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

Abstract

The invention discloses a thin film and a preparation method thereof, a photoelectric device and a display device. The preparation method of the thin film comprises the steps that a first film layer is provided, and the first film layer comprises oxide particles; performing atmosphere treatment on the first film layer to obtain a thin film; wherein gas used in the atmosphere treatment comprises hydrogen sulfide gas, the volume fraction of the hydrogen sulfide gas is smaller than or equal to 10%, and through the atmosphere treatment of the low-concentration hydrogen sulfide gas, defects in the oxide particles in the first film layer can be passivated, and the vulcanization degree can be accurately regulated and controlled; therefore, the material stability and the performance stability of the thin film can be improved, and meanwhile, the thin film can have relatively good carrier mobility.

Description

Technical Field

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

[0002] Carrier functional layers, such as electron transport layers, hole transport layers, hole injection layers and other film layers, can be applied to various optoelectronic devices such as OPV, OFET, perovskite solar cells, organic electrophotoelectric devices (OLED), quantum dot electrophotoelectric devices (QLED), etc., to improve the transport and injection of carriers and improve the optoelectronic performance of optoelectronic devices. Taking OLED and QLED, which are optoelectronic devices with luminescence, as an example, the charge functional layers included in them will directly affect the carrier mobility, the amount of carrier injection, etc., thereby affecting the composite luminescence, and affecting the luminescence performance and life of the optoelectronic device.

[0003] However, the charge functional layer is affected by its material, such as surface defects of oxide particles, which affects the stability and life of the charge functional layer, thereby limiting the performance of the optoelectronic device to a certain extent. Summary of the invention

[0004] In view of this, the present application provides a thin film and a preparation method thereof, an optoelectronic device and a display device, aiming to improve the material stability of the thin film.

[0005] An embodiment of the present application is implemented by providing a method for preparing a thin film, comprising: providing a first film layer, wherein the first film layer comprises oxide particles; performing atmosphere treatment on the first film layer to obtain a thin film; wherein the working gas used in the atmosphere treatment comprises hydrogen sulfide gas, and the volume percentage of the hydrogen sulfide gas in the working gas is less than or equal to 10%.

[0006] Optionally, in some embodiments of the present application, the working gas consists of the hydrogen sulfide gas and an inert gas; and / or the volume fraction of the hydrogen sulfide gas is 2 to 5%; and / or the temperature of the atmosphere treatment is less than or equal to 200°C; and / or the time of the atmosphere treatment is 30 to 120 minutes.

[0007] Optionally, in some embodiments of the present application, the temperature of the atmosphere treatment is 150-200° C.; and / or the time of the atmosphere treatment is 30-90 min; and / or the inert gas includes one or more of helium, neon, argon, and nitrogen.

[0008] Optionally, in some embodiments of the present application, the oxide particles may include doped or undoped oxide particles, and the undoped oxide particles are selected from one or more of zinc oxide, titanium dioxide, tin dioxide, gallium oxide, nickel oxide, molybdenum trioxide, tungsten trioxide, vanadium pentoxide, chromium trioxide, and copper oxide; the doped oxide particles include the undoped oxide particles and doping elements, and the doping elements are selected from one or more of Mg, Ca, Li, Ga, Al, Co, Mn, In, Zr, W, Ti, and Y; and / or the average particle size of the oxide particles is 2 to 15 nm; and / or the thickness of the first film layer is 10 to 70 nm.

[0009] Optionally, in some embodiments of the present application, the performing atmosphere treatment on the first film layer includes: placing the first film layer in a first atmosphere and performing the atmosphere treatment, wherein the gas composition of the first atmosphere includes the hydrogen sulfide gas.

[0010] Optionally, in some embodiments of the present application, providing the first film layer includes: providing a solution of the oxide particles; providing a substrate, placing the solution of the oxide particles on the substrate, and performing a drying process to form the first film layer.

[0011] Correspondingly, an embodiment of the present application also provides a film, which is prepared by the above-mentioned film preparation method.

[0012] Optionally, in some embodiments of the present application, the mass percentage of sulfur element in the film is less than or equal to 5%.

[0013] Correspondingly, an embodiment of the present application also provides a photoelectric device, comprising a first electrode and a second electrode arranged opposite to each other; and a carrier functional layer arranged between the first electrode and the second electrode; wherein the carrier functional layer comprises a thin film prepared by the above-mentioned thin film preparation method, or the carrier functional layer comprises the above-mentioned thin film.

[0014] Optionally, in some embodiments of the present application, the carrier functional layer includes one or more of an electron functional layer and a hole functional layer; and / or the first electrode and the second electrode are independently selected from metal electrodes, carbon electrodes, doped or undoped metal oxide particle electrodes and composite electrodes; wherein the material of the metal electrode is selected from at least one of Al, Ag, Cu, Mo, Au, Ba, Ca and Mg; the material of the carbon electrode is selected from at least one of graphite, carbon nanotubes, graphene and carbon fiber; the material of the doped or undoped metal oxide particle electrode is selected from at least one of ITO, FTO, ATO, AZO, GZO, IZO, MZO and AMO; the material of the composite electrode is selected from 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 and ZnS / Al / ZnS; and / or the optoelectronic device further comprises a light-emitting layer, the material of the light-emitting layer is selected from one or more of organic light-emitting materials or quantum dots; the organic light-emitting material is selected from at least one of diaromatic anthracene derivatives, distilbene aromatic derivatives, pyrene derivatives or fluorene derivatives, TBPe fluorescent materials emitting blue light, TTPA fluorescent materials emitting green light, TBRb fluorescent materials emitting orange light and DBP fluorescent materials emitting red light;The quantum dots are selected from at least one of single structure quantum dots, core-shell structure quantum dots and perovskite semiconductor materials, the single structure quantum dots are selected from at least one of II-VI group compounds, IV-VI group compounds, III-V group compounds and I-III-VI group compounds, the II-VI group compounds are selected from CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHg The IV-VI group compound is selected from at least one of SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, SnPbSeTe, SnPbSTe, and the III - Group V compounds are selected from the group consisting of GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, In NP, InNAs, InNSb, InPAs, InPSb, GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InA At least one of lNSb, InAlPAs and InAlPSb, the I-III-VI group compound is selected from at least one of CuInS, CuInSe and AgInS; the core of the quantum dots of the core-shell structure is selected from any one of the above-mentioned single structure quantum dots, and the shell material of the quantum dots of the core-shell structure is selected from at least one of CdS, CdTe, CdSeTe, CdZnSe, CdZnS, CdSeS, ZnSe, ZnSeS and ZnS; the perovskite semiconductor material is selected from doped or undoped inorganic perovskite semiconductors, or organic-inorganic hybrid perovskite semiconductors; the general structural formula of the inorganic perovskite semiconductor is AMX3, wherein A is Cs; +ion, M is a divalent metal cation selected from Pb 2+ Sn 2+ , Cu 2+ 、Ni 2+ 、Cd 2+ Cr 2+ , Mn 2+ 、Co 2+ , Fe 2+ ,Ge 2+ , Yb 2+ 、Eu 2+ At least one of, X is a halogen anion selected from Cl - Br - ,I - At least one of the following; the general structural formula of the organic-inorganic hybrid perovskite semiconductor is BMX3, wherein B is an organic amine cation selected from CH3(CH2) n-2 NH3 + or [NH3(CH2) n NH3] 2+ , where n≥2, M is a divalent metal cation selected from Pb 2+ Sn 2+ , Cu 2+ 、Ni 2+ 、Cd 2+ Cr 2+ , Mn 2+ 、Co 2+ , Fe 2+ ,Ge 2+ , Yb 2+ 、Eu 2+ At least one of, X is a halogen anion selected from Cl - Br - ,I - At least one of .

[0015] Correspondingly, an embodiment of the present application further provides a display device, including a thin film produced by the above-mentioned thin film preparation method, or including the above-mentioned optoelectronic device.

[0016] The method for preparing a thin film of the present application comprises: providing a first film layer, wherein the first film layer comprises oxide particles; performing an atmosphere treatment on the first film layer to obtain a thin film; wherein the gas used in the atmosphere treatment comprises hydrogen sulfide gas, and the volume fraction of the hydrogen sulfide gas is less than or equal to 10%. By performing an atmosphere treatment of a low-concentration hydrogen sulfide gas on the first film layer comprising oxide particles, defects in the oxide particles in the first film layer can be passivated, thereby improving the stability of the thin film, and also enabling the thin film to have a better carrier mobility, thereby improving the luminous performance and life of the light-emitting device. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings required for use in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present application. For those skilled in the art, other drawings can be obtained based on these drawings without creative work.

[0018] Figure 1 A schematic flow chart of an embodiment of a method for preparing a thin film is provided for the present application;

[0019] Figure 2 A schematic structural diagram of an embodiment of a photoelectric device provided in the present application.

[0020] Reference numerals:

[0021] Optoelectronic device 100 ; first electrode 10 ; second electrode 20 ; carrier functional layer 30 , electron functional layer 31 , hole functional layer 32 ; light emitting layer 40 . DETAILED DESCRIPTION

[0022] The following will be combined with the drawings in the embodiments of the present application to clearly and completely describe the technical solutions in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, not all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative work belong to the scope of protection of the present application. In addition, it should be understood that the specific implementation methods described herein are only used to illustrate and explain the present application, and are not used to limit the present application. In the present application, unless otherwise specified, the directional words such as "upper" and "lower" used are specifically the directions of the drawings in the accompanying drawings. In addition, in the description of the present application, the term "including" means "including but not limited to". Various embodiments of the present invention 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 simplicity, and should not be understood as a rigid limitation on the scope of the present invention; therefore, it should be considered that the range description has specifically disclosed all possible sub-ranges and single values ​​within the range. For example, description of a range from 1 to 6 should be considered to have 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., as well as single numbers within the stated range, such as 1, 2, 3, 4, 5, and 6, regardless of the range. In addition, whenever a numerical range is indicated herein, it is meant to include any cited numeral (fractional or integral) within the stated range.

[0023] In this application, "and / or" describes the association relationship of associated objects, indicating that there may be three relationships. For example, A and / or B can mean: A exists alone, A and B exist at the same time, and B exists alone. A and B can be singular or plural.

[0024] In the present application, "at least one" means one or more, and "plurality" means two or more. "At least one", "at least one of the following" or similar expressions refer to any combination of these items, including any combination of single items or plural items. For example, "at least one of a, b, or c", or "at least one of a, b, and c" can all mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, c can be single or multiple, respectively.

[0025] See also Figure 1 , Figure 1 The present application provides a flow chart of an embodiment of a method for preparing a thin film, wherein the method comprises the following steps:

[0026] Step S11: providing a first film layer, wherein the first film layer comprises oxide particles;

[0027] Step S12: performing atmosphere treatment on the first film layer to obtain a thin film;

[0028] Wherein, the gas used in the atmosphere treatment includes hydrogen sulfide gas, and the volume fraction of the hydrogen sulfide gas is less than or equal to 10%.

[0029] In this embodiment, by subjecting the first film layer including oxide particles to an atmosphere treatment including hydrogen sulfide gas, defects in the oxide particles in the first film layer can be passivated, such as filling oxygen vacancies, passivating dangling bonds, etc., and the degree of sulfidation can be precisely controlled so that part of the oxide particles form sulfides, which can improve the material stability and performance stability of the film and increase the service life of the film. Moreover, the atmosphere treatment with a relatively low concentration of hydrogen sulfide gas can sulfidate part of the oxide particles to form sulfides, that is, the obtained film contains part of the sulfides, so that the material stability of the film can be improved while also having good carrier mobility.

[0030] When the oxide particles have electron transport and injection properties, the film preparation method of the present application can also adjust the energy level to block the injection of excess electrons, thereby improving the electron transport stability of the film while making the film have better electron mobility.

[0031] The material stability specifically includes the chemical stability and crystal stability of the material.

[0032] Furthermore, when the film is used as a charge functional layer in a photoelectric device, it can increase the electron injection barrier, reduce the electron injection amount, and avoid the injection of excessive electrons, thereby improving the carrier balance of the photoelectric device and improving the service life and reliability of the photoelectric device.

[0033] In the step S11:

[0034] In one embodiment, the oxide particles may include doped or undoped oxide particles, and the undoped oxide particles are selected from one or more of zinc oxide (ZnO), titanium dioxide (TiO2), tin dioxide (SnO2), gallium oxide (Ga2O3), zirconium dioxide (ZrO2), nickel oxide (NiO), molybdenum trioxide (MoO3), tungsten trioxide (WO3), vanadium pentoxide (V2O5), chromium trioxide (CrO3), and copper oxide (CuO); the doped oxide particles include the undoped oxide particles and doping elements, and the doping elements are selected from one or more of Mg, Ca, Li, Ga, Al, Co, Mn, In, Zr, W, Ti, and Y.

[0035] In one embodiment, the oxide particles may include one or more of doped or undoped zinc oxide (ZnO), titanium dioxide (TiO2), tin dioxide (SnO2), gallium oxide (Ga2O3), and zirconium dioxide (ZrO2). In this embodiment, the atmosphere treatment can passivate the surface defects of the oxide particles and accurately control the amount of sulfide introduced, thereby improving the chemical stability of the film and enabling the film to have better electron mobility.

[0036] In another embodiment, the oxide particles may include one or more of doped or undoped nickel oxide (NiO), molybdenum trioxide (MoO3), tungsten trioxide (WO3), vanadium pentoxide (V2O5), chromium trioxide (CrO3), and copper oxide (CuO). In this embodiment, the atmosphere treatment can passivate the surface defects of the oxide particles and introduce a small amount of sulfide, which can improve the chemical stability of the film with little effect on the energy level and carrier injection.

[0037] In this embodiment, there are some defects on the surface of the oxide particles, such as oxygen vacancies, cation dangling bonds and the like. The defects can be passivated by the atmosphere treatment, and part of the oxides in the oxide particles are sulfurized to form sulfur oxides. Forming a certain ratio on the surface of the oxide particles can greatly improve the material stability and charge transfer stability of the film.

[0038] Among them, dangling bonds are chemical bonds. Generally, because the crystal lattice suddenly terminates at the surface, each atom in the outermost layer of the surface will have an unpaired electron, that is, an unsaturated bond, which is called a dangling bond. Cationic dangling bonds refer to some unpaired cations on the surface of oxides. For example, there are some uncoordinated Zn on the surface of zinc oxide particles. 2+ , Zn 2+ That is the cationic dangling bond.

[0039] In a specific embodiment, the oxide particles are selected from doped or undoped zinc oxide particles. Zinc oxide is a semiconductor material with a direct wide bandgap and has very excellent electron migration performance. In this specific embodiment, defects such as oxygen vacancies on the surface of the zinc oxide particles can be filled, so that the zinc oxide on the surface of the zinc oxide particles is reacted to form zinc oxide sulfur, and a shell of zinc oxide sulfur is formed on the surface of the zinc oxide particles. In addition to reacting with the zinc oxide to form zinc sulfide, hydrogen sulfide can also fill a small amount of Zn defects (such as Zn dangling bonds) on the surface of zinc oxide by coordination adsorption.

[0040] Among them, zinc oxide reacts to form zinc sulfide, and the reaction formula is as follows:

[0041] ZnO+H2S→ZnS+H2O.

[0042] It can be understood that the working principle of passivating dangling bonds can be as follows:

[0043] Zn dangling bond + H2S = H2S → Zn.

[0044] In one embodiment, the average particle size of the oxide particles is 2 to 15 nm. Specifically, the average particle size of the oxide particles may be 2 to 13 nm, 3 to 13 nm, 3 to 10 nm, 4 to 8 nm, 4 to 7 nm, 5 to 7 nm, 5 to 6 nm, etc. The shape of the oxide particles may be one or more of spherical, flake, rod-shaped, polyhedral, etc. Specifically, the polyhedron may be a tetrahedron, a hexagon, an octahedron, etc.

[0045] In one embodiment, the average particle size of the oxide particles is 2-5 nm, specifically 2-4 nm, 3-4 nm, 2-3 nm, 4-5 nm, etc.

[0046] In one embodiment, the thickness of the first film layer is 10-70 nm, specifically 10-60 nm, 20-60 nm, 20-50 nm, 30-50 nm, 30-40 nm, etc. In one embodiment, the thickness of the first film layer may be the same as the thickness of the thin film obtained in the end. That is, during the process of subjecting the first film layer to the atmosphere treatment, the thickness of the first film layer may not change.

[0047] In one embodiment, the first film layer may be a solid film. Compared with a liquid film or a liquid-state film, the solid film is solid, contains no or a trace amount of solvent, and the main material is the film layer of the oxide particles.

[0048] It is understandable that the first film layer can be prepared by conventional techniques in the art, such as chemical methods or physical methods. Among them, the chemical method includes chemical vapor deposition, continuous ion layer adsorption and reaction, first electrode oxidation, electrolytic deposition, and coprecipitation. The physical method includes physical coating and solution method, among which the physical coating method includes: thermal evaporation coating, electron beam evaporation coating, magnetron sputtering, multi-arc ion coating, physical vapor deposition, atomic layer deposition, pulsed laser deposition, etc.; the solution method can be spin coating, printing, inkjet printing, blade coating, printing, dip-coating, immersion, spraying, roll coating, casting, slit coating, and strip coating, etc.

[0049] In a specific embodiment, the first film layer is prepared by a solution method, that is, a solution containing the oxide particles is formed into a liquid film, and then a solid first film layer whose main material is the oxide particles is formed by drying to remove the solvent.

[0050] In one embodiment, the providing of the first film layer in step S11 includes:

[0051] Step S111: providing the oxide particles and a first solvent, and mixing them to obtain an oxide particle solution;

[0052] Step S112: providing a substrate, placing the oxide particle solution on the substrate, and performing a drying process to form the first film layer.

[0053] In one embodiment, the first solvent may include an alcohol solvent, specifically one or more of ethanol, butanol, triethylene glycol, tetraethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 3-methoxybutanol, and the like.

[0054] The solution of the oxide particles may be a dispersion of the oxide particles or a colloidal solution of the oxide particles. The concentration of the oxide particle solution may be 10 to 80 mg / mL, specifically 10 to 70 mg / mL, 20 to 70 mg / mL, 20 to 60 mg / mL, 30 to 60 mg / mL, 30 to 50 mg / mL, 40 to 50 mg / mL, etc. This concentration may evenly disperse the zinc oxide particles and evenly spread them on the substrate.

[0055] The drying process may be vacuum drying or heat drying to remove the first solvent in the oxide particle solution as much as possible. The vacuum drying pressure may be 0.01-10 Pa and the time may be 5-30 min. The heat drying temperature may be 40-150° C. and the time may be 5-60 min.

[0056] Specifically, the pressure of the vacuum drying can be 0.01-0.1Pa, 0.1-1Pa, 1-5Pa, 5-10Pa, etc., and the time can be 5-10min, 10-20min, 20-30min, etc. Specifically, the temperature of the heating drying can be 40-12°C, 60-120°C, 60-100°C, 80-100°C, 100-150°C, etc., and the time can be 5-10min, 10-20min, 20-30min, 30-40min, 40-50min, 50-60min, etc.

[0057] In step S12:

[0058] In one embodiment, the gas used in the atmosphere treatment is composed of the hydrogen sulfide and an inert gas, and the inert gas includes one or more of argon, nitrogen, helium, neon, etc. It can be understood that the inert gas will not react with the material in the first film layer and will not react with the oxide particles.

[0059] In a specific embodiment, the inert gas is selected from one or more of argon and nitrogen. The density difference between the inert gas and the hydrogen sulfide gas is small, and a uniformly mixed gas can be formed to perform the atmosphere treatment.

[0060] In one embodiment, in the gas used in the atmosphere treatment, the volume fraction (volume percentage) of the hydrogen sulfide gas is less than or equal to 10%, specifically 1-10%, 2-10%, 1-5%, 2-5%, 5-10%, etc. In a specific embodiment, the volume percentage of the hydrogen sulfide gas is 2-5%, specifically 2-4.5%, 2.5-4.5%, 2.5-4.0%, 3.0-4.0%, 3.0-3.5%, etc. The volume percentage of the hydrogen sulfide gas can provide an atmosphere treatment environment with a lower concentration of hydrogen sulfide gas, can passivate the defects in the oxide particles in the first film layer, and perform a lower degree of sulfurization on the first film layer, specifically, about 0.5-1% of the oxide is sulfurized, so that the material stability of the film can be improved while the film can also have a better electron mobility. Specifically, the sulfur content (mass percentage) in the final film can be less than or equal to 5%, such as 0.1-4.51%, 0.24-4.51%, 0.24-2.40%, 0.85-2.40%, 0.85-1.50%, 1.10-1.50%, 0.95-1.25%, etc.

[0061] In one embodiment, the temperature of the atmosphere treatment is less than or equal to 200°C, and can be specifically 20-30°C, 30-50°C, 50-100°C, 100-150°C, 150-200°C, etc. Carrying out the atmosphere treatment at the temperature can cause the hydrogen sulfide gas to react with the oxide particles, fill the surface defects of the oxide particles, and form zinc oxide ZnOS on the surface of the oxide particles. And the temperature can also avoid the high temperature causing thermal damage to the first film layer and the optoelectronic device containing the first film layer, and the excessive degree of sulfurization reaction, so that the carrier mobility of the obtained film is significantly reduced, the energy level is significantly deepened, and the band gap is significantly enlarged, affecting the carrier transport performance of the film and further application in optoelectronic devices. In a specific embodiment, the temperature of the atmosphere treatment is 150-200°C.

[0062] In the above embodiment, a lower concentration of hydrogen sulfide gas is used for atmosphere treatment at a lower temperature. Hydrogen sulfide will preferentially sulfidize the oxide molecules with high reaction activity and poor chemical stability (such as oxygen vacancies, dangling bonds, etc.) on the surface of the oxide particles. After these sites are converted into sulfides, the chemical stability of the oxide particles can be greatly improved, thereby extending the material service life of the oxide particles.

[0063] In one embodiment, the atmosphere treatment time is 30 to 120 minutes, specifically 30 to 90 minutes, 50 to 90 minutes, 50 to 70 minutes, 90 to 120 minutes, 30 to 50 minutes, etc. Within the time range, a suitable degree of vulcanization can be provided, the material stability of the film can be improved, and the mobility can be reduced to a certain extent.

[0064] In one implementation, the performing atmosphere treatment on the first film layer includes: placing the first film layer in a first atmosphere to perform the atmosphere treatment, wherein the gas composition of the first atmosphere includes hydrogen sulfide gas.

[0065] In one embodiment, the preparation method further comprises: providing a first atmosphere. Specifically, providing the first atmosphere can be achieved by using a sealable container.

[0066] In another embodiment, the atmosphere treatment of the first film layer includes: placing the first film layer in the first airflow, wherein the gas composition of the first airflow includes the hydrogen sulfide gas. Specifically, the composition of the gas in the first airflow can refer to the relevant content of the atmosphere treatment described above, which will not be repeated here.

[0067] In this embodiment, by placing in the first airflow for treatment, the flow of the first airflow can take away other products generated in the sulfurization reaction, such as water molecules, etc., thereby preventing the generated other products from having a negative impact on the film.

[0068] In one embodiment, after the first film layer is subjected to the atmosphere treatment, a drying treatment may also be included.

[0069] In one embodiment, the oxide particles may be connected with ligands. Specifically, the ligands may be selected from one or more of hydroxyl ligands, amine ligands, thiol ligands, carboxyl ligands, and pyridine ligands.

[0070] Specifically, the amino ligand may include one or more of ethylamine (1-aminoethane), 1-octylamine (1-aminooctane), 1,2-propylenediamine, 1,4-butylenediamine, 9-octadeceneamine, aniline, and p-phenylenediamine. The sulfhydryl ligand may include one or more of ethanethiol, octanethiol, mercaptoethylamine, and 3-mercapto-1-propylamine. The carboxyl ligand may include one or more of propionic acid, butyric acid, (Z)-9-octadecene acid, and thioglycolic acid. The pyridine ligand may include one or more of pyridine and picoline. It is understandable that the ligand may be a single ligand or a mixed ligand comprising two or more.

[0071] The present application provides a film, which is prepared by the above-mentioned film preparation method.

[0072] The thin film includes an oxide and a sulfide, wherein the cationic metal in the sulfide is the same as that in the oxide.

[0073] The thin film prepared by the thin film preparation method provided in the present application greatly reduces the surface defects of the oxide particles, thereby improving the material stability and life of the thin film, and adjusting the energy level, carrier mobility, etc. of the thin film.

[0074] In one embodiment, the content (mass percentage) of sulfur element in the film is less than or equal to 5%, specifically 0.1-4.51%, 0.24-4.51%, 0.24-2.40%, 0.85-2.40%, 0.85-1.50%, 1.10-1.50%, 0.95-1.25%, etc.

[0075] The present application provides a photoelectric device, including the film provided by the present application.

[0076] See also Figure 2 , Figure 2 This is a schematic diagram of the structure of an embodiment of a photoelectric device provided by the present application. The present application also provides a photoelectric device 100, comprising a first electrode 10, a second electrode 20 and a carrier functional layer 30, wherein the first electrode 10 and the second electrode 20 are arranged opposite to each other, and the carrier functional layer 30 is arranged between the first electrode 10 and the second electrode 20. The carrier functional layer 30 comprises the above-mentioned thin film or comprises a thin film prepared by the above-mentioned thin film preparation method.

[0077] In this embodiment, the carrier functional layer 30 includes the thin film provided in the present application or a thin film prepared by the thin film preparation method provided in the present application, which greatly reduces the defects of the oxide particles in the thin film, improves the stability and life of the carrier functional layer 30 of the thin film, and improves the electron injection barrier of the thin film to a certain extent, thereby reducing the electron injection amount and electron mobility to a certain extent, avoiding the problem of a lower life of the optoelectronic device 100 due to excessive electron injection, improving the carrier balance in the optoelectronic device, and improving the life of the carrier functional layer 30.

[0078] In addition, although a certain proportion of zinc oxysulfide is formed in the film, the working voltage of the optoelectronic device 100 is slightly increased, but the material stability and carrier transport stability of the carrier functional layer 30 can be greatly improved, thereby improving the performance stability and extending the working life of the optoelectronic device 100. When the optoelectronic device 100 is a light-emitting device, the light-emitting stability of the light-emitting device can be improved, so that the light-emitting device can maintain consistent light-emitting performance when it is powered on for multiple times, and the recombination efficiency of the light-emitting device can be improved, thereby improving the light-emitting performance of the light-emitting device, such as the light-emitting efficiency.

[0079] Furthermore, the optoelectronic device 100 includes a light-emitting layer 40 , and the light-emitting layer 40 is disposed between the first electrode 10 and the second electrode 20 .

[0080] In one embodiment, the carrier functional layer 30 includes an electronic functional layer 31 , and the electronic functional layer 31 is disposed between the second electrode 20 and the light emitting layer 40 .

[0081] In one embodiment, the carrier functional layer 30 includes a hole functional layer 32 , and the hole functional layer 32 is disposed between the first electrode 10 and the light emitting layer 40 .

[0082] It can be understood that when the carrier functional layer 30 is a single-layer structure, the carrier functional layer 30 can be the above-mentioned thin film or a thin film prepared by the above-mentioned thin film preparation method. When the carrier functional layer 30 includes two or more film layers, one or more layers of the carrier functional layer 30 are the above-mentioned thin films or a thin film prepared by the above-mentioned thin film preparation method.

[0083] The first electrode 10 and the second electrode 20 form a pair of electrodes. When the first electrode 10 is an anode, the second electrode 20 is a cathode; when the first electrode 10 is a cathode, the second electrode 20 is an anode.

[0084] In a specific embodiment, the electronic functional layer 31 includes an electron transport layer and / or an electron injection layer, and the electron injection layer is arranged close to the cathode. The electron transport layer and / or the electron injection layer can be the above-mentioned thin film or a thin film prepared by the above-mentioned thin film preparation method.

[0085] In a specific embodiment, the hole functional layer 32 may include a hole injection layer and / or a hole transport layer. When the hole functional layer 32 includes a hole injection layer and a hole transport layer, the hole injection layer is disposed close to the anode, and the hole transport layer is disposed close to the light emitting layer.

[0086] In one embodiment, the carrier functional layer 30 includes an electron transport layer, and the electron transport layer is the above-mentioned thin film or includes a thin film prepared by the above-mentioned thin film preparation method.

[0087] The material of the hole transport layer may include poly(9,9-dioctylfluorene-co-N-(4-butylphenyl)diphenylamine) (TFB), polyvinylcarbazole (PVK), poly(N,N'-bis(4-butylphenyl)-N,N'-bis(phenyl)benzidine) (poly-TPD), poly(9,9-dioctylfluorene-co-bis-N,N-phenyl-1,4-phenylenediamine) (PFB), 4,4',4"-tri(carbazole-9-yl)triphenylamine (TCATA), 4,4'-bis(9-carbazole)biphenyl (CBP), N,N'-diphenyl-N,N'-bis(3 -methylphenyl)-1,1'-biphenyl-4,4'-diamine (TPD), N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine (NPB), poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonic acid) (PEDOT:PSS), Spiro-NPB, Spiro-TPD, doped or undoped NiO, MoO3, WO3, V2O5, P-type gallium nitride, CrO3, CuO, MoS2, MoSe2, WS3, WSe3, CuS, CuSCN or more.

[0088] The material of the hole injection layer is a material with hole injection capability, and may include one or more of poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid (PEDOT:PSS), 2,3,5,6-tetrafluoro-7,7',8,8'-tetracyanoquinone-dimethane (F4-TCNQ), 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (HATCN), copper phthalocyanine (CuPc), transition metal oxide particles, and transition metal sulfur compounds; wherein the transition metal oxide particles include one or more of NiO, MoO2, WO3, and CuO; the metal sulfur compounds include one or more of MoS2, MoSe2, WS3, WSe3, and CuS.

[0089] In one embodiment, the material of the light-emitting layer 40 may be selected from one or more of organic light-emitting materials or quantum dot materials; the organic light-emitting material is selected from at least one of diaromatic anthracene derivatives, distilbene aromatic derivatives, pyrene derivatives or fluorene derivatives, TBPe fluorescent materials emitting blue light, TTPA fluorescent materials emitting green light, TBRb fluorescent materials emitting orange light, and DBP fluorescent materials emitting red light;

[0090] The quantum dot material is selected from at least one of a single structure quantum dot, a core-shell structure quantum dot and a perovskite semiconductor material. The single structure quantum dot is selected from at least one of a II-VI group compound, a IV-VI group compound, a III-V group compound and a I-III-VI group compound. The II-VI group compound is selected from CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, Cd At least one of HgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe and HgZnSTe; the IV-VI group compound is selected from at least one of SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, SnPbSeTe and SnPbSTe; the I Group II-V compounds are selected from the group consisting of GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, I nNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, In At least one of AlNSb, InAlPAs and InAlPSb, the I-III-VI group compound is selected from at least one of CuInS, CuInSe and AgInS; the core of the quantum dot with core-shell structure is selected from any one of the above-mentioned single structure quantum dots, and the shell material of the quantum dot with core-shell structure is selected from at least one of CdS, CdTe, CdSeTe, CdZnSe, CdZnS, CdSeS, ZnSe, ZnSeS and ZnS; the perovskite semiconductor material is selected from doped or undoped inorganic perovskite semiconductor, or organic-inorganic hybrid perovskite semiconductor; the general structural formula of the inorganic perovskite semiconductor is AMX3, wherein A is Cs +ion, M is a divalent metal cation selected from Pb 2+ Sn 2+ , Cu 2+ 、Ni 2+ 、Cd 2 + Cr 2+ , Mn 2+ 、Co 2+ , Fe 2+ ,Ge 2+ , Yb 2+ 、Eu 2+ At least one of, X is a halogen anion selected from Cl - Br - ,I - At least one of the following; the general structural formula of the organic-inorganic hybrid perovskite semiconductor is BMX3, wherein B is an organic amine cation selected from CH3(CH2) n-2 NH3 + or [NH3(CH2) n NH3] 2+ , where n≥2, M is a divalent metal cation selected from Pb 2+ Sn 2+ , Cu 2+ 、Ni 2+ 、Cd 2+ Cr 2+ , Mn 2+ 、Co 2+ , Fe 2+ ,Ge 2+ , Yb 2+ 、Eu 2+ At least one of, X is a halogen anion selected from Cl - Br - ,I - At least one of .

[0091] In a specific embodiment, the material of the light-emitting layer 40 is selected from the core-shell structured quantum dots.

[0092] In one embodiment, the quantum dot material is an oil-soluble quantum dot, specifically including binary phase, ternary phase, and quaternary phase quantum dots; wherein the binary phase quantum dots include CdS, CdSe, CdTe, InP, AgS, PbS, PbSe, HgS, etc., but are not limited thereto; the ternary phase quantum dots include Zn X Cd 1-X S, Cu X In 1-X S, Zn X Cd 1-X Se, Zn X Se 1-X S, ZnX Cd 1-X Te、PbSe X S 1-X The quaternary phase quantum dots include, but are not limited to, Zn X Cd 1-X S / ZnSe、Cu X In 1-X S / ZnS, Zn X Cd 1-X Se / ZnS, CuInSeS, Zn X Cd 1- X Te / ZnS、PbSe X S 1-X / ZnS etc. are not limited thereto.

[0093] In one embodiment, the quantum dot material is an oily quantum dot, and the oily quantum dot is coordinated and connected with a ligand, thereby increasing the solubility of the quantum dot material in an organic solvent, such as making the quantum dot material soluble in a solvent with a lower polarity. Wherein, the ligand includes at least one of an acid ligand, a thiol ligand, an amine ligand, a (oxygen) phosphine ligand, a phospholipid, a soft phosphine, and polyvinyl pyridine. As a specific embodiment, the acid ligand is at least one of deca-acid, undecylenic acid, tetradecanoic acid, oleic acid, and stearic acid; the thiol ligand is at least one of octadecyl mercaptan, dodecyl mercaptan, and octadecyl mercaptan; the amine ligand includes at least one of oleylamine, octadecylamine, and octaamine; the (oxygen) phosphine ligand is at least one of trioctylphosphine and trioctylphosphine oxide. Specifically, the quantum dot material can be configured into a quantum dot ink for use. In the quantum dot ink, the concentration of the quantum dots is 10 to 100 mg / mL, preferably 20 to 50 mg / mL. Within this concentration range, the solution processing performance of the quantum dots is good and the dispersibility is good.

[0094] It can be understood that when the material of the light-emitting layer 40 is an organic light-emitting material, the optoelectronic device 100 is an organic electrophotoelectric device. When the material of the light-emitting layer 40 is a quantum dot light-emitting material, the optoelectronic device 100 is a quantum dot electrophotoelectric device.

[0095] In one embodiment, the first electrode 10 and the second electrode 20 are independently selected from metal electrodes, carbon electrodes, doped or undoped metal oxide particle electrodes and composite electrodes; wherein the material of the metal electrode is selected from at least one of Al, Ag, Cu, Mo, Au, Ba, Ca and Mg; the material of the carbon electrode is selected from at least one of graphite, carbon nanotubes, graphene and carbon fiber; the material of the doped or undoped metal oxide particle electrode is selected from at least one of ITO, FTO, ATO, AZO, GZO, IZO, MZO and AMO; the material of the composite electrode is selected from at least one 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 and ZnS / Al / ZnS. Here, “ / ” represents a stacked structure. For example, the composite electrode AZO / Ag / AZO represents an electrode with a composite structure of three stacked layers consisting of an AZO layer, an Ag layer and an AZO layer.

[0096] It is understandable that, in addition to the above-mentioned functional layers, the optoelectronic device 100 may also be provided with some functional layers conventionally used in optoelectronic devices that help improve the performance of the optoelectronic device, such as an electron blocking layer, a hole blocking layer and / or an interface modification layer.

[0097] It can be understood that the material and thickness of each layer of the optoelectronic device 100 can be set and adjusted accordingly according to the light emitting requirements of the optoelectronic device 100 .

[0098] The optoelectronic device 100 further includes a substrate (not shown). The substrate may be a rigid substrate or a flexible substrate. The rigid substrate may be a ceramic material or various glass materials. The flexible substrate may be a substrate formed of materials such as polyimide film (PI) and its derivatives, polyethylene naphthalate (PEN), phosphoenolpyruvic acid (PEP) or diphenylene ether resin.

[0099] It can be understood that the photoelectric device 100 can be an upright photoelectric device or an inverted photoelectric device. When the photoelectric device 100 is an upright photoelectric device, the substrate is combined with the side of the anode away from the light-emitting layer 40. When the photoelectric device 100 is an inverted photoelectric device, the substrate is combined with the side of the cathode away from the light-emitting layer 40.

[0100] The present application also provides a method for preparing a photoelectric device. In one embodiment, the method for preparing a photoelectric device comprises the following steps:

[0101] Step S31: providing a prefabricated device, wherein the prefabricated device includes a first electrode;

[0102] Step S32: forming a carrier functional layer on the prefabricated device;

[0103] Step S33: forming a second electrode on the functional layer.

[0104] Wherein, the carrier functional layer may include one or more of an electron functional layer and a hole functional layer. The carrier functional layer includes a thin film prepared by the thin film preparation method provided in the present application, or a thin film provided in the present application. That is, one or more film layers in the electron functional layer and the hole functional layer can be prepared by the thin film preparation method provided in the present application.

[0105] In one embodiment, the first electrode is a cathode, and the second electrode is an anode. The photoelectric device prepared in this embodiment is an inverted photoelectric device.

[0106] Furthermore, in one embodiment, the carrier functional layer includes an electronic functional layer, and the electronic functional layer is prepared by the thin film preparation method provided in the present application.

[0107] In another embodiment, the first electrode is an anode, and the second electrode is a cathode. The upright photoelectric device prepared in this embodiment.

[0108] Furthermore, in one embodiment, the electronic functional layer is prepared by the thin film preparation method provided in the present application.

[0109] It can be understood that in this embodiment, the functional layer, anode, and cathode can refer to the relevant descriptions in the film preparation method and optoelectronic device provided in this application, and will not be repeated here.

[0110] It is understood that the method for preparing the optoelectronic device may further include a packaging step, and the packaging material used for packaging may be selected from at least one of UV glue, metal film, and glass glue. In a specific embodiment, the packaging material may be acrylic resin or epoxy resin. The packaging may be machine packaging or manual packaging, and may be sealed with UV curing glue. The concentrations of oxygen and water in the environment of the packaging step are both lower than 0.1ppm to ensure the stability of the optoelectronic device.

[0111] In the preparation method of the optoelectronic device provided in the present application, the preparation method of each film layer such as the first electrode, the hole functional layer, the light-emitting layer and the second electrode can be achieved by conventional techniques in the art, such as chemical methods or physical methods. Among them, the chemical method includes chemical vapor deposition, continuous ion layer adsorption and reaction method, first electrode oxidation method, electrolytic deposition method, and coprecipitation method. The physical method includes physical plating method and solution method, among which the physical plating method includes: thermal evaporation coating method, electron beam evaporation coating method, magnetron sputtering method, multi-arc ion plating method, physical vapor deposition method, atomic layer deposition method, pulsed laser deposition method, etc.; the solution method can be spin coating, printing method, inkjet printing method, scraping method, printing method, dip pulling method, immersion method, spraying method, roll coating method, casting method, slit coating method and strip coating method, etc.

[0112] The present application also relates to a display device, which includes the optoelectronic device provided in the present application. The display device can be any electronic product with a display function, including but not limited to smart phones, tablet computers, laptop computers, digital cameras, digital video cameras, smart wearable devices, smart weighing electronic scales, car displays, televisions or e-book readers, wherein the smart wearable device can be, for example, a smart bracelet, a smart watch, a virtual reality (VR) helmet, etc.

[0113] The present application is described in detail below through specific embodiments. The following embodiments are only partial embodiments of the present application and are not limitations of the present application.

[0114] Example 1

[0115] Provided is a film and a method for preparing the same, comprising the following steps:

[0116] Step 1: prepare a standard zinc oxide solution (the particle size of zinc oxide is in the range of 2 to 5 nm) with a concentration of 30 mg / mL.

[0117] Step 2: On a white glass substrate, use the zinc oxide solution to spin-coat a zinc oxide nanocrystalline film layer, and dry it at 80° C. for 10 minutes to obtain a first film layer with a thickness of 50 nm.

[0118] Step 3, placing the first film layer in a first atmosphere for atmosphere treatment to obtain a thin film; wherein the first atmosphere is composed of hydrogen sulfide gas and argon gas, the volume percentage of hydrogen sulfide gas is 2%, the volume percentage of argon gas is 98%, the temperature of the atmosphere treatment is 150°C, and the time is 30 minutes.

[0119] Example 2

[0120] This embodiment is basically the same as the embodiment 1, and the only difference is that in step 3, the volume percentage of hydrogen sulfide gas in the first atmosphere is 5%, and the rest is argon gas.

[0121] Example 3

[0122] This embodiment is basically the same as the embodiment 1, and the only difference is that in step 3, the volume percentage of hydrogen sulfide gas in the first atmosphere is 1%, and the rest is argon gas.

[0123] Example 4

[0124] This embodiment is basically the same as the embodiment 1, and the only difference is that in step 3, the volume percentage of hydrogen sulfide gas in the first atmosphere is 10%, and the rest is argon gas.

[0125] Example 5

[0126] This embodiment is basically the same as Embodiment 1, and the only difference is that in step 3, the temperature of the atmosphere treatment is 200°C.

[0127] Example 6

[0128] This embodiment is basically the same as Embodiment 1, except that in step 3, the temperature of the atmosphere treatment is 100°C.

[0129] Example 7

[0130] This embodiment is basically the same as Embodiment 1, and the only difference is that in step 3, the temperature of the atmosphere treatment is 250°C.

[0131] Example 8

[0132] This embodiment is basically the same as Embodiment 1, except that in step 3, the time of atmosphere treatment is 90 minutes.

[0133] Example 9

[0134] This embodiment is basically the same as Embodiment 1, except that in step 3, the time of atmosphere treatment is 10 minutes.

[0135] Example 10

[0136] This embodiment is basically the same as Embodiment 1, except that in step 3, the time of atmosphere treatment is 120 minutes.

[0137] Comparative Example 1

[0138] This comparative example is basically the same as Example 1, except that in step 2, after spin coating the zinc oxide nanocrystal film layer and drying, a thin film is obtained, and step 3 is not performed.

[0139] Comparative Example 2

[0140] This comparative example is basically the same as Example 1, except that in step 3, the volume percentage of hydrogen sulfide gas in the first atmosphere is 15%, and the rest is argon gas.

[0141] Test: Comparative Example 1 and Experimental Example 1 were subjected to X-ray photoelectron spectroscopy (XPS) characterization test, and the O1s peak of the test results was separated, where Ov (O-Vacancy) represents oxygen vacancy, O M (O-Metal) represents oxygen bonded to Zn (i.e. oxygen forming a Zn-O bond), O H represents hydroxyl oxygen.

[0142] The results are shown in Table 1 below.

[0143] Table 1

[0144]

[0145] It can be seen from Table 1 that, compared with Comparative Example 1, in the films of Examples 1-10, the number and proportion of Ov bonds are reduced, while the content of S element is increased, indicating that the film prepared by the film preparation method of the present application generates sulfur-containing zinc oxide and can reduce defects such as oxygen vacancy defects on the surface of nano zinc oxide. It can be seen from Comparative Example 1 and Example 1 that in O M The S content increased without a significant change in the number of bonds, indicating that the film prepared by the film preparation method of the present application will preferentially introduce the S element by filling defects such as oxygen vacancies, that is, hydrogen sulfide will first react with zinc oxide molecules with higher activity, and then react with zinc sulfide molecules without defects.

[0146] Device Example 1

[0147] The device embodiment provides a quantum dot light emitting diode and a method for preparing the same, which specifically includes the following steps.

[0148] Step 1: Pretreatment of ITO substrate (the thickness of the ITO layer is 120 nm): The ITO substrate is cleaned with a detergent to preliminarily remove stains on the surface, and then ultrasonically cleaned in deionized water, acetone, anhydrous ethanol, and deionized water for 20 minutes respectively to remove impurities on the surface, and finally blown dry with high-purity nitrogen.

[0149] Step 2: Spin-coat PEDOT:PSS (mass fraction of 2.8%, molar ratio of PEDOT to PSS of 1:1) on the ITO substrate at a rotation speed of 4000 rpm for 30 seconds, and then heat on a 150°C hot plate for 20 minutes to obtain a hole injection layer with a thickness of 80 nm.

[0150] Step 3: In an inert atmosphere, spin-coat TFB (concentration of 8 mg / mL) on the hole injection layer at a rotation speed of 3000 rpm for 30 s, and then heat on a heating plate at 120° C. for 20 min to obtain a hole transport layer with a thickness of 70 nm.

[0151] Step 4: Spin-coat CdSeS / ZnS green quantum dot solution (concentration of 30 mg / mL, with octanethiol ligands attached to the surface, and 0.2 mmol of ligands for every 1 mg of quantum dots) on the hole transport layer at a speed of 3000 rpm for 30 s, and then heat on a heating plate at 80°C for 5 min to obtain a light-emitting layer with a thickness of 70 nm.

[0152] Step 5: Prepare an electron transport layer on the light-emitting layer according to the thin film preparation method of Example 1, with a thickness of 50 nm.

[0153] Step 6: By thermal evaporation, the vacuum degree is not higher than 3×10 -4 Pa, Al was evaporated on the electronic functional layer at a rate of 1 angstrom / second for 200 seconds to obtain a second electrode with a thickness of 60 nm, and then packaged to obtain a quantum dot light-emitting diode.

[0154] Device Example 2

[0155] This device embodiment is basically the same as device embodiment 1, and the only difference is that in step 5, an electron transport layer is prepared on the light-emitting layer according to the thin film preparation method of embodiment 2.

[0156] Device Example 3

[0157] This device embodiment is basically the same as device embodiment 1, and the only difference is that in step 5, an electron transport layer is prepared on the light-emitting layer according to the thin film preparation method of embodiment 3.

[0158] Device Example 4

[0159] This device embodiment is basically the same as device embodiment 1, and the only difference is that in step 5, an electron transport layer is prepared on the light-emitting layer according to the thin film preparation method of embodiment 4.

[0160] Device Example 5

[0161] This device embodiment is basically the same as device embodiment 1, and the only difference is that in step 5, an electron transport layer is prepared on the light-emitting layer according to the thin film preparation method of embodiment 5.

[0162] Device Example 6

[0163] This device embodiment is basically the same as device embodiment 1, and the only difference is that in step 5, an electron transport layer is prepared on the light-emitting layer according to the thin film preparation method of embodiment 6.

[0164] Device Example 7

[0165] This device embodiment is basically the same as device embodiment 1, and the only difference is that in step 5, an electron transport layer is prepared on the light-emitting layer according to the thin film preparation method of embodiment 7.

[0166] Device Example 8

[0167] This device embodiment is basically the same as device embodiment 1, and the only difference is that in step 5, an electron transport layer is prepared on the light-emitting layer according to the thin film preparation method of embodiment 8.

[0168] Device Example 9

[0169] This device embodiment is basically the same as device embodiment 1, and the only difference is that in step 5, an electron transport layer is prepared on the light-emitting layer according to the thin film preparation method of embodiment 9.

[0170] Device Example 10

[0171] This device embodiment is basically the same as device embodiment 1, and the only difference is that in step 5, an electron transport layer is prepared on the light-emitting layer according to the thin film preparation method of embodiment 10.

[0172] Device Comparison Example 1

[0173] This device embodiment is basically the same as device embodiment 1, and the only difference is that in step 5, an electron transport layer is prepared on the light-emitting layer according to the thin film preparation method of comparative example 1.

[0174] Device Comparison Example 2

[0175] This device embodiment is basically the same as device embodiment 1, and the only difference is that in step 5, an electron transport layer is prepared on the light-emitting layer according to the thin film preparation method of comparative example 2.

[0176] test:

[0177] The quantum dot light-emitting diodes of device examples 1-10 and device comparative examples 1-2 were subjected to performance tests, and the test indicators and test methods were as follows:

[0178] Luminous efficiency CE (cd / A): measured using optical testing instruments;

[0179] Device lifespan T95_1knit (h): refers to the lifespan of the device when the brightness decays to 95% at a starting brightness of 1000 nits;

[0180] Device on / off efficiency fluctuation: The device operates at 1000 nits and the efficiency fluctuation when it is restarted after being turned off for 1 minute; and the turn-on voltage / V when it is restarted.

[0181] Table 2

[0182]

[0183] As can be seen from Table 2, compared with device comparative example 1, the start-up voltage of device embodiments 1-10 is slightly increased, indicating that the treatment of hydrogen sulfide gas slightly increases the voltage of the device, but can greatly improve the device life T95_1knit and luminous efficiency CE of the light-emitting device, and reduce the efficiency fluctuation when the device is turned on / off, that is, the light-emitting device of the present application includes a thin film prepared by the thin film preparation method provided by the present application, which can improve the luminous efficiency, life and stability of the light-emitting device. Device comparative example 1 shows that the thin film is treated with an atmosphere containing 15% volume percentage of hydrogen sulfide, and too many zinc oxide molecules are sulfided to form zinc sulfide, which will reduce the electron mobility and the recombination efficiency, thereby reducing the luminous efficiency of the light-emitting device, and the carrier imbalance will damage the functional layer in the light-emitting device and reduce the life of the light-emitting device.

[0184] The thin film and its preparation method, optoelectronic device and display device provided in the embodiments of the present application are introduced in detail above. Specific examples are used in this article to illustrate the principles and implementation methods of the present application. The description of the above embodiments is only used to help understand the method of the present application and its core idea; at the same time, for technical personnel in this field, according to the idea of ​​the present application, there will be changes in the specific implementation method and application scope. In summary, the content of this specification should not be understood as a limitation on the present application.

Claims

1. A method for preparing a thin film, characterized in that: include: Providing a first film layer, wherein the first film layer includes oxide particles; Performing atmosphere treatment on the first film layer to obtain the film; Wherein, the working gas used in the atmosphere treatment includes hydrogen sulfide gas, and the volume fraction of the hydrogen sulfide gas in the working gas is less than or equal to 10%.

2. The preparation method according to claim 1, characterized in that The working gas consists of the hydrogen sulfide gas and an inert gas; and / or The volume fraction of the hydrogen sulfide gas is 2-5%; and / or The temperature of the atmosphere treatment is less than or equal to 200° C.; and / or The time of the atmosphere treatment is 30 to 120 minutes.

3. The preparation method according to claim 2, characterized in that: The temperature of the atmosphere treatment is 150-200°C; and / or The time of the atmosphere treatment is 30 to 90 minutes; and / or The inert gas includes one or more of argon, nitrogen, helium and neon.

4. The preparation method according to claim 1, characterized in that: The oxide particles may include doped oxide particles or undoped oxide particles, wherein the undoped oxide particles are selected from one or more of zinc oxide, titanium dioxide, tin dioxide, gallium oxide, nickel oxide, molybdenum trioxide, tungsten trioxide, vanadium pentoxide, chromium trioxide, and copper oxide; the doped oxide particles include the undoped oxide particles and doping elements, wherein the doping elements are selected from one or more of Mg, Ca, Li, Ga, Al, Co, Mn, In, Zr, W, Ti, and Y; and / or The average particle size of the oxide particles is 2 to 15 nm; and / or The thickness of the first film layer is 10-70 nm.

5. The preparation method according to claim 1, characterized in that: The performing atmosphere treatment on the first film layer comprises: placing the first film layer in a first atmosphere and performing the atmosphere treatment, wherein the first atmosphere comprises the hydrogen sulfide gas.

6. The preparation method according to claim 1, characterized in that: The preparation method further includes providing a solution of the oxide particles and a substrate, placing the solution of the oxide particles on the substrate, and performing a drying process to form the first film layer.

7. A film, characterized in that: The film is prepared by the method for preparing the film according to any one of claims 1 to 6.

8. The film according to claim 7, characterized in that The mass fraction of sulfur element in the film is less than or equal to 5%.

9. A photoelectric device, characterized in that: include: A first electrode and a second electrode arranged opposite to each other; A carrier functional layer is arranged between the first electrode and the second electrode; wherein the carrier functional layer includes a thin film prepared by the method for preparing a thin film as described in any one of claims 1 to 6, or the carrier functional layer includes a thin film as described in any one of claims 7 to 8.

10. The optoelectronic device according to claim 9, characterized in that The carrier functional layer includes one or more of an electron functional layer and a hole functional layer; and / or The first electrode and the second electrode are independently selected from metal electrodes, carbon electrodes, doped or undoped metal oxide particle electrodes and composite electrodes; wherein the material of the metal electrode is selected from at least one of Al, Ag, Cu, Mo, Au, Ba, Ca and Mg; the material of the carbon electrode is selected from at least one of graphite, carbon nanotubes, graphene and carbon fiber; the material of the doped or undoped metal oxide particle electrode is selected from at least one of ITO, FTO, ATO, AZO, GZO, IZO, MZO and AMO; the material of the composite electrode is selected from at least one 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 and ZnS / Al / ZnS; and / or The optoelectronic device further comprises a light-emitting layer, wherein the material of the light-emitting layer is an organic light-emitting material or a quantum dot material; the organic light-emitting material is selected from at least one of diaromatic anthracene derivatives, distilbene aromatic derivatives, pyrene derivatives or fluorene derivatives, TBPe fluorescent materials emitting blue light, TTPA fluorescent materials emitting green light, TBRb fluorescent materials emitting orange light and DBP fluorescent materials emitting red light; the quantum dot material is selected from at least one of single-structure quantum dots, core-shell structure quantum dots and perovskite semiconductor materials, and the single-structure quantum dots are selected from at least one of II-VI compounds, IV-VI compounds, III-V compounds and I-III-VI compounds. species, the II-VI compound is selected from CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, At least one of HgZnSeTe and HgZnSTe, the IV-VI group compound is selected from at least one of SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, SnPbSeTe, SnPbSTe, the III-V group compound is selected from at least one of GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, GaNP, GaNAs, GaNS b, at least one of GaPAs, GaPSb, AlNPs, 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, and the I-III-VI group compound is at least one of CuInS, CuInSe and AgInS;The core of the quantum dots of the core-shell structure is selected from any one of the above-mentioned single-structure quantum dots, and the shell material of the quantum dots of the core-shell structure is selected from at least one of CdS, CdTe, CdSeTe, CdZnSe, CdZnS, CdSeS, ZnSe, ZnSeS and ZnS; the perovskite semiconductor material is selected from doped or undoped inorganic perovskite semiconductors, or organic-inorganic hybrid perovskite semiconductors; the general structural formula of the inorganic perovskite semiconductor is AMX3, wherein A is Cs; + ion, M is a divalent metal cation selected from Pb 2+ Sn 2+ , Cu 2+ 、Ni 2+ 、Cd 2+ Cr 2+ , Mn 2+ 、Co 2+ , Fe 2+ ,Ge 2+ , Yb 2+ 、Eu 2+ At least one of, X is a halogen anion selected from Cl - Br - ,I - At least one of the following; the general structural formula of the organic-inorganic hybrid perovskite semiconductor is BMX3, wherein B is an organic amine cation selected from CH3(CH2) n-2 NH3 + or [NH3(CH2) n NH3] 2+ , where n≥2, M is a divalent metal cation selected from Pb 2+ Sn 2+ , Cu 2+ 、Ni 2+ 、Cd 2+ Cr 2+ , Mn 2+ 、Co 2+ , Fe 2+ ,Ge 2+ , Yb 2+ 、Eu 2+ At least one of, X is a halogen anion selected from Cl - Br - ,I - At least one of .

11. A display device, characterized in that: The display device comprises a thin film prepared by the method according to any one of claims 1 to 6, or comprises a photoelectric device according to any one of claims 9 to 10.

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