical AND").

[0023] In this application, descriptions such as "layer A is formed on one side of layer B," "layer A is formed on the side of layer B away from layer C," or similar expressions can mean that layer A is directly formed on one side of layer B or on the side of layer B away from layer C, i.e., layer A and layer B are in direct contact; or they can mean that layer A is indirectly formed on one side of layer B or on the side of layer B away from layer C, i.e., other spacer structures can be formed between layer A and layer B. Similarly, "layer A is disposed on one side of layer B" or "layer A is disposed on the side of layer B away from layer C" can mean that layer A and layer B are in direct contact, or that other spacer structures are provided between layer A and layer B; "layer A is disposed between layer B and layer C" can mean that layer A and layer B are in direct contact and layer A and layer C are in direct contact, or layer A and layer B are in direct contact and one or more spacer structures are provided between layer A and layer C, or layer A and layer B are provided and one or more spacer structures are provided between layer A and layer C, or layer A and layer B are provided and layer A and layer C are in direct contact.

[0024] The term "average particle size" refers to the area-average particle size of a particle swarm. Area-average particle size is calculated by dividing the total volume of the particle swarm by its total area, which is the reciprocal of the surface area per unit volume. If an imaginary swarm of particles with uniform size is used to replace the original swarm, and the total volume and area of ​​this imaginary swarm are identical to the original swarm, then the diameter of this imaginary swarm is the area-average particle size of the original swarm. Area-average particle size can be obtained through statistical analysis, using transmission electron microscopy to statistically analyze the particle size of each particle in the swarm.

[0025] In this application, the thickness of the thin film refers to the average thickness of the thin film, and the thickness of a certain functional layer refers to the average thickness of the functional layer. The thickness is obtained by measuring a step tester.

[0026] This application provides a composite material comprising nanoparticles having a core-shell structure. The core of the nanoparticles is made of at least one P-type inorganic compound or at least one N-type inorganic compound, and the shell of the nanoparticles is made of at least one polymer.

[0027] In the composite material provided in the embodiments of this application, the nanoparticles have a core-shell structure, and the shell material includes at least one polymer. Based on the shell's coating of the core, the surface defect states of the core can be effectively passivated, thereby improving the problem of easy agglomeration of nanoparticles in solution, and making the composite material have good performance stability.

[0028] In some embodiments of this application, at least one p-type inorganic compound is selected from one or more of NiO, MoO3, WO3, V2O5, Cr2O3, CuO, Cu2O, and CuI.

[0029] In some embodiments of this application, at least one N-type inorganic compound is selected from ZnO, TiO2, SnO2, BaO, Ta2O3, Al2O3, ZrO2, Zn (1-x) Mg x O, Zn (1-x) Ca x O, Zn (1-x) Zr x O, Zn (1-x) Ga x O, Zn (1-x) Al x O, Zn (1-x) Li x O, Al (1-x) Zn x O, Zn (1-x) Ti x O, Zn (1-x) Y x O、In (1-x) Snx O and Ti (1-x) Li x One or more of O, where 0 < x ≤ 0.5.

[0030] In some embodiments of this application, at least one polymer is selected from one or more of thermoplastic resins and thermosetting resins. The thermoplastic resins include, but are not limited to, one or more of polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyamide, polycarbonate, polyoxymethylene, polyphenylene ether, polysulfone, and polytetrafluoroethylene. The thermosetting resins include, but are not limited to, one or more of epoxy resin, polyester resin, vinyl resin, bismaleimide resin, phenolic resin, and melamine-formaldehyde resin.

[0031] In some embodiments of this application, the average particle size of the nanoparticles is 2nm to 50nm, for example, it can be 2nm, 5nm, 10nm, 20nm, 30nm, 40nm, 50nm or any two of the aforementioned values; and / or, the thickness of the shell of the nanoparticles is 2nm to 5nm, for example, it can be 2nm, 3nm, 4nm, 5nm or any two of the aforementioned values.

[0032] In some embodiments of this application, for nanoparticles, the shell-to-core coverage rate is 30% to 100%, for example, it can be 30%, 40%, 50%, 60%, 70%, 80%, 90%, 100%, or any value between any two of the foregoing.

[0033] In order to further improve the carrier transport performance of nanoparticles, in some embodiments of this application, the mass ratio of shell to core is 1:(20-100), for example, it can be 1:20, 1:30, 1:40, 1:50, 1:60, 1:70, 1:80, 1:90, 1:100 or any value between the two aforementioned values.

[0034] It should be noted that the methods for preparing nanoparticles include, but are not limited to, sol-gel methods, vapor deposition methods, solution chemistry methods, atomic layer deposition methods, or electrochemical methods. For example, a method for preparing nanoparticles may include the steps of: providing a solution containing a shell material (at least one polymer), immersing a solid core in the solution containing the shell material to form a shell on the surface of the core, and then removing the solvent by curing and drying to obtain solid nanoparticles; or, another method may include the steps of: providing a solution containing a shell material, and atomizing and spraying the solution containing the shell material onto the surface of the core to form a shell to obtain nanoparticles.

[0035] To further improve the conductivity of the nanoparticles, in some embodiments of this application, the composite material further includes a first conductive agent, which includes a first metal and / or carbon material.

[0036] In some embodiments of this application, the first metal is selected from one or more of copper, aluminum, and silver.

[0037] In some embodiments of this application, the first carbon material is selected from one or more of graphite, carbon nanotubes, graphene, and carbon fiber.

[0038] In order to further improve the conductivity of the composite material and further improve the solution film quality of the composite material, in some embodiments of this application, the mass ratio of nanoparticles to the first conductive agent is 1:(0.03 to 0.1), for example, it can be 1:0.03, 1:0.05, 1:0.08, 1:0.1 or any two of the aforementioned values.

[0039] This application also provides a thin film, the material of which includes any of the composite materials described above, and / or the thin film is prepared using any of the composite materials described above, and the thin film has good surface flatness.

[0040] In some embodiments of this application, the surface roughness Ra of the thin film is 0.3 nm to 0.5 nm, for example, it can be 0.3 nm, 0.4 nm, 0.5 nm or any value between the two aforementioned values.

[0041] In some embodiments of this application, the thickness of the thin film is 20nm to 50nm, for example, it can be 20nm, 30nm, 40nm, 50nm or any two of the aforementioned values.

[0042] This application also provides a method for preparing a thin film, which can be used to prepare any of the thin films described above. The method for preparing the thin film includes the steps of: depositing a dispersion containing nanoparticles, drying the deposited dispersion to form a film, and obtaining a thin film; wherein, the nanoparticles refer to the description of nanoparticles in the composite materials section above.

[0043] Specifically, the deposition method of the dispersion includes, but is not limited to, one or more of the following: spin coating deposition, inkjet printing deposition, blade coating deposition, dip-coating deposition, immersion deposition, spraying deposition, roller coating deposition, casting deposition, slot coating deposition, and strip coating deposition.

[0044] In some embodiments of this application, the dispersion medium of the dispersion is selected from one or more of alkanes, aromatic hydrocarbons, halogenated hydrocarbons, alcohols, ethers, ketones, esters, furans, pyridines, amides, and sulfones. Specifically, the alkanes include, but are not limited to, one or more of nonane, decane, dodecane, terpenes, butylcyclohexane, n-octane, n-hexane, n-heptane, n-nonane, n-decane, cyclohexane, and cyclopentane; and / or the aromatic hydrocarbons include, but are not limited to, one or more of diethylbenzene, trimethylbenzene, propylbenzene, isopropylbenzene, p-toluene, butylbenzene, and 1-methylnaphthalene or indene; the halogenated hydrocarbons include, but are not limited to, one or more of dichloromethane, chloroform, and carbon tetrachloride; the alcohols include, but are not limited to, one or more of methanol, ethanol, propanol, butanol, ethylene glycol, and glycerol; and the ethers... The compounds include, but are not limited to, one or more of ethylene glycol monomethyl ether, diethyl ether, and propylene oxide; the ketone compounds include, but are not limited to, one or more of acetone, butanone, and N-methylpyrrolidone; the ester compounds include, but are not limited to, one or more of ethyl formate, ethyl acetate, and propyl acetate; 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; and / or the amide compounds include, but are not limited to, N,N-dimethylformamide; and the sulfone compounds include, but are not limited to, dimethyl sulfoxide. The dispersion medium for the dispersion is selected, for example, one or more of ethanol, toluene, chlorobenzene, chloroform, carbon tetrachloride, dimethyl sulfoxide, N,N-dimethylformamide, tetrahydrofuran, N-methylpyrrolidone, tetrahydronaphthalene, and chloronaphthalene.

[0045] To further improve the conductivity of the film, in some embodiments of this application, the dispersion further includes a second conductive agent, which includes a second metal and / or a second carbon material. The second metal includes, but is not limited to, one or more of copper, aluminum, and silver, and the second carbon material includes, but is not limited to, one or more of graphite, carbon nanotubes, graphene, and carbon fibers.

[0046] In order to further improve the conductivity of the film and ensure that the film has a high surface smoothness, in some embodiments of this application, when the dispersion further includes a second conductive agent, the mass ratio of nanoparticles to the second conductive agent in the dispersion is 1:(0.03 to 0.1), for example, it can be 1:0.03, 1:0.05, 1:0.08, 1:0.1 or any two of the aforementioned values.

[0047] In order to further improve the density of the film and ensure that the film has a high surface smoothness, in some embodiments of this application, the concentration of nanoparticles in the dispersion is 5 mg / mL to 10 mg / mL, for example, it can be 5 mg / mL, 6 mg / mL, 7 mg / mL, 8 mg / mL, 9 mg / mL, 10 mg / mL or any value between the two aforementioned values.

[0048] In some embodiments of this application, the drying method of the deposited dispersion is selected from one or more of heat treatment and vacuum drying.

[0049] This application also provides an optoelectronic device, which includes, but is not limited to, light-emitting devices, solar cells, or photodetectors, such as... Figure 1 As shown, the optoelectronic device 10 includes an anode 101, a cathode 102, and multiple functional layers. The anode 101 and cathode 102 are disposed opposite each other, and the multiple functional layers are disposed between the anode 101 and cathode 102. At least one of the multiple functional layers includes a composite material as described above, or a thin film as described above, or a thin film prepared by a method described above. Alternatively, at least one of the multiple functional layers may be prepared using a composite material as described above, which can improve the surface flatness of the functional layers, thereby improving the leakage current phenomenon of the optoelectronic device, and thus improving the current efficiency and device life of the optoelectronic device.

[0050] In some embodiments of this application, multiple functional layers include a hole functional layer 103. The hole functional layer 103 comprises any of the composite materials described above, or any of the thin films described above, or a thin film prepared by any of the methods described above, or the hole functional layer 103 is prepared using any of the composite materials described above. The core material of the nanoparticles comprises at least one p-type inorganic compound, and the selection range of p-type inorganic compounds is as described above. It should be noted that the hole functional layer 103 can be a single-layer structure or a multi-layer structure. When the hole functional layer 103 is a multi-layer structure, at least one layer comprises any of the composite materials described above, or any of the thin films described above, or a thin film prepared by any of the methods described above, or at least one layer is prepared using any of the composite materials described above.

[0051] To improve the hole transport efficiency of the optoelectronic device 10, further reference is made to some embodiments of this application. Figure 1The hole functional layer 103 includes a hole injection layer 1031 and / or a hole transport layer 1032. For the hole functional layer 103 including the hole injection layer 1031 and the hole transport layer 1032, the hole injection layer 1031 is closer to the anode 101 than the hole transport layer 1032. At least one of the hole injection layer 1031 and the hole transport layer 1032 comprises a composite material as described above, a thin film as described above, or a thin film prepared by a method described above, or at least one of the hole injection layer 1031 and the hole transport layer 1032 is prepared using a composite material as described above. The thickness of the hole functional layer 103 is, for example, 10 nm to 100 nm.

[0052] To further improve the current efficiency and device lifetime of the optoelectronic device 10, in some embodiments of this application, the hole functional layer 103 includes a hole injection layer 1031 and a hole transport layer 1032. The hole transport layer 1032 includes any of the composite materials described above, or any of the thin films described above, or thin films prepared by any of the methods described above, or the hole transport layer 1032 is prepared using any of the composite materials described above. The material of the hole injection layer 1031 can be a conventional material in the art, including but not limited to poly(3,4-vinyldioxythiophene):poly(styrene sulfonic acid) (PEDOT:PSS, CAS No. 155090-83-8), copper phthalocyanine (CAS No. 147-14-8), titanium phthalocyanine (CAS No. 26201-32-1), 2,3,5,6-tetrafluoro-7,7',8,8'-tetracyanodimethyl-p-benzoquinone (CAS No. 29261-33-4), and 2, One or more of the following: 3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazabenzophenanthrene (CAS No. 105598-27-4), nickel oxide (e.g., NiO), molybdenum oxide (e.g., MoO3), tungsten oxide (e.g., WO3), vanadium oxide (e.g., V2O5), p-type gallium nitride, chromium oxide (e.g., Cr2O3), copper oxide (e.g., CuO or Cu2O), copper sulfide (e.g., CuS), molybdenum sulfide (e.g., MoS2), and tungsten sulfide (e.g., WS2).

[0053] In some embodiments of this application, multiple functional layers include an electronic functional layer 105. For the optoelectronic device 10, which includes a hole functional layer 103, please refer to [reference needed]. Figure 1An electronic functional layer 105 is disposed between the hole functional layer 103 and the cathode 102. The electronic functional layer 105 comprises any of the composite materials described above, or any of the thin films described above, or a thin film prepared by any of the methods described above, or the electronic functional layer 105 is prepared using any of the composite materials described above. The core material of the nanoparticles comprises at least one N-type inorganic compound, and the selection range of the N-type inorganic compound is as described above. The thickness of the electronic functional layer 105 is, for example, 10 nm to 100 nm.

[0054] The electronic functional layer 105 can be a single-layer or multi-layer structure. When the electronic functional layer 105 is a multi-layer structure, it includes, for example, one or more of an electron injection layer, an electron transport layer, and a hole blocking layer. For an electronic functional layer 105 including an electron injection layer, an electron transport layer, and a hole blocking layer, the electron transport layer is located between the electron injection layer and the hole blocking layer, and the electron injection layer is closer to the cathode 102 than the hole blocking layer. For an electronic functional layer 105 including an electron transport layer and a hole blocking layer, the electron transport layer is closer to the cathode 102 than the hole blocking layer. For an electronic functional layer 105 including an electron injection layer and an electron transport layer, the electron injection layer is closer to the cathode 102 than the electron transport layer. When the electronic functional layer 105 is a multi-layer structure, at least one layer (e.g., an electron transport layer) includes a composite material as described above, a thin film as described above, or a thin film prepared by a method described above, or at least one layer (e.g., an electron transport layer) is prepared using a composite material as described above.

[0055] It is understood that when the hole functional layer 103 comprises any of the composite materials described above, or any of the thin films described above, or a thin film prepared by any of the methods described above, or when the hole functional layer 103 is prepared using any of the composite materials described above, and the material of the electronic functional layer 105 is a conventional material in the art, the material of the electronic functional layer 105 includes one or more of the following: a first inorganic compound material, a second inorganic compound material, a group IIB-VIA semiconductor material, a group IIIA-VA semiconductor material, and a group IB-IIIA-VIA semiconductor material. The first inorganic compound material includes, but is not limited to, one or more of ZnO, TiO2, SnO2, BaO, Ta2O3, Al2O3, and ZrO2; the IIB-VIA group semiconductor material includes, but is not limited to, one or more of ZnS, ZnSe, and CdS; the IIIA-VA group semiconductor material includes, but is not limited to, one or more of InP and GaP; the IB-IIIA-VIA group semiconductor material includes, but is not limited to, one or more of CuInS and CuGaS; the second inorganic compound material includes one or more doped first compounds, wherein the host material of the doped first compound is selected from ZnO, TiO2, SnO2, BaO, Ta2O3, Al2O3, or ZrO2, and the doping element of the doped first compound includes, but is not limited to, one or more of Mg, Ca, Zr, W, Ga, Li, Al, Ti, Y, In, and Sn. The doped first compound is, for example, selected from, one or more of zinc magnesium oxide, zinc calcium oxide, zinc zirconium oxide, zinc gallium oxide, zinc aluminum oxide, zinc lithium oxide, zinc titanium oxide, yttrium zinc oxide, indium tin oxide, and lithium titanium oxide, with Zn as an example. (1-x) Mg x O, Zn (1-x) Ca x O, Zn (1-x) Zr x O, Zn (1-x) Ga x O, Zn (1-x) Al x O, Zn (1-x) Li x O, Al (1-x) Zn x O, Zn (1-x) Ti x O, Zn (1-x) Y x O、In (1-x) Sn x O and Ti (1-x) Li xOne or more of O, wherein 0 < x ≤ 0.5. It should be noted that the first inorganic compound material and the doped first compound can be, for example, in the form of nanoparticles, nanosheets, nanoneedles or nanorods, respectively, with nanoparticles as an example, and the average particle size of the nanoparticles being, for example, 2 nm to 50 nm.

[0056] When the electronic functional layer 105 comprises any of the composite materials described above, or any of the thin films described above, or a thin film prepared by any of the methods described above, or when the electronic functional layer 105 is prepared using any of the composite materials described above, and the material of the hole functional layer 103 is a conventional material in the art, the material of the hole functional layer 103 includes one or more of organic materials, third inorganic compound materials, and fourth inorganic compound materials. Among them, organic materials include, but are not limited to, poly(3,4-vinyldioxythiophene):poly(styrene sulfonic acid) (PEDOT:PSS, CAS No. 155090-83-8), copper phthalocyanine (CAS No. 147-14-8), titanium phthalocyanine (CAS No. 26201-32-1), 2,3,5,6-tetrafluoro-7,7',8,8'-tetracyanodimethyl-p-benzoquinone (CAS No. 29261-33-4), and 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazabenzophenanthrene (CAS No. 10559). 8-27-4), polyaniline (CAS No. 25233-30-1), polypyrrole (CAS No. 30604-81-0), 3-hexyl-substituted polythiophene (CAS No. 104934-50-1), poly(9-vinylcarbazole) (abbreviated as PVK, CAS No. 25067-59-8), 4,4'-bis(9-carbazole)biphenyl (abbreviated as CBP, CAS No. 58328-31-7), poly[bis(4-phenyl)(4-butylphenyl)amine], 4,4'-cyclohexylbis[N,N-bis(4-methylphenyl)aniline] (abbreviated as TAPC, C CAS No. 58473-78-2), poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(4,4'-(N-(4-sec-butylphenyl)diphenylamine)] (abbreviated as TFB, CAS No. 220797-16-0), poly[(N,N'-(4-n-butylphenyl)-N,N'-diphenyl-1,4-phenylenediamine)-ALT-(9,9-di-n-octylfluorenyl-2,7-diyl)] (CAS No. 223569-31-1), 4,4',4'-tris(N-3-methylphenyl-N-phenylamino)triphenylamine (CAS No. 124) 729-98-2), 4,4',4”-tris(carbazole-9-yl)triphenylamine (abbreviated as TCTA, CAS number 139092-78-7), 4,4',4'-tris(2-naphthylphenylamino)triphenylamine (CAS number 185690-41-9), N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine (abbreviated as NPB, CAS number 123847-85-8), N,N'-diphenyl-N,N'-di(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine (abbreviated as TPD),CAS No. 65181-78-4), N,N'-bis[4-(diphenylamino)phenyl]-N,N'-diphenylbenzidine (CAS No. 209980-53-0), N,N'-bis(3-methylphenyl)-N,N'-diphenyl-9,9-spirodifluorene-2,7-diamine (Spiro-TPD, CAS No. 1033035-83-4), N2,N7-di-1-naphthyl-N2,N7-diphenyl-9, The following are listed: 9'-spirodi[9H-fluorene]-2,7-diamine (CAS No. 932739-76-9), poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTTA, CAS No. 1333317-99-9), and 2,2',7,7'-tetratetra[N,N-di(4-methoxyphenyl)amino]-9,9'-spirodifluorene (Spiro-omeTAD, CAS No. 207739-72-8). One or more; and / or, the third inorganic compound material includes, but is not limited to, graphene, C60, nickel oxide, molybdenum oxide, tungsten oxide, vanadium oxide, p-type gallium nitride, chromium oxide, copper oxide, copper sulfide, molybdenum sulfide, and tungsten sulfide; and / or, the fourth inorganic compound material includes one or more doped second compounds, the host material of which is selected from graphene, C60, nickel oxide (e.g., NiO), molybdenum oxide (e.g., MoO3), tungsten oxide (e.g., WO3), vanadium oxide (e.g., V2O5), p-type gallium nitride, chromium oxide (e.g., Cr2O3), copper oxide (e.g., CuO or Cu2O), copper sulfide (e.g., CuS), molybdenum sulfide (e.g., MoS2), or tungsten sulfide (e.g., WS2), and the doping element of which is selected from nickel, molybdenum, tungsten, vanadium, chromium, copper, and platinum group metals, and the molar amount of the doping element accounts for no more than 50% of the total molar amount of the doped second compound.

[0057] In some embodiments of this application, the optoelectronic device 10 is a light-emitting device, and the multiple functional layers include a light-emitting layer 104. For the optoelectronic device 10 including a hole functional layer 103 and an electron functional layer 105, please refer to the following. Figure 1 The light-emitting layer 104 is disposed between the hole functional layer 103 and the electron functional layer 105. The material of the light-emitting layer 104 includes one or more of organic light-emitting materials and light-emitting quantum dots, and the thickness of the light-emitting layer 104 is, for example, 10 nm to 100 nm.

[0058] Among them, organic light-emitting materials include, but are not limited to, one or more of the following: 4,4'-bis(N-carbazole)-1,1'-biphenyl:tri[2-(p-tolyl)pyridinium(III), 4,4',4”-tri(carbazole-9-yl)triphenylamine:tri[2-(p-tolyl)pyridinium, diaromatic anthracene derivatives, stilbene aromatic derivatives, pyrene derivatives, fluorene derivatives, TBPe fluorescent materials, TTPX fluorescent materials, TBRb fluorescent materials, DBP fluorescent materials, delayed fluorescent materials, TTA materials, thermally activated delayed materials, polymers containing BN covalent bonds, hybrid local charge transfer excited state materials, excitopolymer light-emitting materials, polyacetylene and its derivatives, poly(p-phenylene) and its derivatives, polythiophene and its derivatives, and polyfluorene and its derivatives.

[0059] The luminescent quantum dots include, but are not limited to, one or more of red, green, and blue quantum dots. Furthermore, the luminescent quantum dots include, but are not limited to, one or more of single-component quantum dots, core-shell quantum dots, inorganic perovskite quantum dots, organic perovskite quantum dots, and organic-inorganic hybrid perovskite quantum dots, wherein the core-shell quantum dots have one or more shells. The average particle size of the luminescent quantum dots can be, for example, 2 nm to 20 nm, with examples being 2 nm, 5 nm, 6 nm, 7 nm, 8 nm, 9 nm, 10 nm, 15 nm, 20 nm, or any value between any two of the aforementioned values.

[0060] For single-component quantum dots and core-shell quantum dots, the material of the single-component quantum dot, the material of the core of the core-shell quantum dot, or the material of the shell of the core-shell quantum dot includes, but is not limited to, at least one of group II-VI compounds, group III-V compounds, group III-VI compounds, group IV-VI compounds, or group I-III-VI compounds. Among them, the II-VI group compounds include, but are not limited to, one or more of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, MgSe, MgS, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, MgZnSe, MgZnS, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, and HgZnSTe. III-VI group compounds include, but are not limited to, one or more of In2S3, In2Se3, InGaS3, and InGaSe3. III-V group compounds include, but are not limited to, one or more of GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, and InAlPSb. Group IV-VI compounds include, but are not limited to, one or more of SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, SnPbSeTe, and SnPbSTe. Group I-III-VI compounds include, but are not limited to, one or more of AgInS, AgInS2, CuInS, CuInS2, AgGaS2, CuGaS2, CuGaO2, AgGaO2, AgAlO2, AgInGaS2, and CuInGaS2.

[0061] For inorganic perovskite quantum dots, the general structural formula is AMX3, where A is Cs. + M is a divalent metal cation, and M includes, but is not limited to, Pb. 2+ Sn 2+ Cu 2+ Ni 2+ Cd 2+ Cr 2+ Mn 2+ Co 2+ Fe 2+ 、Ge 2+ Yb 2+ Or Eu 2+ X is a halide anion, including but not limited to Cl. - ,Br - or I - .

[0062] For organic perovskite quantum dots, the general structural formula is CMX3, where C is a formamidinyl group and M is a divalent metal cation, which may include, but is not limited to, Pb. 2+ Sn 2+ Cu 2+ Ni 2+ Cd 2+ Cr 2+ Mn 2+ Co 2+ Fe 2+ 、Ge 2+ Yb 2+ Or Eu 2+ X is a halide anion, including but not limited to Cl. - ,Br - or I - .

[0063] For organic-inorganic hybrid perovskite quantum dots, the general structural formula is BMX3, where B is selected from organic amine cations, including but not limited to CH3(CH2). n-2 NH 3+ (n≥2) or NH3(CH2) n NH3 2+ (n≥2), M is a divalent metal cation, and M includes, but is not limited to, Pb. 2+ Sn 2+ Cu 2+ Ni 2+ Cd 2+ Cr 2+ Mn 2+ Co 2+ Fe2+ 、Ge 2+ Yb 2+ Or Eu 2+ X is a halide anion, including but not limited to Cl. - ,Br - or I - .

[0064] When the material of the light-emitting layer 104 includes light-emitting quantum dots, in order to improve the solution processing performance of the light-emitting quantum dots and further enhance the device efficiency of the optoelectronic device 10, in some embodiments of this application, ligands are also attached to the surface of the light-emitting quantum dots. The ligands can be common ligands in the art, including but not limited to C1 to C2. 30 aliphatic carboxylic acid ligands, C6-C 30 Aromatic carboxylic acid ligands, C1-C 30 Aliphatic thiol ligands, C6-C 30 Thiol aromatic ligands, C1-C 30 fatty amine ligands, C6-C 30 Aromatic amine ligands, C1-C 30 Aliphatic phosphine ligands, C6~C 30 Aromatic phosphine ligands and C6-C 30 One or more of aromatic phosphate ligands and halogen ligands.

[0065] Among them, C1~C 30 The aliphatic carboxylic acid ligands include, but are not limited to, one or more of the following: octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, octadecanoic acid, eicosanoic acid, teicosanoic acid, oleic acid, linoleic acid, arachidic acid, arachidonic acid, erucic acid, and docosahexaenoic acid; C6~C 30 Aromatic carboxylic acid ligands include, but are not limited to, one or more of benzoic acid, biphenylic acid, and 1-naphthoic acid. (C1-C2) 30 The aliphatic thiol ligands include, but are not limited to, one or more of hexamethylenetetramine, octanethiol, nonanethiol, decanethiol, undecylthiol, dodecathiol, hexadecylthiol, and octadecylthiol, C6–C6. 30 Thiol aromatic ligands include, but are not limited to, one or more of benzenethiol, triphenylmethanethiol, and p-terphenyl-4,4”-dithiol. C1~C 30 The aliphatic amine ligands include, but are not limited to, one or more of hexylamine, octylamine, dioctylamine, trioctylamine, nonylamine, decylamine, dodecylamine, trideamine, tetradeamine, pentadecylamine, hexadecylamine, heptadecanamine, octadecylamine, and oleylamine, C6-C6. 30 The aromatic amine ligands include, but are not limited to, one or more of aniline, indenepropylamine, 4-octylaniline, and benzidine. (C1-C2) 30The aliphatic phosphine ligands include, but are not limited to, one or more of trimethylphosphine, triethylphosphine, tripropylphosphine, tributylphosphine, trihexylphosphine, trioctylphosphine, tridecylphosphine, tributylphosphine oxide, trihexylphosphine oxide, trioctylphosphine oxide, and tridecylphosphine oxide, C6–C6. 30 Aromatic phosphine ligands include, but are not limited to, one or more of bis(2-diphenylphosphineethyl)phenylphosphine and triphenylphosphine oxide, C6-C6. 30 The aromatic phosphate ligands include, but are not limited to, one or more of tetraethyl p-xylene diphosphate and ethyl diphenyl phosphate. Halogen ligands include, but are not limited to, -Cl, -F, -I, or -Br.

[0066] In some embodiments of this application, the materials of the anode 101 and the cathode 102 are independently selected from one or more of a third metal, a third carbon material, and a first metal oxide material. The third metal includes, but is not limited to, one or more of Al, Ag, Cu, Mo, Au, Ba, Pt, Ca, Ir, Ni, and Mg. The third carbon material includes, but is not limited to, one or more of graphite, carbon nanotubes, graphene, and carbon fibers. The first metal oxide material includes, but is not limited to, one or more of indium tin oxide (ITO), fluorine-doped tin oxide (FTO), antimony tin oxide (ATO), aluminum-doped zinc oxide (AZO), gallium-doped zinc oxide (GZO), indium-doped zinc oxide (IZO), magnesium-doped zinc oxide (MZO), TiO2, SnO2, ZnO, and In2O3.

[0067] The anode 101 or cathode 102 can also be a composite electrode with a sandwich-like structure. The upper and lower layers are independently selected from a first metal oxide or metal sulfide, and the middle layer is a second metal, such as 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, TiO2 / Ag / TiO2, and TiO2 / Al / TiO2. The thickness of the middle layer does not exceed 35 nm. The thickness of the anode 101 can be, for example, 20 nm to 300 nm, and the thickness of the cathode 102 can be, for example, 20 nm to 300 nm.

[0068] It should be noted that the preparation methods for each film layer in optoelectronic devices include, but are not limited to, chemical and / or physical methods. Chemical methods include, but are not limited to, one or more of chemical vapor deposition, continuous ion layer adsorption and reaction, anodic oxidation, electrolytic deposition, and co-precipitation. Physical methods include, but are not limited to, physical deposition and solution methods. Physical deposition methods include, but are not limited to, one or more of thermal evaporation deposition, electron beam evaporation deposition, magnetron sputtering, multi-arc ion deposition, physical vapor deposition, atomic layer deposition, and pulsed laser deposition. Solution methods include, but are not limited to, one or more of spin coating, printing, inkjet printing, blade coating, dip coating, immersion coating, spray coating, roller coating, casting, slot coating, and strip coating. After preparing each film layer of the optoelectronic device, an encapsulation process is required. Encapsulation can be performed using common machine encapsulation or manual encapsulation. In the encapsulation environment, the oxygen and water content are both below 0.1 ppm to ensure the stability of the optoelectronic device.

[0069] This application also provides an electronic device, which includes any of the optoelectronic devices described above. The electronic device can be, for example, any electronic product with a display function, including but not limited to smartphones, tablet personal computers, mobile phones, video phones, e-book readers, laptop PCs, netbook computers, workstations, servers, personal digital assistants, portable multimedia players, MP3 players, mobile medical devices, cameras, game consoles, digital cameras, car navigation systems, electronic billboards, ATMs, smart bracelets, smartwatches, virtual reality (VR) devices, or wearable devices.

[0070] The technical solutions and effects of this application will be described in detail below through specific embodiments, comparative examples and experimental examples. The following embodiments are only some embodiments of this application and are not intended to limit this application.

[0071] Material Example 1

[0072] This embodiment provides a composite material, a thin film, and a method for preparing the same. The composite material includes core-shell nanoparticles and a first conductive agent. The core of the nanoparticles is made of nano-NiO, the shell of the nanoparticles is made of polyvinyl chloride, and the first conductive agent is copper. The mass ratio of the nanoparticles to the first conductive agent is 1:0.06. The average particle size of the nanoparticles is 25 nm, and the thickness of the shell of the nanoparticles is 5 nm.

[0073] The preparation method of the composite material includes the following steps: 100 mg of nanoparticles are dispersed in 10 mL of ethanol, then 6 mg of copper powder is added, and the mixture is ultrasonically dispersed evenly to obtain a dispersion containing the composite material.

[0074] The preparation method of nanoparticles includes the following steps: 3000 mg of polyvinyl chloride (product model P434341, purchased from Aladdin) is dissolved in 10 mL of tetrahydrofuran to obtain a polyvinyl chloride solution; then, 100 mg of powdered nano-NiO (average particle size of 20 nm) is immersed in the polyvinyl chloride solution for 30 min to form a polyvinyl chloride shell on the surface of the nano-NiO, and then dried at 80 °C to remove the solvent to obtain nanoparticles.

[0075] The material of the thin film in this embodiment includes the composite material of this embodiment, and the thickness of the thin film is 40 nm.

[0076] The thin film preparation method in this embodiment includes the following steps: providing a substrate, spin-coating the dispersion containing the composite material prepared in this embodiment onto one side of the substrate under a nitrogen atmosphere at room temperature and pressure, and then heat-treating it at a constant temperature of 120°C for 30 minutes under a nitrogen atmosphere to obtain a thin film.

[0077] Material Example 2

[0078] This embodiment provides a composite material, a thin film, and a method for preparing the same. Compared with the composite material in Material Example 1, the difference in this embodiment is that the mass ratio of nanoparticles to the first conductive agent is 1:0.1.

[0079] Compared to the preparation method of the composite material in Material Example 1, the difference in the preparation method of the composite material in this example is that the mass of copper powder is replaced with "10mg".

[0080] The preparation method of the nanoparticles in this embodiment is consistent with the preparation method of the nanoparticles in Material Example 1.

[0081] The material of the thin film in this embodiment includes the composite material of this embodiment, and the thickness of the thin film is 40 nm.

[0082] The thin film preparation method in this embodiment is the same as that in Material Example 1.

[0083] Material Example 3

[0084] This embodiment provides a composite material, a thin film, and a method for preparing the same. Compared with the composite material in Material Example 1, the difference in this embodiment is that the mass ratio of nanoparticles to the first conductive agent is 1:0.03.

[0085] Compared to the preparation method of the composite material in Material Example 1, the difference in the preparation method of the composite material in this example is that the mass of copper powder is replaced with "3mg".

[0086] The preparation method of the nanoparticles in this embodiment is consistent with the preparation method of the nanoparticles in Material Example 1.

[0087] The material of the thin film in this embodiment includes the composite material of this embodiment, and the thickness of the thin film is 40 nm.

[0088] The thin film preparation method in this embodiment is the same as that in Material Example 1.

[0089] Material Example 4

[0090] This embodiment provides a composite material, a thin film, and a method for preparing the same. The composite material in this embodiment is the nanoparticle with a core-shell structure as described in Material Example 1.

[0091] The material of the thin film in this embodiment includes the composite material of this embodiment, and the thickness of the thin film is 40 nm.

[0092] Compared to the film preparation method in Material Example 1, the difference in the film preparation method in this example is that: under a nitrogen atmosphere at room temperature and pressure, a dispersion containing nanoparticles is spin-coated onto one side of a substrate, and then subjected to constant temperature heat treatment at 120°C under a nitrogen atmosphere for 30 minutes to obtain a film. The preparation method of the dispersion containing nanoparticles includes the following steps: dispersing 100 mg of nanoparticles in 10 mL of ethanol, ultrasonically dispersing until uniform, to obtain a dispersion containing nanoparticles.

[0093] Material Example 5

[0094] This embodiment provides a composite material, a thin film, and a method for preparing the same. Compared with the composite material in Material Example 1, the difference in this embodiment is that the first conductive agent is replaced with "aluminum".

[0095] Compared with the preparation method of the composite material in Material Example 1, the difference in the preparation method of the composite material in this example is that "6mg of copper powder" is replaced with "6mg of aluminum powder".

[0096] The preparation method of the nanoparticles in this embodiment is consistent with the preparation method of the nanoparticles in Material Example 1.

[0097] The material of the thin film in this embodiment includes the composite material of this embodiment, and the thickness of the thin film is 40 nm.

[0098] The thin film preparation method in this embodiment is the same as that in Material Example 1.

[0099] Material Example 6

[0100] This embodiment provides a composite material, a thin film, and a method for preparing the same. Compared with the composite material in Material Example 1, the difference in this embodiment is that the first conductive agent is replaced with "silver".

[0101] Compared with the preparation method of the composite material in Material Example 1, the difference in the preparation method of the composite material in this example is that "6mg of copper powder" is replaced with "6mg of silver powder".

[0102] The preparation method of the nanoparticles in this embodiment is consistent with the preparation method of the nanoparticles in Material Example 1.

[0103] The material of the thin film in this embodiment includes the composite material of this embodiment, and the thickness of the thin film is 40 nm.

[0104] The thin film preparation method in this embodiment is the same as that in Material Example 1.

[0105] Material Example 7

[0106] This embodiment provides a composite material, a thin film, and a method for preparing the same. Compared with the composite material in Material Example 1, the difference in this embodiment is that "polyvinyl chloride" in the shell material of the nanoparticles is replaced with "polyamide".

[0107] The preparation method of the composite material includes the following steps: 100 mg of nanoparticles are dispersed in 10 mL of ethanol, then 6 mg of copper powder is added, and the mixture is ultrasonically dispersed evenly to obtain a dispersion containing the composite material.

[0108] The preparation method of nanoparticles in this embodiment includes the following steps: 3000 mg of polyamide (product model P111447, purchased from Aladdin) is dissolved in 10 mL of 3-methylphenol to obtain a polyamide solution; then, powdered nano-NiO (average particle size of 20 nm) is immersed in the polyamide solution for 30 min to form a polyamide shell on the surface of the nano-NiO, and then dried at 200 °C to remove the solvent to obtain nanoparticles.

[0109] The material of the thin film in this embodiment includes the composite material of this embodiment, and the thickness of the thin film is 40 nm.

[0110] The thin film preparation method in this embodiment is the same as that in Material Example 1.

[0111] Material Example 8

[0112] This embodiment provides a composite material, a thin film, and a method for preparing the same. The composite material includes core-shell structured nanoparticles and a first conductive agent. The core material of the nanoparticles includes nano-Zn. 0.85 Mg 0.15 The nanoparticles (average particle size 5 nm) have a shell material comprising polyvinyl chloride and a first conductive agent of copper powder, wherein the mass ratio of nanoparticles to the first conductive agent is 1:0.06. The average particle size of the nanoparticles is 7 nm.

[0113] The preparation method of the composite material includes the following steps: 100 mg of nanoparticles are dispersed in 10 mL of ethanol, then 6 mg of copper powder is added, and the mixture is ultrasonically dispersed evenly to obtain a dispersion containing the composite material.

[0114] The preparation method of the nanoparticles includes the following steps: dissolving 3000 mg of polyvinyl chloride (product model P434341, purchased from Aladdin) in 10 mL of tetrahydrofuran to obtain a polyvinyl chloride solution; then, taking 100 mg of powdered nano-Zn 0.85 Mg 0.15 O (average particle size of 5 nm) is immersed in a polyvinyl chloride solution for 30 minutes to allow the nano-Zn to be absorbed. 0.85 Mg 0.15 A polyvinyl chloride shell is formed on the surface of O, and then it is dried at 80°C to remove the solvent, thereby obtaining nanoparticles. The material of the film in this embodiment includes the composite material of this embodiment, and the thickness of the film is 40 nm.

[0115] The thin film preparation method in this embodiment includes the following steps: providing a substrate, spin-coating the dispersion containing the composite material prepared in this embodiment onto one side of the substrate under a nitrogen atmosphere at room temperature and pressure, and then heat-treating it at a constant temperature of 120°C for 30 minutes under a nitrogen atmosphere to obtain a thin film.

[0116] Material Example 9

[0117] This embodiment provides a composite material, a thin film, and a method for preparing the same. The composite material includes nanoparticles with a core-shell structure and a first conductive agent. The core material of the nanoparticles includes nano-MoO3 (average particle size of 30 nm), the shell material of the nanoparticles includes polyvinyl chloride, and the first conductive agent is copper powder. The mass ratio of nanoparticles to the first conductive agent is 1:0.06. The average particle size of the nanoparticles is 35 nm.

[0118] The preparation method of the composite material includes the following steps: 100 mg of nanoparticles are dispersed in 10 mL of ethanol, then 6 mg of copper powder is added, and the mixture is ultrasonically dispersed evenly to obtain a dispersion containing the composite material.

[0119] The preparation method of the nanoparticles includes the following steps: 3000 mg of polyvinyl chloride (product model P434341, purchased from Aladdin) is dissolved in 10 mL of tetrahydrofuran to obtain a polyvinyl chloride solution; then, 100 mg of powdered nano-MoO3 (average particle size of 10 nm) is immersed in the polyvinyl chloride solution for 30 min to form a polyvinyl chloride shell on the surface of the nano-MoO3, and then dried at 80 °C to remove the solvent to obtain nanoparticles. The material of the film in this embodiment includes the composite material of this embodiment, and the thickness of the film is 40 nm.

[0120] Material Comparison Example 1

[0121] This comparative example provides a thin film made of nano-NiO (average particle size of 20 nm) and with a thickness of 40 nm.

[0122] The preparation method of the thin film in this comparative example includes the following steps: providing a substrate, spin-coating a nano-NiO dispersion on one side of the substrate under a nitrogen atmosphere at room temperature and pressure, wherein the concentration of nano-NiO in the nano-NiO dispersion is 10 mg / mL, the dispersion medium of the nano-NiO dispersion is ethanol, and then heat-treating it at a constant temperature of 120°C under a nitrogen atmosphere for 30 min to obtain the thin film.

[0123] Material Comparison Example 2

[0124] This comparative example provides a thin film, the material of which is nano-Zn. 0.85 Mg 0.15 O (average particle size of 5nm), and the thickness of the film is 40nm.

[0125] The thin film preparation method in this comparative example includes the following steps: providing a substrate, and spin-coating nano-Zn onto one side of the substrate under a nitrogen atmosphere at room temperature and pressure. 0.85 Mg 0.15 O dispersion, nano Zn 0.85 Mg 0.15 Nano Zn in O dispersion0.85 Mg 0.15 The concentration of O is 30 mg / mL, and the nano-Zn 0.85 Mg 0.15 The dispersion medium for the O dispersion was ethanol, and then it was subjected to constant temperature heat treatment at 100°C under a nitrogen atmosphere for 15 minutes to obtain a thin film.

[0126] Material Comparison Example 3

[0127] This comparative example provides a thin film made of nano-MoO3 (average particle size of 30 nm) with a thickness of 40 nm.

[0128] The preparation method of the thin film in this comparative example includes the following steps: providing a substrate, and spin-coating a nano-MoO3 dispersion on one side of the substrate under a nitrogen atmosphere at room temperature and pressure. The concentration of nano-MoO3 in the nano-MoO3 dispersion is 10 mg / mL, and the dispersion medium of the nano-NiO dispersion is ethanol. Then, the substrate is subjected to constant temperature heat treatment at 120°C under a nitrogen atmosphere for 30 min to obtain the thin film.

[0129] Device Example 1

[0130] This embodiment provides an optoelectronic device and its fabrication method. The optoelectronic device is a quantum dot light-emitting diode with a positive-position structure, such as... Figure 1 As shown, in the direction from bottom to top, the optoelectronic device 10 includes an anode 101, a hole functional layer 103, a light-emitting layer 104, an electron functional layer 105, and a cathode 102 stacked sequentially. The hole functional layer 103 is composed of a hole injection layer 1031 and a hole transport layer 1032 stacked together. The hole injection layer 1031 is closer to the anode 101 than the hole transport layer 1032. The electron functional layer 105 is a single-layer structure and is an electron transport layer.

[0131] The materials and thicknesses of each layer in optoelectronic device 10 are as follows:

[0132] The anode 101 is made of ITO and has a thickness of 100 nm.

[0133] The cathode 102 is made of Ag and has a thickness of 50 nm.

[0134] Hole injection layer 1031 is the thin film in material comparative example 3;

[0135] Hole transport layer 1032 is the thin film in Material Example 1;

[0136] The material of the light-emitting layer 104 includes CdZnSe / CdZnS / ZnS light-emitting quantum dots, the light-emitting quantum dots have an emission wavelength of 545nm, and the thickness of the light-emitting layer 104 is 10nm;

[0137] The electronic functional layer 105 is the thin film in material comparison example 2.

[0138] The fabrication method of the light-emitting device in this embodiment includes the following steps:

[0139] S10.1 Provide a substrate (material is glass and thickness is 1mm), sputter ITO on one side of the substrate to obtain an ITO layer, use a cotton swab dipped in a small amount of soapy water to wipe the surface of the ITO layer to remove visible impurities, and then sequentially ultrasonically clean the substrate including ITO with deionized water for 15min, acetone for 15min, ethanol for 15min and isopropanol for 15min, dry it and then perform ultraviolet-ozone surface treatment for 15min to obtain a substrate containing an anode.

[0140] S10.2, Referring to the thin film preparation method in Comparative Example 3, a hole injection layer is formed on the side of the anode away from the substrate;

[0141] S10.3, Referring to the thin film preparation method in Material Example 1, a hole transport layer is formed on the side of the hole injection layer away from the anode;

[0142] S10.4 Under a nitrogen atmosphere at room temperature and pressure, spin-coat a quantum dot solution (quantum dot concentration of 40 mg / mL, solvent of n-octane) onto the side of the hole transport layer away from the hole injection layer, and then place it under a vacuum of no more than 3 × 10⁻⁶. -4 The light-emitting layer is obtained by vacuum drying in the vapor deposition chamber of Pa for 15 min, followed by constant temperature heat treatment at 100°C for 10 min in a nitrogen atmosphere.

[0143] S10.5, Referring to the preparation method of the thin film in Comparative Example 2, an electronic functional layer is formed on the side of the light-emitting layer away from the hole transport layer;

[0144] S10.6. Place the laminated structure that has completed step S10.5 in a vacuum with a vacuum level not exceeding 3×10⁻⁶. -4 In the vapor deposition chamber of Pa, Ag is thermally vaporized on the side of the electronic functional layer away from the light-emitting layer through a mask to obtain the cathode, and then encapsulated with epoxy resin to obtain the optoelectronic device.

[0145] Device Examples 2 to 7

[0146] Device Example n is essentially the same as Device Example 1, except that in Device Example n, the hole transport layer is the thin film in Material Example n, and correspondingly, the hole transport layer in Device Example n is prepared by referring to the preparation method of the thin film in Material Example n, where n is a positive integer from 2 to 7. For example, in Device Example 2, the hole transport layer is the thin film in Material Example 2, and the hole transport layer in Device Example 2 is prepared by referring to the preparation method of the thin film in Material Example 2, and so on.

[0147] Device Example 8

[0148] This embodiment provides an optoelectronic device and its fabrication method. Compared with the optoelectronic device in Device Embodiment 1, the difference of the optoelectronic device in this embodiment is that the electronic functional layer is the thin film in Material Embodiment 8.

[0149] Compared to the method for preparing the optoelectronic device in Material Example 1, the method for preparing the optoelectronic device in this example differs in that step S10.5 is replaced with "forming an electronic functional layer on the side of the light-emitting layer away from the hole transport layer, referring to the method for preparing the thin film in Material Example 8".

[0150] Device Example 9

[0151] This comparative example provides an optoelectronic device and its fabrication method. Compared with the optoelectronic device in Device Example 1, the difference of the optoelectronic device in this comparative example is that the electronic functional layer is the thin film in Material Example 8, and the hole transport layer is the thin film in Material Comparative Example 1.

[0152] Compared to the method for preparing the optoelectronic device in Material Example 1, the method for preparing the optoelectronic device in this example differs in that: step S10.3 is replaced with "forming a hole transport layer on the side of the hole injection layer away from the anode, referring to the method for preparing the thin film in Material Comparative Example 1", and step S10.5 is replaced with "forming an electronic functional layer on the side of the light-emitting layer away from the hole transport layer, referring to the method for preparing the thin film in Material Example 8".

[0153] Device Example 10

[0154] This embodiment provides an optoelectronic device and its fabrication method. Compared with the optoelectronic device in Device Example 1, the difference of the optoelectronic device in this embodiment is that the material of the electronic functional layer includes the core-shell structured nanoparticles in Material Example 8, and the hole transport layer is the thin film in Material Comparative Example 1.

[0155] Compared to the method for preparing the optoelectronic device in Device Example 1, the method for preparing the optoelectronic device in this example differs in that: step S10.3 is replaced with "forming a hole transport layer on the side of the hole injection layer away from the anode by referring to the thin film preparation method in Material Comparative Example 1", and step S10.5 is replaced with "spin-coating a dispersion containing the nanoparticles with the core-shell structure in Material Example 8 on the side of the light-emitting layer away from the hole transport layer under normal temperature and pressure nitrogen atmosphere, and then placing it under constant temperature heat treatment at 100°C for 15 min to obtain an electronic functional layer with a thickness of 40 nm". The method for preparing the dispersion containing the nanoparticles with the core-shell structure in Material Example 8 includes the following steps: taking 100 mg of the nanoparticles with the core-shell structure in Example 8 and dispersing them in 10 mL of ethanol, ultrasonically dispersing them evenly to obtain a dispersion containing nanoparticles.

[0156] Device Example 11

[0157] This embodiment provides an optoelectronic device and its fabrication method. Compared with the optoelectronic device in Device Embodiment 1, the difference of the optoelectronic device in this embodiment is that the material of the electronic functional layer includes nanoparticles with a core-shell structure as in Material Embodiment 8, and the hole transport layer is the thin film as in Material Embodiment 4.

[0158] Compared to the fabrication method of the optoelectronic device in Device Example 1, the difference in the fabrication method of the optoelectronic device in this example is that step S10.3 is replaced with "forming a hole transport layer on the side of the hole injection layer away from the anode by referring to the thin film fabrication method in Material Example 4", and step S10.5 is replaced with "spin-coating a dispersion containing nanoparticles with a core-shell structure as described in Material Example 8 (the preparation method is described in the relevant part of Device Example 10) on the side of the light-emitting layer away from the hole transport layer under normal temperature and pressure nitrogen atmosphere, and then placing it under constant temperature heat treatment at 100°C for 15 min to obtain an electronic functional layer with a thickness of 40 nm".

[0159] Device Example 12

[0160] This embodiment provides an optoelectronic device and its fabrication method. Compared with the optoelectronic device in Device Embodiment 1, the difference of the optoelectronic device in this embodiment is that the electronic functional layer is the thin film in Material Embodiment 8, and the hole transport layer is the thin film in Material Embodiment 4.

[0161] Compared to the method for preparing the optoelectronic device in Material Example 1, the method for preparing the optoelectronic device in this example differs in that: step S10.3 is replaced with "forming a hole transport layer on the side of the hole injection layer away from the anode, referring to the thin film preparation method in Material Example 4", and step S10.5 is replaced with "forming an electronic functional layer on the side of the light-emitting layer away from the hole transport layer, referring to the thin film preparation method in Material Example 8".

[0162] Device Example 13

[0163] This embodiment provides an optoelectronic device and its fabrication method. Compared with the optoelectronic device in Device Example 1, the difference of the optoelectronic device in this embodiment is that the material of the hole injection layer is the core-shell structured nanoparticle in Material Example 9, and the hole transport layer is the thin film in Material Comparative Example 1.

[0164] Device Example 14

[0165] This embodiment provides an optoelectronic device. Compared with the optoelectronic device in Device Embodiment 1, the difference of the optoelectronic device in this embodiment is that the hole injection layer is the thin film in Material Embodiment 9, and the hole transport layer is the thin film in Material Comparative Embodiment 1.

[0166] Device Example 15

[0167] This embodiment provides an optoelectronic device. Compared with the optoelectronic device in Device Embodiment 1, the difference of the optoelectronic device in this embodiment is that: the hole injection layer is the thin film in Material Embodiment 9, and the hole transport layer is the thin film in Material Comparative Example 1, and the material of the electronic functional layer includes nanoparticles with a core-shell structure in Material Embodiment 8.

[0168] Device Example 16

[0169] This embodiment provides an optoelectronic device. Compared with the optoelectronic device in Device Embodiment 1, the difference of the optoelectronic device in this embodiment is that: the hole injection layer is the thin film in Material Embodiment 9, the hole transport layer is the thin film in Material Comparative Example 1, and the material of the electronic functional layer includes the thin film in Material Embodiment 8.

[0170] Device Comparison

[0171] This comparative example provides an optoelectronic device and its fabrication method. Compared with the optoelectronic device in Device Example 1, the difference of the optoelectronic device in this comparative example is that the hole transport layer is the thin film in Material Comparative Example 1.

[0172] Compared with the method for preparing the optoelectronic device in Material Example 1, the method for preparing the optoelectronic device in this comparative example differs in that step S10.3 is replaced with "the method for preparing the thin film in Material Comparative Example 1 is used to form a hole transport layer on the side of the hole injection layer away from the anode".

[0173] Experimental Example 1

[0174] The thin films from Material Examples 1 to 9 and the comparative examples were subjected to performance testing. The surface roughness Ra of each thin film was measured using an atomic force microscope. The test results are shown in Table 1 below.

[0175] Table 1

[0176]

[0177]

[0178] As shown in Table 1, compared to the film in Material Comparative Example 1, the films in Material Examples 1 to 7 have lower surface roughness Ra; compared to the film in Material Comparative Example 2, the film in Material Example 8 has lower surface roughness Ra; and compared to the film in Material Comparative Example 3, the film in Material Example 9 has lower surface roughness Ra. This is because the films in Material Examples 1 to 9 include nanoparticles with a core-shell structure. The shell material of the nanoparticles includes polymers, which can effectively passivate the surface defect states of the core, thereby improving the problem of easy aggregation of nanoparticles in solution and thus improving the film quality. The film in Material Comparative Example 1 was prepared using single-component nano-NiO, and the film in Material Comparative Example 2 was prepared using single-component nano-Zn. 0.85 Mg 0.15 In the preparation of O, and in the material comparative example 3, the thin film was prepared using single-component nano-MoO3. When the thin film was prepared by solution method, the crystal particles agglomerated due to orientation stress, resulting in poor film quality.

[0179] Experiment Example 2

[0180] The performance of the optoelectronic devices in Device Examples 1 to 16 and the comparative device were tested after 1 hour of encapsulation. The performance tests were conducted at a temperature of 25°C and a relative humidity of 50%.

[0181] The testing instruments include the Fostar FPD optical characteristic measurement equipment and the external quantum efficiency optical testing instrument. The Fostar FPD optical characteristic measurement equipment is an efficiency testing system constructed from components such as a Marine Optics USB2000, a LabVIEW-controlled QE-PRO spectrometer, a Keithley 2400, a high-precision digital source meter Keithley 6485, a 50μm inner diameter optical fiber, device test probes and fixtures, various connecting cables and data cards, an efficiency testing cassette, and a data acquisition system. This system acquires the turn-on voltage (Ub) of each optoelectronic device. T The parameters such as current, brightness, and emission spectrum are obtained, and then key parameters such as external quantum efficiency and power efficiency are calculated.

[0182] The current efficiency detection method includes the following steps: intermittently acquiring the brightness values ​​of the photoelectric device within the driving voltage range of 0V to 8V, with the acquired luminous area being 0.04cm². 2 The initial voltage for acquiring brightness is 3V, and measurements are taken every 0.2V. The brightness value acquired each time is divided by the corresponding current density to obtain the current efficiency of the optoelectronic device under that acquisition condition. The maximum current efficiency (CE) is then obtained. max The current density of the optoelectronic device at 1000 nits (J@1000nit, A / m) was obtained. 2 ).

[0183] The device lifetime testing method includes the following steps: Under constant current (2mA) driving, a 128-channel QLED lifetime testing system is used to perform electroluminescence lifetime analysis on each optoelectronic device, record the time (T95,h) required for each optoelectronic device to decay from maximum brightness to 95%, and calculate the time (T95@1000nit,h) required for each optoelectronic device to decay from 100% brightness to 95% brightness at 1000nit using the decay fitting formula.

[0184] The formula for calculating device lifetime is as follows:

[0185]

[0186] In the above formula, T95 L For longer lifespan at low brightness, T95 H For the measured lifetime under high brightness, L H To accelerate the device to its maximum brightness, L L The value is 1000 nits, and A is the acceleration factor, which is usually between 1.6 and 2. In this experimental example, the value of A for the optoelectronic device is 1.7.

[0187] In addition, the leakage current of optoelectronic devices is detected using the following method: 25 parallel samples are set up for each type of optoelectronic device, and four light-emitting test points are set up in each parallel sample. The positions of the light-emitting test points are basically the same across the parallel samples. The number of light-emitting test points where leakage occurs is counted, and the leakage rate is calculated. The formula for calculating the leakage rate is:

[0188] Leakage current (%) = Number of light-emitting test points where leakage occurs / 100 × 100%.

[0189] The performance test data for each optoelectronic device are detailed in Table 2 below:

[0190] Table 2

[0191]

[0192]

[0193] As shown in Table 2, compared to the optoelectronic devices in the comparative examples, the optoelectronic devices in Device Examples 1 to 16 exhibit superior overall performance. Specifically, the optoelectronic devices in Device Examples 1 to 16 have higher current efficiency, longer device lifespan, and lower leakage current. Taking the optoelectronic device in Device Example 1 as an example, the CE of the optoelectronic device in Device Example 1... max The CE of the optoelectronic device in the device comparison example max The T95@1000nit of the optoelectronic device in Device Example 1 is 2.3 times that of the optoelectronic device in Device Comparative Example 2.4 times that of the optoelectronic device in Device Comparative Example 3. The leakage rate of the optoelectronic device in Device Example 1 is 40% lower than that of the optoelectronic device in Device Comparative Example 4.

[0194] This demonstrates that the materials of the hole transport layer in optoelectronic devices, including nanoparticles with core-shell structures and / or the materials of the electron transport layer, including nanoparticles with core-shell structures, can improve the surface smoothness of the film, thereby reducing leakage current in optoelectronic devices and thus improving the current efficiency and device lifespan.

[0195] The foregoing has provided a detailed description of a composite material, a thin film, and an optoelectronic device provided in the embodiments of this application. Specific examples have been used to illustrate the principles and implementation methods of this application. The descriptions of the embodiments above are merely for the purpose of helping to understand the technical solutions and core ideas of this application. Those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features; and these modifications or substitutions do not cause the corresponding technical solutions to deviate from the scope of the technical solutions in the embodiments of this application.

Claims

1. A composite material, characterized by, The composite material comprises nanoparticles having a core-shell structure, a material of a core of the nanoparticles comprises at least one P-type inorganic compound or at least one N-type inorganic compound, and a material of a shell of the nanoparticles comprises at least one polymer.

2. The composite material of claim 1, wherein, At least one of the P-type inorganic compound is selected from one or more of NiO, MoO3, WO3, V2O5, Cr2O3, CuO, Cu2O and CuI; and / or, at least one of the N-type inorganic compounds is selected from the group consisting of ZnO, TiO2, SnO2, BaO, Ta2O3, Al2O3, ZrO2, Zn (1-x) Mg x O, Zn (1-x) Ca x O, Zn (1-x) Zr x O, Zn (1-x) Ga x O, Zn (1-x) Al x O, Zn (1-x) Li x O, Al (1-x) Zn x O, Zn (1-x) Ti x O, Zn (1-x) Y x O, In (1-x) Sn x O, and Ti (1-x) Li x O, wherein 0 At least one of the polymer is selected from one or more of a thermoplastic resin and a thermosetting resin; optionally, the thermoplastic resin is selected from one or more of polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyamide, polycarbonate, polyoxymethylene, polyphenylene ether, polysulfone and polytetrafluoroethylene, and / or the thermosetting resin is selected from one or more of an epoxy resin, a polyester resin, a vinyl resin, a bismaleimide resin, a phenolic resin and a melamine formaldehyde resin; The composite material further comprises a first conductive agent, the first conductive agent comprises a first metal and / or a first carbon material; optionally, the first metal is selected from one or more of copper, aluminum and silver, and / or the first carbon material is selected from one or more of graphite, carbon nanotube, graphene and carbon fiber; The average particle size of the nanoparticles is 2 nm to 50 nm; The thickness of the shell of the nanoparticles is 2 nm to 5 nm; The coating rate of the shell to the core is 30% to 100%; The mass ratio of the shell to the core is 1:(20-100).

3. The composite material of claim 2, wherein, When the composite material comprises the first conductive agent, in the composite material, the mass ratio of the nanoparticles to the first conductive agent is 1:(0.03-0.1).

4. A film characterized by, The material of the thin film comprises the composite material as claimed in any one of claims 1 to 3, and / or the thin film is prepared by using the composite material as claimed in any one of claims 1 to 3.

5. The film of claim 4, wherein The surface roughness Ra of the thin film is 0.3 nm to 0.5 nm; The thickness of the thin film is 20 nm to 50 nm.

6. A method of producing a film, characterized by, The method comprises the steps of: providing a dispersion liquid comprising nanoparticles, depositing the dispersion liquid, drying to form a film, and obtaining a thin film; The nanoparticles are as claimed in any one of claims 1 to 3.

7. The method of claim 6, wherein the film is prepared by a method comprising: The dispersion liquid further comprises a second conductive agent, the second conductive agent comprises a second metal and / or a second carbon material; optionally, the second metal is selected from one or more of copper, aluminum and silver, and / or the second carbon material is selected from one or more of graphite, carbon nanotube, graphene and carbon fiber; and / or, the dispersing medium of the dispersion is selected from one or more of alkanes, aromatic hydrocarbons, halogenated hydrocarbons, alcohol compounds, ether compounds, ketone compounds, ester compounds, furan compounds, pyridine compounds, amide compounds, and sulfone compounds; optionally, the alkanes are selected from one or more of nonane, decane, dodecane, terpane, butylcyclohexane, n-octane, n-hexane, n-heptane, n-nonane, n-decane, cyclohexane, and cyclopentane, and / or the aromatic hydrocarbons are selected from one or more of diethylbenzene, mesitylene, propylbenzene, cumene, p-cymene, butylbenzene, and 1-methylnaphthalene or indene, and / or the halogenated hydrocarbons are selected from one or more of dichloromethane, chloroform, and carbon tetrachloride, and / or the alcohol compounds are selected from one or more of methanol, ethanol, propanol, butanol, ethylene glycol, and glycerol, and / or the ether compounds are selected from one or more of ethylene glycol monomethyl ether, diethyl ether, and propylene oxide, and / or the ketone compounds are selected from one or more of acetone, butanone, and N-methylpyrrolidone, and / or the ester compounds are selected from one or more of ethyl acetate, ethyl acetate, and propyl acetate, and / or the furan compounds are selected from one or more of tetrahydrofuran and 2-methylfuran, and / or the pyridine compounds are selected from pyridine, and / or the amide compounds are selected from N,N-dimethylformamide, and / or the sulfone compounds are selected from dimethyl sulfoxide; and / or, the concentration of the nanoparticles in the dispersion is 5 mg / mL to 10 mg / mL.

8. The method of claim 6, wherein the film is prepared by a method comprising: When the dispersion further comprises a second conductive agent, the mass ratio of the nanoparticles to the second conductive agent in the dispersion is 1:(0.03-0.1).

9. An optoelectronic device, characterized in that Comprise: a cathode and an anode arranged oppositely; and a plurality of functional layers arranged between the anode and the cathode; wherein at least one of the plurality of functional layers comprises the composite material as claimed in any one of claims 1 to 3, or the film as claimed in claim 4 or 5, or the film prepared by the method as claimed in any one of claims 6 to 8, or at least one of the plurality of functional layers is prepared using the composite material as claimed in any one of claims 1 to 3.

10. The optoelectronic device of claim 9, wherein, The plurality of functional layers comprises a hole functional layer, the hole functional layer comprises the composite material as claimed in any one of claims 1 to 3, or the film as claimed in claim 4 or 5, or the film prepared by the method as claimed in any one of claims 6 to 8, or the hole functional layer is prepared using the composite material as claimed in any one of claims 1 to 3, wherein the material of the core of the nanoparticles comprises at least one of the P-type inorganic compounds; and / or, the plurality of functional layers comprises an electronic functional layer, which comprises the composite material as claimed in any one of claims 1 to 3, or the thin film as claimed in claim 4 or 5, or the thin film prepared by the method as claimed in any one of claims 6 to 8, or the electronic functional layer is prepared by using the composite material as claimed in any one of claims 1 to 3, wherein the material of the core of the nanoparticle comprises at least one of the N-type inorganic compounds; and / or, the plurality of functional layers comprises a light-emitting layer, the material of the light-emitting layer comprises one or more of organic light-emitting materials and light-emitting quantum dots.

Images