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

Abstract

The invention belongs to the technical field of display, and relates to a composite film, a preparation method, a photoelectric device and a display device. The preparation method of the composite film comprises the following steps: preparing a carrier material solution of a carrier functional material and a first solvent; and depositing the carrier material solution to form a carrier functional layer. Arranging a carrier material solution on the substrate to form a carrier functional layer; placing the carrier functional layer in an atmosphere of a set solvent so as to form a protective layer on the carrier functional layer; and performing plasma treatment on the carrier functional layer to enable the surface of the carrier functional layer and / or the protective layer to be charged to obtain the composite film. According to the embodiment of the invention, the protective film is formed on the carrier functional layer and the plasma treatment is carried out, so that the carrier functional layer is prevented from being degraded, the surface of the carrier functional layer is charged, the carrier transmission efficiency of the composite film can be improved, and the service life of the composite film can be prolonged.

Description

Technical Field

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

[0002] Currently, the widely used optoelectronic devices are organic light-emitting diodes (OLEDs) and quantum dot light-emitting diodes (QLEDs). Due to its excellent display performance such as self-luminescence, simple structure, ultra-thinness, fast response speed, wide viewing angle, low power consumption, and flexible display, OLED has become the mainstream technology in the field of display technologies. QLED has the advantages of saturated emission light color and adjustable wavelength, and high photoluminescence and electroluminescence quantum yields. In recent years, it has become a strong competitor to OLED.

[0003] In optoelectronic devices, a carrier functional layer is often provided to improve carrier transport, but there are still problems such as low recombination rate of hole carriers and electron carriers and easy leakage of electrons at the interface of the carrier functional layer. Summary of the Invention

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

[0005] In order to solve the above technical problems, embodiments of the present application provide a preparation method of a composite film. The preparation method of the composite film adopts the following technical solutions:

[0006] Provide a carrier material solution including a carrier functional material and a first solvent;

[0007] Deposit the carrier material solution to form a carrier functional layer;

[0008] Place the carrier functional layer in an atmosphere of a set solvent to form a protective layer on the carrier functional layer;

[0009] Perform plasma treatment on the carrier functional layer to make the surface of the carrier functional layer and / or the protective layer charged, and obtain a composite film.

[0010] Further, the plasma treatment includes providing plasma gas to the surface of the protective layer and / or the carrier functional layer;

[0011] The gas flow rate of the plasma gas is 30 sccm / s to 80 sccm / s; and / or,

[0012] The treatment power of the plasma treatment is 60 W to 100 W; and / or,

[0013] The treatment time of the plasma treatment is 60 s to 150 s; and / or,

[0014] The plasma gas includes at least one of oxygen, inert gas, sulfur tetrafluoride, and carbon tetrafluoride; the inert gas includes at least one of nitrogen, helium, argon, and neon; and / or

[0015] The work function ratio of the composite film to the carrier functional layer before being placed in the atmosphere of the set solvent is (1.4 to 1.6):1.

[0016] Further, the step of placing the carrier functional layer in the atmosphere of the set solvent includes heating the carrier functional layer, and the heating temperature is 150°C to 250°C; and / or, the heating time is 10 min to 60 min.

[0017] Further, the step of depositing the carrier material solution to form a carrier functional layer includes:

[0018] Forming a liquid film of the carrier material solution and performing a first drying treatment;

[0019] Performing a second drying treatment on the liquid film after the first drying treatment to obtain a carrier functional layer;

[0020] The air pressure of the first drying treatment is 8000 Pa to 11000 Pa, and / or, the treatment time of the first drying treatment is 1 min to 5 min; and / or,

[0021] The air pressure of the second drying is 1.333×10 -1 Pa to 1.333×10 -6 Pa, and the treatment time is 1 min to 20 min.

[0022] Further, the carrier material solution includes a carrier functional material and a first solvent.

[0023] Further, the carrier functional material includes any one of a hole functional material and an electron functional material; and / or

[0024] The first solvent and the set solvent independently include any one or a combination of alcohol solvents, ketone solvents, and alcohol ether solvents; and / or,

[0025] The first solvent is the same as the set solvent.

[0026] Further, the carrier functional material is a hole functional material, and the hole functional material includes a hole injection material and / or a hole transport material. The hole injection material includes one or a combination of poly(3,4-ethylenedioxythiophene), poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid, 2,3,5,6-tetrafluoro-7,7',8,8'-tetracyanoquinodimethane, 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene, polycarbonate copper, transition metal oxides, and transition metal chalcogenides; and / or,

[0027] The hole transport material includes poly, 3-hexyl-substituted polythiophene, poly(9-vinylcarbazole), poly[bis(4-phenyl)(4-butylphenyl)amine], poly(N,N'-bis(4-butylphenyl)-N,N'-diphenyl-1,4-phenylenediamine-CO-9,9-dioctylfluorene), 4,4',4”-tris(carbazol-9-yl)triphenylamine, 4,4'-bis(9-carbazolyl)biphenyl, N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine, N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine, poly(3,4-ethylenedioxythiophene):poly(styrene sulfonic acid), doped or undoped graphene, C 60 、NiO、MoO 3 、WO 3 、V 2 O 5 、CrO 3 、CuO or one or a combination of p-type gallium nitride; and / or,

[0028] The alcohol solvents include one or a combination of isopropyl alcohol, diethylene glycol, 1,2-ethylene glycol, and 2-phenoxyethanol; and / or,

[0029] The ketone solvents include one or a combination of N-methylpyrrolidone, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and acetophenone;

[0030] The alcohol ether solvents include one or a combination of diethylene glycol monobutyl ether, diethylene glycol butyl ether, diethylene glycol monomethyl ether, and triethylene glycol monomethyl ether.

[0031] Further, the carrier functional material is an electron functional material, and the electron functional material includes one or a combination of doped or undoped inorganic materials and organic materials;

[0032] The undoped inorganic materials include ZnO, TiO 2 、SnO 2 、Al 2 O 3 、GaO、Ga2 O 3 、ZrO 2 、NiO, ZnS, ZnSe, CdS, InP, GaP, BaTiO 3 、Cs 2 CO 3 、Rb 2 CO 3 、RbBr, LiF, LiF / Yb, MgP, MgF 2 or a combination thereof;

[0033] The doped inorganic material includes an undoped inorganic material and a doping element, and the doping element includes one or a combination of Mg, Ca, Li, Ga, Al, Co, Mn, Zr, W, Ti, Yb;

[0034] The organic material is selected from one or a combination of polymethyl methacrylate, polyvinyl butyral, polycarbonate, and polyurethane; and / or,

[0035] The alcohol compound includes methanol, ethanol, 1,2-ethylene glycol, 2-phenoxyethanol; and / or,

[0036] The thickness of the protective layer is 0.5 nm to 2 nm.

[0037] Correspondingly, the present application also provides a composite film, and the composite film is prepared by using the preparation method of the composite film as described above.

[0038] Correspondingly, the present application also provides an optoelectronic device including a bottom electrode, a functional layer, and a top electrode stacked in sequence, wherein the functional layer includes a composite film prepared by using the above preparation method, or includes the composite film as described above.

[0039] The bottom electrode and the top electrode respectively include a metal oxide electrode or a composite electrode with a metal disposed between doped or undoped transparent metal oxides. The material of the metal oxide electrode includes one or several of ITO, FTO, ATO, AZO, GZO, IZO, MZO, and AMO. The composite electrode includes one or several of AZO / Ag / AZO, AZO / Al / AZO, ITO / Ag / ITO, ITO / Al / ITO, ZnO / Ag / ZnO, ZnO / Al / ZnO, ZnS / Ag / ZnS, ZnS / Al / ZnS, TiO 2 / Ag / TiO 2 and TiO 2 / Al / TiO 2 among others.

[0040] The functional layer includes a stacked carrier functional layer and a protective layer, and one side of the carrier functional layer close to the protective layer and / or the surface of the protective layer is charged;

[0041] The protective layer is close to the top electrode.

[0042] Correspondingly, the present application further provides a display device, and the display device includes the optoelectronic device as described above.

[0043] Compared with the prior art, the embodiments of the present application mainly have the following beneficial effects:

[0044] In the embodiments of the present application, by forming a protective film on the carrier functional layer and performing plasma treatment, the deterioration of the carrier functional layer is avoided. At the same time, its surface is charged, which can improve the carrier transport efficiency and service life of the composite film. Description of the Drawings

[0045] In order to more clearly illustrate the solutions in the present application or the prior art, the following will briefly introduce the drawings required for the description of the embodiments or the prior art. Obviously, the drawings in the following description are some embodiments of the present application. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without creative efforts.

[0046] Figure 1 is a flowchart of the preparation method of the composite film according to the embodiment of the present application;

[0047] Figure 2 is a schematic structural diagram of the composite film according to the embodiment of the present application;

[0048] Figure 3 is a schematic structural diagram of the positive optoelectronic device according to the embodiment of the present application;

[0049] Figure 4 is a schematic structural diagram of the inverted optoelectronic device according to the embodiment of the present application;

[0050] Figure 5 is a test result diagram of the external quantum efficiency EQE of the optoelectronic devices provided in Embodiment 1, 3 and Comparative Example 1;

[0051] Figure 6 is a test result diagram of the working life of the optoelectronic devices provided in Embodiment 1, 3 and Comparative Example 1.

[0052] Reference Signs:

[0053] Composite film 10, protective layer 11, carrier functional layer 12, anode 100, hole injection layer 200, hole injection layer protective layer 210, hole transport layer 300, hole transport layer protective layer 310, light-emitting layer 400, electron transport layer 500, electron transport layer protective layer 510, cathode 600, capping layer 700. Detailed implementation manners

[0054] The following will clearly and completely describe the technical solutions in the embodiments of the present application with reference to the accompanying drawings in the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present application without creative efforts belong to the scope of protection of the present application. In addition, it should be understood that the specific implementation manners described herein are only for explaining and understanding the present application, and are not used to limit the present application.

[0055] In the present application, unless otherwise stated, the orientation terms such as "upper" and "lower" generally refer to the upper and lower in the actual use or working state of the device, specifically the drawing direction in the accompanying 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 for marking and do not impose a numerical requirement or establish an order.

[0056] 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.

[0057] In the present application, "at least one" means one or more, and "a plurality" 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 plural respectively.

[0058] Various embodiments of the present 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 the present application; therefore, it should be considered that the range description has specifically disclosed all possible sub-ranges and individual values within the 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 individual numbers within the 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.

[0059] Please refer to Figure 1 , embodiments of the present application provide a method for preparing a composite film, and the method for preparing the composite film adopts the following technical solutions:

[0060] S110, provide a carrier material solution including a carrier functional material and a first solvent;

[0061] S120, deposit the carrier material solution to form a carrier functional layer;

[0062] S130, place the carrier functional layer in an atmosphere of a set solvent to form a protective layer on the carrier functional layer;

[0063] S140, perform plasma treatment on the carrier functional layer to charge the surface of the carrier functional layer and / or the protective layer, obtaining a composite film.

[0064] Performing plasma treatment on the carrier functional layer can charge the surface of the carrier functional layer. Therefore, the work function of the composite film and the polaron state density between the carrier functional layer and other film layers increase, thereby avoiding electron leakage to the hole transport layer and improving the carrier transport efficiency.

[0065] Meanwhile, in the embodiments of the present application, the carrier functional layer is placed in an atmosphere of a set solvent, so that a protective layer is formed on the surface of the carrier functional layer. The protective layer can prevent the internal materials of the carrier functional layer from reacting with the plasma during plasma treatment, resulting in deterioration of the carrier functional layer, thereby further improving the external quantum efficiency and increasing the service life of the device. In summary, the embodiments of the present application can improve the recombination rate of hole carriers and electron carriers and avoid electron leakage to the hole transport layer.

[0066] It is understandable that the protective layer can be formed on the surface of the carrier functional layer, or a part of it can be mixed with the carrier functional layer, and the other part is located on the surface of the carrier functional layer. It can also be formed by mixing with the part of the carrier functional layer close to the other film layers. In a QLED device, the carrier functional layer includes, but is not limited to, a hole injection layer, a hole transport layer, and an electron transport layer. In an OLED device, the carrier functional layer includes, but is not limited to, a hole injection layer, a hole transport layer, an electron transport layer, and an electron injection layer. It is set that the solvent does not react with the carrier functional layer, or the reaction that occurs does not affect the recombination rate of hole carriers and electron carriers, and a thin film can be formed on the carrier functional layer through annealing. When plasma treatment makes the surfaces of the carrier functional layer and the protective layer charged, the protective layer itself can also play a role in carrying charges, that is, further avoiding electron leakage. The methods for depositing the carrier functional material include, but are not limited to, VCD drying, heating to evaporate the first solvent, etc.

[0067] Furthermore, the plasma treatment includes providing plasma gas to the surface of the protective layer and / or the carrier functional layer. The gas flow rate of the plasma treatment is 30 sccm / s to 80 sccm / s, and / or the treatment power is 60 W to 100 W, and / or the treatment time is 60 s to 150 s. Within the above parameter range of the plasma treatment, the plasma treatment process can reduce the occurrence of side reactions and reduce unnecessary chemical reactions, so as to better retain the original characteristics of the carrier functional layer and avoid damage to the protective layer and the carrier functional layer during the plasma treatment process. It is understandable that the gas flow rate can be any value among 30 sccm / s, 35 sccm / s, 40 sccm / s, 45 sccm / s, 50 sccm / s, 55 sccm / s, 60 sccm / s, 65 sccm / s, 70 sccm / s, 75 sccm / s, 80 sccm / s or the range formed by any two values. The treatment power of the plasma treatment can be any value among 60 W, 65 W, 70 W, 75 W, 80 W, 85 W, 90 W, 95 W, 100 W or the range formed by any two values. The treatment time can be any value among 60 s, 65 s, 70 s, 75 s, 80 s, 85 s, 90 s, 95 s, 100 s, 105 s, 110 s, 115 s, 120 s, 125 s, 130 s, 135 s, 140 s, 145 s, 150 s or the range formed by any two values. The gas for the plasma treatment includes at least one of oxygen, inert gas, sulfur tetrafluoride, and carbon tetrafluoride, where the inert gas includes, but is not limited to, at least one of helium, argon, and neon.

[0068] Further, the step of placing the carrier functional layer in an atmosphere of a set solvent includes heating the carrier functional layer, where the heating temperature is 150°C to 250°C; and / or, the heating time is 10 min to 60 min. The heating temperature and time in the embodiments of the present application can promote the rearrangement of the crystal structure inside the carrier functional layer, making the crystal size increase and the arrangement more orderly, and can improve the charge transport performance in the functional layer, which helps to improve the conductivity and electron mobility of the carrier functional layer, thereby improving the optical display effect of the optoelectronic device. It can be understood that the heating temperature can be any value in the range formed by any one or any two of the values 150°C, 155°C, 160°C, 165°C, 170°C, 175°C, 180°C, 185°C, 190°C, 195°C, 200°C, 205°C, 210°C, 215°C, 220°C, 225°C, 230°C, 235°C, 240°C, 245°C, 250°C. The heating time can be any value in the range formed by any one or any two of the values 10 min, 15 min, 20 min, 25 min, 30 min, 35 min, 40 min, 45 min, 50 min, 55 min, 60 min.

[0069] Further, the step of depositing the carrier material solution to form the carrier functional layer includes:

[0070] Forming a liquid film on the substrate with the carrier material solution and performing a first drying treatment;

[0071] Performing a second drying treatment on the liquid film after the first drying treatment to obtain the carrier functional layer;

[0072] The air pressure of the first drying treatment is 8000 Pa to 11000 Pa, and / or, the treatment time of the first drying treatment is 1 min to 5 min; and / or the air pressure of the second drying is 1.333×10 -1 Pa to 1.333×10 -6 Pa, and the treatment time is 1 min to 20 min. The secondary drying process in this embodiment can make the carrier material solution form a uniform thin film, improve the conductivity and optical display effect, and at the same time avoid over-sintering of the carrier material solution to form an overly dense thin film, which affects the carrier transport efficiency and reduces the performance of the optoelectronic device. It can be understood that the environment of the first drying treatment can be any value in the range formed by any one or any two of the values 8000 Pa, 8500 Pa, 9000 Pa, 9500 Pa, 10000 Pa, 10500 Pa, 11000 Pa, and the first drying treatment time can be any value in the range formed by any one or any two of the values 1 min, 2 min, 3 min, 4 min, 5 min. The second drying time can be 1.333×10 -1 Pa, 1.333×10-e Pa, 1.333×10 -e Pa, 1.333×10 -4 Pa, 1.333×10 -5 Pa, 1.333×10 -6 The second drying time can be any value or a range formed by any two values ​​in Pa. The second drying time can be any value or a range formed by any two values ​​in 1min, 2min, 3min, 4min, 5min, 6min, 7min, 8min, 9min, 10min, 11min, 12min, 13min, 14min, 15min, 16min, 17min, 18min, 19min, 20min.

[0073] Furthermore, the carrier material solution includes a carrier functional material and a first solvent. The first solvent and the set solvent independently include any one of an alcohol solvent, a ketone solvent and an alcohol ether solvent or a combination thereof. When the carrier functional layer is in the atmosphere of the set solvent, it can further avoid the reaction between the carrier functional layer and the set solvent to cause the degradation of the carrier functional layer, thereby increasing the recombination rate of hole carriers and electron carriers and avoiding the leakage of electrons to the hole transport layer.

[0074] Furthermore, the first solvent is the same as the set solvent.

[0075] Further, the work function ratio of the composite film to the carrier functional layer placed before the set solvent atmosphere can be 1.4, 1.41, 1.42, 1.43, 1.44, 1.45, 1.46, 1.47, 1.48, 1.49, 1.5, 1.51, 1.52, 1.53, 1.55, 1.55, 1.56, 1.57, 1.58, 1.59, 1.6, or any two of the values. Further, the carrier functional material includes any one of a hole injection material, a hole transport material, and an electron transport material, and the first solvent includes an alcohol compound and / or a ketone compound. It can be understood that in the OLED device, the carrier functional material also includes the material of the electron injection layer. At this time, the method can prepare a composite electron injection layer, and the composite electron injection layer can also increase the hole carrier and electron carrier load rate to prevent electrons from leaking into the hole transport layer.

[0076] Further, the carrier functional material is a hole injection material, including one or a combination of poly(3,4-ethylenedioxythiophene), poly(3,4-ethylenedioxythiophene)-polystyrenesulfonic acid, 2,3,5,6-tetrafluoro-7,7',8,8'-tetracyanoquinodimethane, 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene, polycarbonate copper, transition metal oxides, and transition metal chalcogenides; and / or, the first solvent includes one or a combination of isopropanol, diethylene glycol, N-methylpyrrolidone, and diethylene glycol butyl ether. At this time, the composite film is a composite hole injection layer.

[0077] Further, the carrier functional material is an electron transport material, including poly(9,9-dioctylfluorene-CO-N-(4-butylphenyl)diphenylamine), 3-hexyl-substituted polythiophene, poly(9-vinylcarbazole), poly[bis(4-phenyl)(4-butylphenyl)amine], poly(N,N'-bis(4-butylphenyl)-N,N'-diphenyl-1,4-phenylenediamine-CO-9,9-dioctylfluorene), 4,4',4”-tris(carbazol-9-yl)triphenylamine, 4,4'-di(9-carbazolyl)biphenyl, N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine, N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine, poly(3,4-ethylenedioxythiophene):poly(styrenesulfonic acid), doped or undoped graphene, C 60 , NiO, MoO 3 , WO 3 , V 2 O 5 , CrO 3 , CuO or one or a combination of p-type gallium nitride.

[0078] Alcohol solvents include one or a combination of isopropanol, diethylene glycol, 1,2-ethylene glycol, and 2-phenoxyethanol; and / or

[0079] Ketone solvents include one or a combination of N-methylpyrrolidone, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and acetophenone;

[0080] Alcohol ether solvents include one or a combination of diethylene glycol monobutyl ether, diethylene glycol butyl ether, diethylene glycol monomethyl ether, and triethylene glycol monomethyl ether.

[0081] Further, the carrier functional material is an electron transport material, including one or a combination of doped or undoped inorganic materials and organic materials. Undoped inorganic materials include ZnO, TiO 2 , SnO 2 , Al 2 O 3, GaO, Ga 2 O 3 、ZrO 2 、NiO, ZnS, ZnSe, CdS, InP, GaP, BaTiO 3 、Cs 2 CO 3 、Rb 2 CO 3 、RbBr, LiF, LiF / Yb, MgP, MgF 2 One or a combination thereof. The doped inorganic material includes an undoped inorganic material and a doping element, and the doping element includes one or a combination of Mg, Ca, Li, Ga, Al, Co, Mn, Zr, W, Ti, Yb. The organic material is selected from one or a combination of polymethyl methacrylate, polyvinyl butyral, polycarbonate, and polyurethane. The alcohol compounds include methanol, ethanol, 1,2-ethylene glycol, 2-phenoxyethanol; and / or, the thickness of the protective layer is 0.5 nm to 2 nm. The smaller the thickness of the protective layer itself, the more it can avoid hindering the transport of electrons or holes. Therefore, when the thickness of the protective layer is 0.5 nm to 2 nm, the carrier transport efficiency of the composite film is relatively high. It can be understood that the thickness of the protection includes any value among 0.5 nm, 1 nm, 1.5 nm, 2 nm or the range formed by any two values.

[0082] Correspondingly, the present application also provides a composite film 10, which is prepared by the preparation method of the composite film as above. Since the composite film of the present application includes a carrier functional layer 11 and a protective layer 12, and the surface of the carrier functional layer 11 is charged. Therefore, the work function of the composite film 10 is relatively large and the polaron state density between the composite film 10 and other film layers is relatively large; at the same time, the protective layer 11 plays a role in preventing the carrier functional layer 12 from deteriorating when being treated by plasma. Therefore, the composite film 10 has a high recombination rate of hole carriers and electron carriers and can effectively avoid electron leakage to the hole transport layer. The composite film is at least one of a composite hole injection layer, a composite hole transport layer, and a composite electron transport layer.

[0083] Correspondingly, the present application also provides a preparation method of an optoelectronic device, and the method includes:

[0084] Providing a bottom electrode;

[0085] Preparing a functional layer on the bottom electrode;

[0086] Preparing a top electrode on the functional layer;

[0087] The functional layer is prepared by the preparation method of the composite film in the above embodiment. The preparation method of the composite film in the optoelectronic device of the present application is specifically embodied in the above embodiment and will not be elaborated here.

[0088] In the method for manufacturing an optoelectronic device according to an embodiment of the present application, when manufacturing at least one of a hole transport layer, a hole injection layer, and an electron transport layer, the method for manufacturing the composite film in the above embodiment is adopted. Therefore, both the work function of the composite film and the polaron state density between the composite film and the remaining film layers are improved, which can avoid electron leakage into the hole transport layer, thereby improving the external quantum efficiency. In addition, the protective layer of the composite film prevents the composite film from being deteriorated by plasma during plasma treatment. In summary, the external quantum efficiency and the device service life of the light-emitting device according to the embodiment of the present application are high. It can be understood that the method for manufacturing an optoelectronic device of the present application can be used to produce both positive and negative optoelectronic devices. The substrate may include a cathode or an anode. The process for manufacturing an anode on the substrate is as follows: Place ITO glass or IZO glass in a glass dish filled with an ethanol solution, and wipe the ITO glass or IZO glass clean with a cotton swab. Then, perform ultrasonic treatment with acetone, deionized water, and ethanol in sequence, with each ultrasonic treatment lasting for 10 minutes; dry the ITO glass or IZO glass with a nitrogen gun, place the ITO glass or IZO glass sheet in an oxygen plasma for cleaning, with the cleaning time being 5 minutes to 15 minutes; put the ITO glass or IZO glass into a vacuum dust-free oven for baking, with the baking temperature being 230°C to 250°C and the baking time being 30 minutes to form an anode. Among them, the cleaning time can be any value from 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes, 10 minutes, 11 minutes, 12 minutes, 13 minutes, 14 minutes, 15 minutes or any range formed by any two values. The baking temperature can be any value from 230°C, 235°C, 240°C, 245°C, 250°C or any range formed by any two values.

[0089] The process for manufacturing a cathode layer and a capping layer includes: depositing a cathode and a capping layer under a pressure of 5 Pa to 10 Pa, where the deposition rate of the cathode is 22 Å / s (angstroms per second) and the deposition rate of the capping layer is 1.52 Å / s to form an optoelectronic device. Among them, the deposition pressure can be any value from 5 Pa, 6 Pa, 7 Pa, 8 Pa, 9 Pa, 10 Pa or any range formed by any two values.

[0090] Correspondingly, please refer to Figure 4 and Figure 5 An embodiment of the present application further provides an optoelectronic device, which is manufactured by using the method for manufacturing an optoelectronic device as described above; the optoelectronic device includes a bottom electrode, a functional layer, and a top electrode stacked in sequence. The bottom electrode and the top electrode can be an anode or a cathode, and the functional layer can include any one or more of an electron functional layer and a hole functional layer, and can also include a light-emitting layer.

[0091] The bottom electrode and the top electrode respectively include a metal oxide electrode or a composite electrode with a metal disposed between doped or undoped transparent metal oxides. The materials of the metal oxide electrodes include one or more of ITO, FTO, ATO, AZO, GZO, IZO, MZO, and AMO. The composite electrodes include AZO / Ag / AZO, AZO / Al / AZO, ITO / Ag / ITO, ITO / Al / ITO, ZnO / Ag / ZnO, ZnO / Al / ZnO, ZnS / Ag / ZnS, ZnS / Al / ZnS, TiO 2 / Ag / TiO 2 and TiO 2 / Al / TiO 2 one or more of them.

[0092] The functional layer includes a stacked carrier functional layer and a protective layer. One side of the carrier functional layer close to the protective layer and / or the surface of the protective layer carries charges;

[0093] The protective layer is close to the top electrode.

[0094] For example, when an anode 100, a hole injection layer 200, a hole transport layer 300, a light-emitting layer 400, an electron transport layer 500, and a cathode 600 are sequentially stacked in a optoelectronic device, the optoelectronic device is a p-type optoelectronic device. Please continue to refer to Figure 5 When a cathode 60, an electron transport layer 500, a light-emitting layer 400, a hole transport layer 300, a hole injection layer 200, and an anode 100 are sequentially stacked, the optoelectronic device is an n-type optoelectronic device. Since at least one of the hole injection layer 200, the hole transport layer 300, and the electron transport layer 500 in the optoelectronic device of the embodiment of the present application is the composite thin film 10 in the above embodiment, the work function of the composite thin film 10 and the polaron state density between the composite thin film 10 and the remaining film layers are both improved, which can avoid electron leakage to the hole transport layer 500, thereby improving the external quantum efficiency. And the protective layer 11 of the composite thin film 10 prevents the composite thin film from deteriorating caused by plasma during plasma treatment.

[0095] In summary, the external quantum efficiency and the device service life of the light-emitting device in the embodiment of the present application are high. It can be understood that the manufacturing method of the optoelectronic device of the present application can be used to produce p-type and n-type optoelectronic devices. It can be understood that the hole injection layer 200, the hole transport layer 300, and the electron transport layer 500 can respectively have a hole injection layer protection 210, a hole transport layer protection layer 310, and an electron transport layer protection layer 510.

[0096] Correspondingly, an embodiment of the present application further provides a display device. The display device includes the optoelectronic device as described above, so it has a high external quantum efficiency and a long device service life. 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 laptop computer, a digital camera, a digital video camera, a smart wearable device, a smart weighing electronic scale, a vehicle-mounted display, a television, or an e-book reader. Among them, the smart wearable device can be, for example, a smart bracelet, a smart watch, a virtual reality (VR) helmet, etc.

[0097] 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.

[0098] Embodiment 1

[0099] This embodiment provides a preparation method for a positive-type optoelectronic device. The preparation method is as follows:

[0100] Step 1, prepare the anode. Place the ITO glass in a glass dish filled with an ethanol solution, wipe the ITO glass clean with a cotton swab, and perform ultrasonic treatment successively with acetone, deionized water, and ethanol, with each ultrasonic treatment time being 10 min; dry the ITO glass with a nitrogen gun, place the ITO glass in an oxygen plasma for cleaning, with the cleaning time being 10 min; put the ITO glass into a vacuum dust-free oven for baking, with the baking temperature being 240 °C and the baking time being 30 min to form a substrate.

[0101] Step 2, prepare the composite hole injection layer. In the air, spin-coat or ink-jet print a hole injection layer solution on the substrate, with the spin-coating speed being 2300 r / min and the spin-coating time being 35 s to form a hole injection layer liquid film; perform two drying treatments on the hole injection layer liquid film. The first drying environment is a pressure of 10000 Pa and the drying time is 5 min. The second drying environment is a high vacuum pressure and the drying time is 2 min to form a hole injection layer; transfer the hole injection layer to a hole injection layer solvent at a temperature of 230 °C for 30 min. Among them, the hole injection layer solution is a mixed solution of isopropanol and 3,4-ethylenedioxythiophene. The hole injection layer solvent is isopropanol to form a hole injection layer protection layer on the hole injection layer; then transfer the hole injection layer to a vacuum plasma device for plasma treatment. The gas for plasma treatment is sulfur tetrafluoride, the gas flow rate is 60 sccm / s, the power is 50 W, and the time is 100 s to obtain a composite hole injection layer;

[0102] Step 3, prepare the composite hole transport layer. Spin-coat or ink-jet print the hole transport layer solution on the above-mentioned composite hole injection layer. The spin-coating speed is 2000 r / min and the spin-coating time is 40 s to form a hole transport layer liquid film; perform two drying treatments on the hole transport layer liquid film. The first drying environment is at a pressure of 10000 Pa and the drying time is 5 min. The second drying environment is at a high vacuum pressure and the drying time is 2 min; to form a hole transport layer; transfer the hole transport layer to a hole transport layer solvent at a temperature of 200 °C for 30 min. Among them, the hole transport layer solution is a mixed solution of poly(9-vinylcarbazole) and isopropanol. The hole transport layer solvent is isopropanol to form a hole transport layer protection layer on the hole transport layer; then transfer the hole transport layer to a vacuum plasma device for plasma treatment. The gas for plasma treatment is sulfur tetrafluoride, the gas flow rate is 60 sccm / s, the power is 80 W, and the time is 100 s to obtain the composite hole transport layer;

[0103] Step 4, prepare the light-emitting layer. Spin-coat or ink-jet print the light-emitting layer solution on the above-mentioned composite hole transport layer. The spin-coating speed is 1600 r / min and the spin-coating time is 30 s to form a light-emitting layer liquid film; perform two drying treatments on the light-emitting layer liquid film. The first liquid film drying environment is 3 Pa and the drying time is 5 min. The second drying environment is at a high vacuum and the drying time is 2 min to form a light-emitting layer dry film; place the light-emitting layer dry film in a nitrogen atmosphere for annealing treatment. The annealing temperature is 100 °C and the annealing time is 5 min;

[0104] Step 5, prepare the composite electron transport layer. Spin-coat or ink-jet print the electron transport layer solution on the above-mentioned light-emitting layer. The spin-coating speed is 3400 r / min and the spin-coating time is 40 s to form an electron transport layer liquid film; perform two drying treatments on the electron transport layer liquid film. The first drying environment is at a pressure of 10000 Pa and the drying time is 2 min. The second drying environment is at a high vacuum pressure and the drying time is 15 min to form an electron transport layer; transfer the electron transport layer to an electron transport layer solvent at a temperature of 100 °C for 15 min. The electron transport layer solution is zinc oxide and ethanol, and the electron transport layer solvent is ethanol to form an electron transport layer protection layer; then transfer it to a vacuum plasma device for treatment; the gas during plasma treatment is sulfur tetrafluoride, the gas flow is 60 sccm / s, the power is 80 W, and the time is 100 s to obtain the composite electron transport layer;

[0105] Step 6, prepare the cathode layer and the capping layer. Transfer the above-mentioned composite electron transport layer to a high-vacuum evaporation device or a sputtering device, and deposit the cathode and the adsorption layer under a pressure of 8 Pa. Among them, the cathode deposition rate is 22 / sec (angstroms / second), and the capping layer deposition rate is 1.52 / sec to form the cathode and the capping layer;

[0106] Step 7, Encapsulation. Encapsulate the above optoelectronic device using an encapsulation adhesive and an encapsulation cover plate. Encapsulate the optoelectronic device with an ultraviolet curable resin (Pulse Puretone 20 - 001) and store it in an N2 environment.

[0107] Example 2

[0108] This example is basically the same as Example 1, except that this example is a preparation method for an inverted optoelectronic device, and the method is as follows:

[0109] Step a, Prepare the cathode layer. Provide a substrate, transfer the substrate to a high - vacuum evaporation device or a sputtering device, and deposit a cathode and an adsorption layer at a pressure of 8 Pa, where the cathode deposition rate is 22 / s to form a cathode;

[0110] Step b, Prepare the composite electron - transport layer. Spin - coat or ink - jet print an electron - transport layer solution on the above - mentioned cathode at a spin - coating speed of 3400 r / min for 40 s to form an electron - transport layer liquid film; perform two drying treatments on the electron - transport layer liquid film. The first drying environment is at a pressure of 10000 Pa for 2 min, and the second drying environment is at a high - vacuum pressure for 15 min to form an electron - transport layer; transfer the electron - transport layer to an electron - transport layer solvent at a temperature of 100 °C for 15 min. The electron - transport layer solution is zinc oxide and ethanol, and the electron - transport layer solvent is ethanol to form an electron - transport layer protection layer; then transfer it to a vacuum plasma device for treatment; the gas during plasma treatment is sulfur tetrafluoride, the gas flow is 60 sccm / s, the power is 80 W, and the time is 100 s to obtain a composite electron - transport layer;

[0111] Step c, Prepare the light - emitting layer. Spin - coat or ink - jet print a light - emitting layer solution on the above - mentioned composite electron - transport layer at a spin - coating speed of 1600 r / min for 30 s to form a light - emitting layer liquid film; perform two drying treatments on the light - emitting layer liquid film. The first liquid - film drying environment is at 3 Pa for 5 min, and the second drying environment is at high - vacuum for 2 min to form a light - emitting layer dry film; place the light - emitting layer dry film in a nitrogen atmosphere for annealing treatment, with an annealing temperature of 100 °C and an annealing time of 5 min;

[0112] Step d, preparing a composite hole transport layer. Spin-coat or inkjet-print a hole transport layer solution on the above-mentioned light-emitting layer at a spin-coating speed of 2000 r / min for 40 s to form a hole transport layer liquid film; perform two drying treatments on the hole transport layer liquid film. The first drying environment is at a pressure of 10000 Pa for 5 min, and the second drying environment is at a high vacuum pressure for 2 min; to form a hole transport layer; transfer the hole transport layer to a hole transport layer solvent at a temperature of 200 °C for 30 min. Among them, the hole transport layer solution is a mixed solution of poly(9-vinylcarbazole) and isopropanol. The hole transport layer solvent is isopropanol to form a hole transport layer protective layer on the hole transport layer; then transfer the hole transport layer to a vacuum plasma device for plasma treatment. The gas for plasma treatment is sulfur tetrafluoride, the gas flow rate is 60 sccm / s, the power is 80 W, and the time is 100 s to obtain a composite hole transport layer;

[0113] Step e, preparing a composite hole injection layer. Spin-coat or inkjet-print a hole injection layer solution on the above-mentioned composite hole transport layer in air at a spin-coating speed of 2300 r / min for 35 s to form a hole injection layer liquid film; perform two drying treatments on the hole injection layer liquid film. The first drying environment is at a pressure of 10000 Pa for 5 min, and the second drying environment is at a high vacuum pressure for 2 min to form a hole injection layer; transfer the hole injection layer to a hole injection layer solvent at a temperature of 230 °C for 30 min. Among them, the hole injection layer solution is a mixed solution of isopropanol and 3,4-ethylenedioxythiophene. The hole injection layer solvent is isopropanol to form a hole injection layer protective layer on the hole injection layer; then transfer the hole injection layer to a vacuum plasma device for plasma treatment. The gas for plasma treatment is sulfur tetrafluoride, the gas flow rate is 60 sccm / s, the power is 50 W, and the time is 100 s to obtain a composite hole injection layer;

[0114] Step f, preparing an anode. Place the ITO glass on the composite hole injection layer, and in a glass dish containing an ethanol solution, wipe the ITO glass clean with a cotton swab, and perform ultrasonic treatment with acetone, deionized water, and ethanol in sequence, with each ultrasonic treatment time being 10 min; dry the ITO glass with a nitrogen gun, place the ITO glass in an oxygen plasma for cleaning, with the cleaning time being 10 min; place the ITO glass in a vacuum dust-free oven for baking, with the baking temperature being 240 °C and the baking time being 30 min to form an anode. At the same time, deposit an adsorption layer under a pressure of 8 Pa, and the deposition rate of the capping layer is 1.52 / s;

[0115] Step g, encapsulation. The same as step 7 of Example 1.

[0116] Comparative Example 1

[0117] This embodiment is basically the same as Embodiment 1, except that in Step 2, the step of transferring the hole injection layer to a hole injection layer solvent at a temperature of 200°C for annealing treatment is omitted, and the step of transferring the hole injection layer into a vacuum plasma device for plasma treatment is omitted;

[0118] In Step 3, the step of transferring the hole transport layer to a hole transport layer solvent at a temperature of 200°C for annealing treatment is omitted, and the step of transferring the hole transport layer into a vacuum plasma device for plasma treatment is omitted; in Step 5, the step of transferring the electron transport layer to an electron transport layer solvent at a temperature of 200°C for annealing treatment is omitted, and the step of transferring the electron transport layer into a vacuum plasma device for plasma treatment is omitted.

[0119] Comparative Example 2

[0120] This embodiment is basically the same as Embodiment 2, except that this embodiment is basically the same as Embodiment 1, except that in Step b, the step of transferring the electron transport layer to an electron transport layer solvent at a temperature of 200°C for annealing treatment is omitted, and the step of transferring the electron transport layer into a vacuum plasma device for plasma treatment is omitted;

[0121] In Step d, the step of transferring the hole transport layer to a hole transport layer solvent at a temperature of 200°C for annealing treatment is omitted, and the step of transferring the hole transport layer into a vacuum plasma device for plasma treatment is omitted; in Step e, the step of transferring the electron injection layer to an electron injection layer solvent at a temperature of 200°C for annealing treatment is omitted, and the step of transferring the electron injection layer into a vacuum plasma device for plasma treatment is omitted.

[0122] Comparative Example 3

[0123] This embodiment is basically the same as Embodiment 1, except that in Step 2, the step of transferring the hole injection layer to a hole injection layer solvent at a temperature of 200°C is omitted, in Step 3, the step of transferring the hole transport layer to a hole transport layer solvent at a temperature of 200°C is omitted, and in Step 5, the step of transferring the electron transport layer to an electron transport layer solvent at a temperature of 200°C is omitted.

[0124] Comparative Example 4

[0125] This embodiment is basically the same as Embodiment 2, except that in Step b, the step of transferring the electron injection layer to an electron injection layer solvent at a temperature of 200°C is omitted, in Step d, the step of transferring the hole transport layer to a hole transport layer solvent at a temperature of 200°C is omitted, and in Step e, the step of transferring the hole injection layer to a hole injection layer solvent at a temperature of 200°C is omitted.

[0126] Comparative Example 5

[0127] This embodiment is basically the same as Embodiment 1, except that in Step 2, the step of transferring the hole injection layer into a vacuum plasma device for plasma treatment is omitted;

[0128] In Step 3, the step of transferring the hole transport layer into a vacuum plasma device for plasma treatment is omitted; in Step 5, the step of transferring the electron transport layer into a vacuum plasma device for plasma treatment is omitted.

[0129] Comparative Example 6

[0130] This embodiment is basically the same as Embodiment 2, except that in Step b, the step of transferring the electron transport layer into a vacuum plasma device for plasma treatment is omitted;

[0131] In Step d, the step of transferring the hole transport layer into a vacuum plasma device for plasma treatment is omitted; in Step e, the step of transferring the electron injection layer into a vacuum plasma device for plasma treatment is omitted.

[0132] The optoelectronic devices of Embodiments 1-2 and the optoelectronic devices of Comparative Examples 1-6 after encapsulation are subjected to heat treatment at a heating temperature of 145 °C and a heating time of 30 min; then, an EQE optical test instrument is used to perform an external quantum efficiency EQE test on the optoelectronic devices of Embodiments 1-2 and the optoelectronic devices of Comparative Examples 1-6. The test conditions are as follows: performed at room temperature, with an air humidity of 30% - 60%, and the following are obtained Figure 5 And a service life test instrument is used to test the JVL data of the optoelectronic devices under a constant current drive condition of 63.7 mA / cm2, and to determine the time and electrical performance for the optoelectronic devices to decrease from the initial brightness (100%) to 95%, and the following are obtained Figure 6 and Table 1.

[0133] The EQE calculation formula is:

[0134] where ηe is the optical output coupling efficiency, ηγ is the ratio of the number of recombined carriers to the number of injected carriers, x is the ratio of the number of excitons generating photons to the total number of excitons, KR is the radiation process rate, and KNR is the non-radiation process rate.

[0135] Table 1:

[0136]

[0137]

[0138] Please refer to Table 1, Figure 5 and Figure 6, according to Embodiment 1, Embodiment 2, and Comparative Examples 1 to 6, it can be seen that when only the thin film serving as the carrier functional layer of the optoelectronic device is placed in the atmosphere of a set solvent for treatment or only the thin film serving as the carrier functional layer of the optoelectronic device is subjected to plasma treatment, the lifespan and external quantum efficiency of the obtained optoelectronic device are slightly greater than those of the optoelectronic device without any treatment; however, when the carrier functional layer in the optoelectronic device is subjected to plasma treatment and annealing treatment, the external quantum efficiency and service life of the optoelectronic device are greatly improved. It can be seen that by forming a protective layer in cooperation with plasma treatment, the external quantum efficiency of the optoelectronic device can be further improved.

[0139] In summary, the optoelectronic device of the embodiment of the present application can improve the external quantum efficiency and the service life of the device.

[0140] The composite thin film and its preparation method, the optoelectronic device and its preparation method, and the display device provided by the embodiments of the present application have been introduced in detail above. Specific examples are used in this article to elaborate on the principle and implementation manner of the present application. The description of the above embodiments is only used to help understand the method and its core idea of the present application; at the same time, for those skilled in the art, according to the idea of the present application, there will be changes in the specific implementation manner and application scope. In summary, the content of this specification should not be construed as a limitation to the present application.

[0141] Obviously, the embodiments described above are only a part of the embodiments of the present application, rather than all the embodiments. The preferred embodiments of the present application are shown in the drawings, but do not limit the patent scope of the present application. The present application can be implemented in many different forms. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure content of the present application more thorough and comprehensive. Although the present application has been described in detail with reference to the foregoing embodiments, for those skilled in the art, they can still modify the technical solutions recorded in the foregoing specific embodiments, or perform equivalent replacements on some of the technical features. Any equivalent structure directly or indirectly using the content of the specification and drawings of the present application in other related technical fields is similarly within the scope of the patent protection of the present application.

[0142] Although the embodiments of the present application have been shown and described, those of ordinary skill in the art can understand that various changes, modifications, combinations, substitutions, and variations can be made to these embodiments without departing from the principle and purpose of the present application. The scope of the present invention is defined by the claims and their equivalents.

Claims

1. A method for preparing a composite film, characterized in that: The method comprises: providing a carrier material solution including a carrier functional material and a first solvent; Depositing the carrier material solution to form a carrier functional layer; placing the carrier functional layer in an atmosphere of a set solvent to form a protective layer on the carrier functional layer; The carrier functional layer is subjected to plasma treatment to make the surface of the carrier functional layer and / or the protective layer carry electric charges, thereby obtaining a composite film.

2. The method for preparing a composite film according to claim 1, characterized in that: The plasma treatment comprises providing plasma gas to the surface of the protective layer and / or the carrier functional layer; The gas flow rate of the plasma gas is 30 sccm / s to 80 sccm / s; and / or, The processing power of the plasma treatment is 60W to 100W; and / or, The plasma treatment time is 60s to 150s; and / or, The plasma gas includes at least one of oxygen, an inert gas, sulfur tetrafluoride, and carbon tetrafluoride; the inert gas includes at least one of nitrogen, helium, argon, and neon; and / or The work function ratio of the composite film to the carrier functional layer before being placed in a set solvent atmosphere is (1.4-1.6):

1.

3. The method for preparing a composite film according to claim 1, characterized in that: The step of placing the carrier functional layer in a set solvent atmosphere includes heating the carrier functional layer at a temperature of 150° C. to 250° C. and / or a heating time of 10 min to 60 min.

4. The method for preparing a composite film according to claim 1, characterized in that: The step of depositing the carrier material solution to form a carrier functional layer comprises: Forming the carrier material solution into a liquid film and performing a first drying process; Performing a second drying process on the liquid film after the first drying process to obtain a carrier functional layer; The air pressure of the first drying process is 8000Pa to 11000Pa, and / or the treatment time of the first drying process is 1min to 5min; and / or, The second drying pressure is 1.333×10 -1 Pa~1.333×10 -6 Pa, processing time is 1min~20min.

5. The method for preparing a composite film according to claim 1, characterized in that: The carrier functional material includes any one of a hole functional material and an electron functional material; and / or The first solvent and the set solvent independently include any one of an alcohol solvent, a ketone solvent and an alcohol ether solvent or a combination thereof; and / or, The first solvent is the same as the set solvent.

6. The method for preparing a composite film according to claim 5, characterized in that: The carrier functional material is a hole functional material, the hole functional material includes a hole injection material and / or a hole transport material, the hole injection material includes one or a combination of poly(3,4-ethylenedioxythiophene), poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid, 2,3,5,6-tetrafluoro-7,7',8,8'-tetracyanoquinone-dimethane, 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene, polyester copper carbonate, transition metal oxides, and transition metal sulfur compounds; and / or, The hole transport material includes poly, 3-hexyl substituted polythiophene, poly (9-vinyl carbazole), poly [bis (4-phenyl) (4-butylphenyl) amine], poly (N, N'-di (4-butylphenyl) -N, N'-diphenyl-1,4-phenylenediamine-CO-9,9-dioctylfluorene), 4,4',4"-tri (carbazole-9-yl) triphenylamine, 4,4'-di (9-carbazole) biphenyl, N, N'-diphenyl-N, N'-di (3-methylphenyl) -1,1'-biphenyl-4,4'-diamine, N, N'-diphenyl-N, N'- (1-naphthyl) -1,1'-biphenyl-4,4'-diamine, poly (3,4-ethylenedioxythiophene): poly (styrene sulfonic acid), doped or undoped graphene, C 60 , NiO, MoO3, WO3, V2O3, CrO3, CuO or P-type gallium nitride or a combination thereof; and / or, The alcohol solvent includes one of isopropyl alcohol, diethylene glycol, 1,2-ethylene glycol, 2-phenoxyethanol or a combination thereof; and / or, The ketone solvent includes one or a combination of N-methylpyrrolidone, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and acetophenone; The alcohol ether solvent includes one of diethylene glycol monobutyl ether, diethylene glycol butyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether or a combination thereof.

7. The method for preparing a composite film according to claim 5, characterized in that: The carrier functional material is an electronic functional material, and the electronic functional material includes one or a combination of doped or non-doped inorganic materials and organic materials; The non-doped inorganic material includes one or a combination of ZnO, TiO2, SnO2, Al2O3, GaO, Ga2O3, ZrO2, NiO, ZnS, ZnSe, CdS, InP, GaP, BaTiO3, Cs2CO3, Rb2CO3, RbBr, LiF, LiF / Yb, MgP, and MgF2; The doped inorganic material includes a non-doped inorganic material and a doping element, and the doping element includes one or a combination of Mg, Ca, Li, Ga, Al, Co, Mn, Zr, W, Ti, and Yb; The organic material is selected from one of polymethyl methacrylate, polyvinyl butyral, polycarbonate, polyurethane or a combination thereof; and / or, The alcohol compound includes methanol, ethanol, 1,2-ethylene glycol, 2-phenoxyethanol; and / or, The thickness of the protective layer is 0.5 nm to 2 nm.

8. A composite film, characterized in that The composite film is prepared by the method for preparing the composite film according to any one of claims 1 to 7.

9. A photoelectric device, characterized in that: It comprises a bottom electrode, a functional layer and a top electrode stacked in sequence, wherein the functional layer comprises a composite film prepared by the preparation method according to any one of claims 1 to 7, or comprises the composite film according to claim 8.

10. The optoelectronic device according to claim 9, characterized in that: The bottom electrode and the top electrode respectively include a metal oxide electrode or a composite electrode in which a metal is arranged between doped or undoped transparent metal oxides. The material of the metal oxide electrode includes one or more of ITO, FTO, ATO, AZO, GZO, IZO, MZO and AMO. The composite electrode includes one or more of AZO / Ag / AZO, AZO / Al / AZO, ITO / Ag / ITO, ITO / Al / ITO, ZnO / Ag / ZnO, ZnO / Al / ZnO, ZnS / Ag / ZnS, ZnS / Al / ZnS, TiO2 / Ag / TiO2 and TiO2 / Al / TiO2.

11. The optoelectronic device according to claim 9, characterized in that: The functional layer comprises a stacked carrier functional layer and a protective layer, wherein the side of the carrier functional layer close to the protective layer and / or the surface of the protective layer are charged; The protection layer is close to the top electrode.

12. A display device, characterized in that: The display device comprises the optoelectronic device according to any one of claims 9 to 11.

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