CN117693274A

CN117693274A - Preparation method of film, photoelectric device and display device

Info

Publication number: CN117693274A
Application number: CN202211048267.9A
Authority: CN
Inventors: 敖资通; 张建新; 严怡然; 洪佳婷
Original assignee: TCL Technology Group Co Ltd
Current assignee: TCL Technology Group Co Ltd
Priority date: 2022-08-30
Filing date: 2022-08-30
Publication date: 2024-03-12

Abstract

The application discloses a preparation method of a film, a photoelectric device and a display device. The preparation method of the film provided by the application comprises the following steps: providing a substrate, and arranging a quantum dot solution on the substrate; treating the quantum dot solution arranged on the substrate by using a supercritical fluid to obtain an initial film; and carrying out infrared irradiation on the initial film to obtain the film. According to the preparation method of the film, the quantum dot solution arranged on the substrate is subjected to supercritical fluid treatment, so that quantum dots in the quantum dot solution are deposited, and then the solvent is removed through infrared irradiation treatment, so that the removal efficiency of the solvent in the quantum dot solution can be greatly improved, and the morphology and film formation uniformity of the film are further improved.

Description

Preparation method of film, photoelectric device and display device

Technical Field

The application relates to the technical field of display, in particular to a preparation method of a film, a photoelectric device and a display device.

Background

QLED (Quantum Dots Light-emission Diode) is an emerging display device, which has a structure similar to an OLED (Organic Light-emission Diode), and is typically a sandwich structure composed of a hole transport layer, an emission layer, and an electron transport layer. The luminescent material of the QLED adopts an inorganic quantum dot material with stable performance, and the unique quantum size effect, macroscopic quantum tunneling effect, quantum size effect and surface effect of the quantum dot lead the quantum dot to show excellent physical properties, especially the optical properties, such as adjustable spectrum, high luminous intensity, high color purity, long fluorescence service life, excitation of multicolor fluorescence by a single light source and the like, so that the QLED has excellent luminous performance and longer service life. In addition, the QLED has the characteristics of simple packaging process or no need of packaging and the like, is hopeful to become a next-generation flat panel display, and has wide development prospect.

However, there are still many problems in developing and mass producing QLEDs. In order to meet the requirements of industrial production, in the preparation process of a luminescent layer, a high-boiling point solvent is generally used for preparing a high-boiling point quantum dot solution, and the high-boiling point quantum dot solution is suitable for performing processes such as ink-jet printing or spin coating, but the high-boiling point solvent is slowly removed, and a coffee ring is often generated in a formed pixel grid, so that the film forming quality is poor, and the development and development progress of a QLED device are greatly restricted.

Disclosure of Invention

In view of the foregoing, the present application provides a method for preparing a thin film, an optoelectronic device and a display device, and aims to provide a novel method for preparing a quantum dot light-emitting layer thin film, which improves the film forming quality of the thin film.

The embodiment of the application is realized in such a way that the preparation method of the film comprises the following steps: providing a substrate and a quantum dot solution, and arranging the quantum dot solution on the substrate to obtain a quantum dot wet film; treating the quantum dot wet film by using a supercritical fluid to obtain an initial film; and carrying out infrared irradiation on the initial film to obtain the film.

Alternatively, in some embodiments of the present application, the infrared radiation has a wavelength of 900nm to 1100nm, preferably 1000 nm to 1100nm.

Alternatively, in some embodiments of the present application, the electron beam spot of the electron beam irradiation annealing treatment has an average power of 1×10 ³ ～1×10 ⁴ W/cm ² The energy density of the electron beam is 0.5-1J/cm ² Annealing time is 1×10 ^-2 ～1×10 ^-1 s。

Optionally, in some embodiments of the present application, an annealing treatment is further included after the infrared irradiation treatment is performed on the initial film and before the film is obtained.

Optionally, in some embodiments of the present application, the annealing process is an electron beam irradiation annealing process or a thermal annealing process.

Optionally, in some embodiments of the present application, the temperature of the thermal annealing treatment is 80 to 100 ℃ for 3 to 5 hours.

Alternatively, in some embodiments of the present application, the supercritical fluid has a critical temperature of 5 to 100 ℃, preferably 30 to 100 ℃.

Optionally, in some embodiments of the present application, the supercritical fluid is selected from at least one of supercritical carbon dioxide, supercritical ethylene, supercritical ethane, supercritical propane, and supercritical propylene.

Optionally, in some embodiments of the present application, the treating the quantum dot wet film with a supercritical fluid may include: and placing the substrate with the quantum dot wet film in an environment with critical temperature and/or critical pressure, spraying a supercritical fluid precursor into the environment to form a supercritical fluid, and processing the quantum dot wet film by the supercritical fluid to obtain the initial film.

Optionally, in some embodiments of the present application, the quantumThe dot solution comprises quantum dots and a solvent, wherein the quantum dots are selected from at least one of single-structure quantum dots, core-shell structure quantum dots, doped or undoped inorganic perovskite type quantum dots or organic-inorganic hybridization perovskite type quantum dots, the single-structure quantum dots are selected from at least one of II-VI compound, III-V compound, II-V compound, III-VI compound, IV-VI compound, I-III-VI compound, II-IV-VI compound and IV simple substance, the II-VI compound is selected from at least one of CdSe, cdS, cdTe, znSe, znS, cdTe, znTe, cdZnS, cdZnSe, cdZnTe, znSeS, znSeTe, znTeS, cdSeS, cdSeTe, cdTeS, cdZnSeS, cdZnSeTe and CdZnSTe, the III-V compound is selected from at least one of InP, inAs, gaP, gaAs, gaSb, alN, alP, inAsP, inNP, inNSb, gaAlNP and InAlNP, and the I-III-VI compound is selected from CuInS ₂ 、CuInSe ₂ AgInS ₂ At least one of (a) and (b); the core of the quantum dot with the core-shell structure is selected from any one of the quantum dots with the single structure, and the shell material of the quantum dot with the core-shell structure is selected from at least one of CdS, cdTe, cdSeTe, cdZnSe, cdZnS, cdSeS, znSe, znSeS and ZnS; the structural general formula of the inorganic perovskite type quantum dot is AMX ₃ 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 halogen anion selected from Cl ^- 、Br ^- 、I ^- At least one of (a) and (b); the organic-inorganic hybridization perovskite type quantum dot has a structural general formula of BMX ₃ Wherein B is an organic amine cation selected from CH ₃ (CH ₂ ) _n- ₂ NH ₃ ⁺ Or [ NH ] ₃ (CH ₂ ) _n NH ₃ ] ²⁺ Wherein n is greater than or equal to 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 halogen anion selected from Cl ^- 、Br ^- 、I ^- At least one of (a) and (b); the average particle size of the quantum dots is 2-20 nm; the solvent is at least one selected from alkane with eighteen carbon atoms, alkene with eighteen carbon atoms, and olefine acid with eighteen carbon atoms.

Correspondingly, the embodiment of the application also provides an optoelectronic device, which comprises a cathode, a light-emitting layer and an anode which are arranged in a stacked manner, wherein the light-emitting layer is prepared by the preparation method of the film.

Optionally, in some embodiments of the present application, the cathode and the anode are each independently selected from one or more of a metal electrode, a carbon electrode, a doped or undoped metal oxide electrode, and a composite electrode; wherein the material of the metal electrode is at least one selected from Al, ag, cu, mo, au, ba, ca and Mg; the material of the carbon electrode is at least one selected from graphite, carbon nano tube, graphene and carbon fiber; the material of the doped or undoped metal oxide electrode is at least one selected from ITO, FTO, ATO, AZO, GZO, IZO, MZO and AMO; the composite electrode is selected from AZO/Ag/AZO, AZO/Al/AZO, ITO/Ag/ITO, ITO/Al/ITO, znO/Ag/ZnO, znO/Al/ZnO, and TiO ₂ /Ag/TiO ₂ 、TiO ₂ /Al/TiO ₂ 、ZnS/Ag/ZnS、ZnS/Al/ZnS、TiO ₂ /Ag/TiO ₂ TiO ₂ /Al/TiO ₂ At least one of them.

Optionally, in some embodiments of the present application, the optoelectronic device further comprises an electron transport layer disposed between the cathode and the light emitting layer and a hole functional layer disposed between the light emitting layer and the anode; the material of the electron transport layer is one or more selected from inorganic nanocrystalline materials, doped inorganic nanocrystalline materials and organic materials; the inorganic nanocrystalline material is selected from one of zinc oxide, titanium dioxide, tin dioxide, aluminum oxide, calcium oxide, silicon dioxide, gallium oxide, zirconium oxide, nickel oxide and zirconium oxide One or more species; the doped inorganic nanocrystalline material is one or more of zinc oxide dopant, titanium dioxide dopant and tin dioxide dopant, wherein the doped inorganic nanocrystalline material is an inorganic material doped with other elements, and the doping elements are at least one of Mg, ca, li, ga, al, co, mn; the organic material is selected from one or two of polymethyl methacrylate and polyvinyl butyral; when the hole functional layer comprises a hole transport layer and/or a hole injection layer, the hole transport layer is arranged close to one side of the light-emitting layer, and the hole injection layer is arranged close to one side of the anode; wherein the material of the hole transport layer is selected from poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine), polyvinylcarbazole, poly (N, N '-bis (4-butylphenyl) -N, N' -bis (phenyl) benzidine), poly (9, 9-dioctylfluorene-CO-bis-N, N-phenyl-1, 4-phenylenediamine), 4 '-tris (carbazole-9-yl) triphenylamine, 4' -bis (9-carbazole) biphenyl, N, N '-diphenyl-N, N' -bis (3-methylphenyl) -1,1 '-biphenyl-4, 4' -diamine, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine, poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid), spiro-NPB, spiro-TPD, doped or undoped graphene, C ₆₀ 、NiO、MoO ₃ 、WO ₃ 、V ₂ O ₅ P-type gallium nitride, crO ₃ 、CuO、MoS _x 、MoSe _x 、WSx、WSe _x And one or more of CuS, cuSCN; the material of the hole injection layer is selected from one or more of poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid, 2,3,5, 6-tetrafluoro-7, 7', 8' -tetracyanoquinone-dimethane, 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazabenzophenanthrene, copper phthalocyanine, transition metal oxide and transition metal chalcogenide; wherein the transition metal oxide is selected from one or more of NiOx, moOx, WOx, crOx, cuO and the transition metal chalcogenide is selected from one or more of MoSx, moSex, WSx, WSex, cuS.

Correspondingly, the embodiment of the application also provides a display device which comprises any one of the photoelectric devices.

According to the preparation method of the film, the quantum dots in the quantum dot solution are deposited at the bottom of the solution by carrying out supercritical fluid treatment on the quantum dot solution arranged on the substrate, and then the solvent on the surface of the solution is removed by infrared irradiation treatment, so that the removal efficiency of the quantum dot solution solvent can be greatly improved, and the morphology and film formation uniformity of the film are improved.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the description of the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.

FIG. 1 is a schematic flow chart of an embodiment of a method for preparing a thin film according to the present application;

FIG. 2 is a schematic structural view of an embodiment of an optoelectronic device provided herein;

FIGS. 3a to 3d are electroluminescent patterns of the light-emitting layer film of Experimental example 1.

Detailed Description

The following description of the embodiments of the present application will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all, of the embodiments of the present application. All other embodiments, based on the embodiments herein, which are obtained by a person skilled in the art without making any inventive effort, are intended to be within the scope of the present application. Furthermore, it should be understood that the detailed description is presented herein for purposes of illustration and explanation only and is not intended to limit the present application.

In this application, unless otherwise indicated, terms of orientation such as "upper" and "lower" are used to generally refer to the upper and lower positions of the device in actual use or operation, and specifically the orientation of the drawing figures; while "inner" and "outer" are for the outline of the device. In addition, in the description of the present application, the term "comprising" means "including but not limited to".

Various embodiments of the present application may exist in a range format; it should be understood that the description in a range format is merely for convenience and brevity and should not be interpreted as a rigid limitation on the scope of the application. It is therefore to be understood that the range description has specifically disclosed all possible sub-ranges and individual values within that range. For example, it should be considered that a description of a range 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., as well as single numbers within the range, such as 1, 2, 3, 4, 5, and 6, wherever applicable. In addition, whenever a numerical range is referred to herein, it is meant to include any reference number (fractional or integer) within the indicated range.

Referring to fig. 1, fig. 1 is a schematic flow chart of an embodiment of a method for preparing a thin film according to the present application, which includes the following steps:

step S11: providing a substrate and a quantum dot solution, wherein the quantum dot solution comprises a solvent and quantum dots dispersed in the solvent, and the quantum dot solution is arranged on the substrate to form a quantum dot wet film;

step S12: treating the quantum dot wet film by using a supercritical fluid to enable quantum dots in the quantum dot wet film to be deposited on a substrate, so as to obtain an initial film, wherein the initial film comprises a solvent and a quantum dot layer deposited at the bottom of the solvent;

Step S13: and carrying out infrared irradiation treatment on the initial film to remove the solvent, thereby obtaining the film.

In the step, the efficiency of removing the solvent can be greatly improved through the infrared irradiation, and the morphology and film formation uniformity of the film are improved. Since the infrared irradiation has good controllability, the preparation stability of the film and the process controllability can be improved.

In the step S11:

the quantum dot solution includes quantum dots and a solvent. It is understood that the quantum dots are dispersed in the solvent in the form of nanoparticles. It is understood that the quantum dot solution is a system (i.e., a dispersion) formed by dispersing the nanoparticles in the solvent, and includes a solution, a suspension, and a colloid.

In some embodiments, the solvent is a high boiling point solvent. In some embodiments, the high boiling point solvent has a boiling point of 200 to 350 ℃.

In some embodiments, the high boiling point solvent is selected from at least one of alkanes having eighteen carbon atoms, alkenes having eighteen carbon atoms, alkenoic acids having eighteen carbon atoms.

Specifically, the high boiling point solvent may be selected from one or more of n-octadecane, 2-methylheptadecane, 3-methylheptadecane, 1-octadecene, (Z) -2-octadecene, 1-octadecenoic acid, cis-9-octadecenoic acid and trans-9-octadecenoic acid. Wherein, cis-9-octadecenoic acid is also called (Z) -9-octadecenoic acid or oleic acid.

In some embodiments, the quantum dot is selected from at least one of a single structure quantum dot selected from at least one of a group II-VI compound, a group III-V compound, a group II-V compound, a group III-VI compound, a group IV-VI compound, a group I-III-VI compound, a group II-IV-VI compound, and a group IV simple substance, a core-shell structure quantum dot, a doped or undoped inorganic perovskite type quantum dot, or an organic-inorganic hybrid perovskite type quantum dot, the group II-VI compound is selected from at least one of CdSe, cdS, cdTe, znSe, znS, cdTe, znTe, cdZnS, cdZnSe, cdZnTe, znSeS, znSeTe, znTeS, cdSeS, cdSeTe, cdTeS, cdZnSeS, cdZnSeTe and CdZnSTe, the group III-V compound is selected from at least one of InP, inAs, gaP, gaAs, gaSb, alN, alP, inAsP, inNP, inNSb, gaAlNP and InAlNP, and the group I-III-VI compound is selected from CuInS ₂ 、CuInSe ₂ AgInS ₂ At least one of (a) and (b); the core of the quantum dot with the core-shell structure is selected from any one of the quantum dots with the single structure, and the shell material of the quantum dot with the core-shell structure is selected from at least one of CdS, cdTe, cdSeTe, cdZnSe, cdZnS, cdSeS, znSe, znSeS and ZnS The method comprises the steps of carrying out a first treatment on the surface of the The structural general formula of the inorganic perovskite type quantum dot is AMX ₃ 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 halogen anion selected from Cl ^- 、Br ^- 、I ^- At least one of (a) and (b); the organic-inorganic hybridization perovskite type quantum dot has a structural general formula of BMX ₃ Wherein B is an organic amine cation selected from CH ₃ (CH ₂ ) _n-2 NH ₃ ⁺ Or [ NH ] ₃ (CH ₂ ) _n NH ₃ ] ²⁺ Wherein n is greater than or equal to 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 halogen anion selected from Cl ^- 、Br ^- 、I ^- At least one of them.

In some embodiments, the quantum dots have an average particle size of 2 to 20nm, such as 2 to 18nm, 5 to 15nm, 10 to 18nm, and the like.

It is understood that the concentration of the quantum dot solution is not particularly limited in the present application. In at least some embodiments, the concentration of the quantum dot solution is 20 to 40mg/mL, such as 20 to 35mg/mL, 25 to 40mg/mL, 25 to 35mg/mL, 30 to 35mg/mL, and the like. The quantum dots can be uniformly dispersed in the concentration range, and the aggregation of the quantum dot particles can be reduced, so that the film forming property can be improved.

In the step S12:

it will be appreciated that because the supercritical fluid is a substance at a critical temperature and/or critical pressure, the use of the supercritical fluid to treat the quantum dot wet film is performed at the critical temperature and/or critical pressure of the supercritical fluid.

In some embodiments, the critical temperature of the supercritical fluid is 5 to 100 ℃, e.g., the critical temperature may be 5 to 90 ℃, 30 to 80 ℃, 30 to 70 ℃, 30 to 60 ℃, 30 to 50 ℃, 30 to 40 ℃, 80 to 100 ℃, 90 to 100 ℃, 30 to 100 ℃, etc. The quantum dots in the quantum dot wet film can be prevented from being damaged by treating the quantum dot wet film with the supercritical fluid with the critical temperature.

In some embodiments, the supercritical fluid is selected from at least one of supercritical carbon dioxide, supercritical ethylene, supercritical ethane, supercritical propane, supercritical propylene, and supercritical chloroform.

Wherein the supercritical carbon dioxide has a critical temperature of about 31.4 ℃ and a critical pressure of about 4.91Mpa. The critical temperature of the supercritical ethylene is about 9.5 ℃ and the critical pressure is about 5.06Mpa. The critical temperature of the supercritical ethane is about 32.5 ℃ and the critical pressure is about 4.91Mpa. The critical temperature of the supercritical propane is about 96.8 ℃ and the critical pressure is about 4.26Mpa. The critical temperature of the supercritical propylene is about 92 ℃ and the critical pressure is about 4.5MPa. The critical temperature of the supercritical chloroform is about 263.4 ℃ and the critical pressure is about 5.47MPa.

In at least one embodiment, the supercritical fluid is supercritical ethane.

The supercritical fluid can not dissolve the quantum dots in the quantum dot solution, but can be mutually dissolved with the solvent in the quantum dot solution, when the supercritical fluid is contacted with the quantum dot solution, the supercritical fluid rapidly diffuses into the quantum dot solution, so that the volume of the quantum dot solution rapidly expands, the solubility of the quantum dots in the solvent is greatly reduced, and a great supersaturation degree is formed in a very short time, thereby promoting the crystallization of the quantum dots and depositing the quantum dots on the substrate to obtain the quantum layer. The process is finished instantaneously, and a film with uniform distribution and good appearance can be formed. In addition, the supercritical fluid is used for treating the quantum dot wet film, so that the damage of the device caused by conventional heat treatment can be avoided.

It will be appreciated that as the supercritical fluid leaves the solvent, some of the solvent is carried away.

In some embodiments, the treatment of the quantum dot wet film with supercritical fluid is specifically: and placing the substrate with the quantum dot wet film in an environment with critical temperature and/or critical pressure, and then spraying a supercritical fluid precursor into the environment to form a supercritical fluid, so that the supercritical fluid is used for treating the quantum dot wet film.

The critical temperature and critical pressure are as described above.

The supercritical fluid precursor is a substance that can form a supercritical fluid at a critical temperature and/or a critical pressure, and may be, for example, at least one selected from, but not limited to, carbon dioxide, ethylene, ethane, propane, propylene, and chloroform.

In some embodiments, the supercritical fluid precursor is sprayed into the environment using an ultrasonic atomizer. Further, in some embodiments, the oscillation frequency of the ultrasonic atomizing nozzle is 1.7-2.5 MHz, and the liquid pressure is 1.2-2 bar.

In some embodiments, the supercritical fluid precursor is sprayed into the environment for a time of 10 to 30 seconds.

In some embodiments, spraying the supercritical fluid precursor into the environment further comprises: standing for 10-30 min to fully treat the quantum dot wet film by the supercritical fluid.

In some embodiments, after the resting, further comprising: and replacing the ambient temperature and the ambient pressure with normal temperature and normal pressure to carry out subsequent treatment. The normal temperature and pressure are not particularly limited, and the basic concept of normal temperature and pressure (generally, the temperature is 25 ℃ and the pressure is one atmosphere) known to those skilled in the art may be adopted.

It will be appreciated that the treatment of the wet film of quantum dots with supercritical fluid may be performed in a closed apparatus to facilitate temperature and pressure regulation.

In one embodiment, the supercritical fluid precursor is sprayed into the environment, the substrate is controlled to rotate along the central line of the substrate as an axis, and the supercritical fluid is used for uniformly and fully contacting the quantum dot wet film on the substrate so as to process the wet film.

The rotation speed of the rotation may be 1500rpm to 4500rpm, such as 1500rpm to 2000rpm, 2000rpm to 2500rpm, 2500rpm to 3000rpm, 3000rpm to 3500rpm, 3500rpm to 4000rpm, 4000rpm to 4500rpm, etc. In the rotating speed range, the quantum dots in the quantum dot wet film can be prevented from being thrown out.

It can be understood that when the substrate rotates, part of the solvent in the wet film of the quantum dots can be thrown away, which is favorable for removing the solvent, thereby being favorable for preparing the quantum dot layer with stable structure and uniform film formation.

In the step S13:

in an embodiment, the infrared irradiation is performed at the critical temperature and/or critical pressure, which may be in step S12, or at normal temperature and pressure.

In one embodiment, the infrared radiation has a wavelength of 900-1100 nm, such as 900-1053 nm, 1000-1100 nm, 1000-1053 nm, 1053-1100 nm, etc. When the speed of light is constant, the shorter the wavelength, the higher the frequency and the higher the energy of the photon. Therefore, the laser of the near infrared short wave (750 nm-1100 nm) has enough photon energy, and can effectively perform infrared irradiation treatment, while the near infrared wave beyond the range cannot achieve the ideal external irradiation treatment effect due to the smaller photon energy. In the laser of infrared shortwave, the infrared laser with the wavelength of more than 900nm has better controllability, can directly act on the film, and cannot influence the performance of the quantum dots in the film due to the fact that photon energy is too high.

Further, the pulse width of the infrared irradiation is 100-120 fs, the repetition frequency is 1 kHz-1.5 kHz, and the beam quality factor is 1-1.2. The process parameters of infrared irradiation in this embodiment can effectively remove the solvent, and simultaneously ensure that infrared light energy cannot penetrate the solvent due to too high intensity to affect the overall performance of the quantum dot and avoid excessive heat accumulation from affecting the performance of the quantum dot.

In one embodimentIn an embodiment, the irradiation time of the infrared irradiation is 1×10 ^-2 ～1×10 ^-1 s, the irradiation time can not only effectively treat the initial film to remove the solvent, but also avoid the quantum dot thermal damage caused by the overlong infrared irradiation treatment time.

In one embodiment, the infrared radiation also has a certain beam diameter, which may be determined according to the area size of the initial film.

In a specific embodiment, the initial film is subjected to the infrared irradiation using an infrared laser. Since the infrared laser has high collimation and high focusing, only the surface layer of the initial film can be controlled to be heated, so that the solvent in the initial film is removed, and the performance of the quantum dots in the initial film is not affected.

In one embodiment, the method further comprises the step of annealing after the initial film is subjected to infrared irradiation and before the film is obtained.

The annealing treatment can further remove the solvent possibly remained in the initial film after the infrared irradiation treatment, and enable the film to have better crystallinity and more orderly arrangement of molecules, thereby improving the carrier mobility in the film and being beneficial to uniform luminescence.

Further, the annealing treatment may be an electron beam irradiation annealing treatment or a thermal annealing treatment.

In one embodiment, the average power of the electron beam spot in the electron beam irradiation annealing treatment is 1×10 ³ W/cm ² ～1×10 ⁴ W/cm ² The energy density in the electron beam irradiation annealing treatment is 0.5-1J/cm ² The electron beam irradiation annealing treatment time is 1×10 ^-2 s～1×10 ^-1 s. The average power, the energy density, and the time being too high or too long may result in the initial film temperature being too high, resulting in damage to the treated film layer; at the same time, the heat generated by the long time can be conducted to the quantum dot film layerThe shell structure is broken, and the luminous performance of the film is affected. If the average power, the energy density, and the time are too low or too short, the desired treatment effect cannot be achieved due to insufficient treatment time or strength. Further, the acceleration voltage of the electron beam in the electron beam irradiation annealing treatment is 1×10 ² V～1×10 ³ V, wherein the accelerating voltage determines the energy density of the electron beam irradiation annealing treatment, thereby controlling the energy density to be 0.5-1J/cm ² 。

In this embodiment, by the electron beam irradiation annealing treatment, due to the characteristics of the electron beam, the depth and the intensity of the electron beam irradiation annealing treatment on the thin film can be controlled by controlling parameters such as the average power of the electron beam spot, the accelerating voltage of the electron beam, the energy density and the like, and the time of the electron beam irradiation annealing treatment is controlled, so that damage to the thin film caused by overhigh temperature of the thin film is avoided, and the annealing treatment with controllable depth and controllable power on the thin film is realized on the premise that the material or the core-shell structure of the quantum dot and the like cannot be damaged by the electron beam irradiation annealing treatment, thereby rapidly improving the performance of the thin film.

Specifically, the accelerating voltage of the electron beam is positively correlated with the penetration depth of the electron beam, and the damage to the quantum dots in the thin film at the electron beam is avoided by adjusting the accelerating voltage of the electron beam within the above range.

In this embodiment, an Electron Beam (EB) irradiation technique used in the Electron beam irradiation annealing treatment irradiates a substance with an Electron beam after acceleration in a high-voltage electric field, and ionizes and excites molecules of various substances by interaction of high-energy electrons with the substance. The electron beam irradiation technology has higher stability and energy efficiency, and can avoid damage to the quantum dots caused by high-temperature treatment.

In a specific embodiment, the temperature of the heating annealing treatment is 80-100 ℃ and the time is 3-5 h.

The present application further relates to an optoelectronic device, and referring to fig. 2, fig. 2 is a schematic structural diagram of an embodiment of an optoelectronic device provided in the present application. The optoelectronic device 100 comprises a cathode 10, a light-emitting layer 20 and an anode 30 which are stacked, wherein the light-emitting layer 20 is prepared by the preparation method of the thin film.

In one embodiment, the cathode 10 and the anode 30 are each independently selected from one or more of a metal electrode, a carbon electrode, a doped or undoped metal oxide electrode, and a composite electrode; wherein the material of the metal electrode is at least one selected from Al, ag, cu, mo, au, ba, ca and Mg; the material of the carbon electrode is at least one selected from graphite, carbon nano tube, graphene and carbon fiber; the material of the doped or undoped metal oxide electrode is at least one selected from ITO, FTO, ATO, AZO, GZO, IZO, MZO and AMO; the composite electrode is selected from AZO/Ag/AZO, AZO/Al/AZO, ITO/Ag/ITO, ITO/Al/ITO, znO/Ag/ZnO, znO/Al/ZnO, and TiO ₂ /Ag/TiO ₂ 、TiO ₂ /Al/TiO ₂ 、ZnS/Ag/ZnS、ZnS/Al/ZnS、TiO ₂ /Ag/TiO ₂ TiO ₂ /Al/TiO ₂ At least one of them. Wherein "/" represents a laminated structure, for example, the composite electrode AZO/Ag/AZO represents an electrode of a composite structure in which AZO layers, ag layers, and AZO layers are laminated in three layers.

In an embodiment, the optoelectronic device 100 further comprises an electron transport layer 40, said electron transport layer 40 being arranged between said cathode 10 and said light emitting layer 20. The material of the electron transport layer 40 is one or more selected from inorganic nanocrystalline material, doped inorganic nanocrystalline material and organic material; the inorganic nanocrystalline material is selected from one or more of zinc oxide, titanium dioxide, tin dioxide, aluminum oxide, calcium oxide, silicon dioxide, gallium oxide, zirconium oxide, nickel oxide and zirconium oxide; the doped inorganic nanocrystalline material comprises one or more of zinc oxide dopant, titanium dioxide dopant and tin dioxide dopant, wherein the doped inorganic nanocrystalline material is an inorganic material doped with other elements, and the doping elements are selected from at least one of Mg, ca, li, ga, al, co, mn; the organic material may include one or both of polymethyl methacrylate and polyvinyl butyral.

In an embodiment, the optoelectronic device 100 further comprises a hole-functional layer 50, said hole-functional layer 50 being arranged between said light-emitting layer 20 and said anode 30. The hole-transporting layer 50 includes a hole-transporting layer and/or a hole-injecting layer, and when the hole-transporting layer 50 includes two layers, namely, a hole-transporting layer and a hole-injecting layer, the hole-transporting layer is disposed near the light-emitting layer 20, and the hole-injecting layer is disposed near the anode 30. Wherein the material of the hole transport layer is selected from poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine), polyvinylcarbazole, poly (N, N '-bis (4-butylphenyl) -N, N' -bis (phenyl) benzidine), poly (9, 9-dioctylfluorene-CO-bis-N, N-phenyl-1, 4-phenylenediamine), 4 '-tris (carbazole-9-yl) triphenylamine, 4' -bis (9-carbazole) biphenyl, N, N '-diphenyl-N, N' -bis (3-methylphenyl) -1,1 '-biphenyl-4, 4' -diamine, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine, poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid), spiro-NPB, spiro-TPD, doped or undoped graphene, C60, niO, moO ₃ 、WO ₃ 、V ₂ O ₅ P-type gallium nitride, crO ₃ 、CuO、MoS _x 、MoSe _x 、WSx、WSe _x And one or more of CuS, cuSCN; the material of the hole injection layer is selected from one or more of poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid, 2,3,5, 6-tetrafluoro-7, 7', 8' -tetracyanoquinone-dimethane, 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazabenzophenanthrene, copper phthalocyanine, transition metal oxide and transition metal chalcogenide; wherein the transition metal oxide comprises one or more of NiOx, moOx, WOx, crOx, cuO and the metal chalcogenide comprises one or more of MoSx, moSex, WSx, WSex, cuS.

The application also relates to a display device comprising the optoelectronic device provided by the application. The display device may be any electronic product with a display function, including but not limited to a smart phone, a tablet computer, a notebook computer, a digital camera, a digital video camera, a smart wearable device, a smart weighing electronic scale, a vehicle-mounted display, a television set or an electronic book reader, wherein the smart wearable device may be, for example, a smart bracelet, a smart watch, a Virtual Reality (VR) helmet, etc.

The present application is specifically illustrated by the following examples, which are only some of the examples of the present application and are not limiting of the present application.

Example 1

The embodiment provides an optoelectronic device, and the preparation of the optoelectronic device includes the following steps:

step 1: PEDOT was spin coated on an ITO substrate (thickness of ITO layer 50 nm): PSS material, wherein spin coating rotation speed is 5000r/min for 30 seconds, and then heating is carried out at 150 ℃ for 15 minutes, so as to obtain a hole injection layer with thickness of 50 nm;

step 2: spin-coating a TFB material with a concentration of 8mg/mL on the hole injection layer, wherein the spin-coating speed is 3000r/min, the time is 30 seconds, and then heating is carried out at 120 ℃ for 10 minutes to obtain a hole transport layer with a thickness of 30 nm;

step 3: spin-coating CdZnSe quantum material with concentration of 20mg/ml on the hole transport layer, wherein the spin-coating rotating speed is 2000rpm, and the spin-coating time is 30s, so as to form a quantum dot wet film; the ambient temperature was replaced with 32.2 ℃, the ambient pressure was replaced with 4.89Mpa, an ultrasonic atomizer (oscillation frequency 1.7MHz, liquid pressure 1.2 bar) was used, and ethane spraying was performed to form supercritical ethane, which was allowed to treat the quantum dot wet film for 10 seconds, followed by standing for 20 minutes.

After the standing is finished, the CdZnSe film is subjected to infrared irradiation by using a femtosecond laser, wherein the light emitting diameter of the infrared irradiation is 3mm, the wavelength is 1053nm, the pulse width is 120fs, the repetition frequency is 1kHz, the beam quality factor is 1.2, and the time is 1 multiplied by 10 ^-2 Second.

Step 4: spin-coating a ZnO solution with a concentration of 30mg/mL on the light-emitting layer, wherein the spin-coating speed is 3000r/min for 30 seconds, followed by 1X 10 ^-2 Standing for 15min under the MPa environment to obtain an electron transport layer with the thickness of 30 nm;

step 5: by thermal evaporation, at a low vacuum levelAt 3X 10 ^-4 Evaporating Ag on the electron transport layer under Pa, wherein the evaporation speed is 1 angstrom/second, and the evaporation time is 200 seconds, so as to obtain a cathode with the thickness of 20 nm;

step 6: and (5) encapsulating the epoxy resin to obtain the photoelectric device.

Example 2

This embodiment is substantially the same as embodiment 1 except that: the wavelength of the infrared radiation in step 3 is 900nm.

Example 3

This embodiment is substantially the same as embodiment 1 except that: the wavelength of the infrared radiation in step 3 is 1100nm.

Example 4

This embodiment is substantially the same as embodiment 1 except that: the wavelength of the infrared radiation in step 3 is 800nm.

Example 5

This embodiment is substantially the same as embodiment 1 except that: the wavelength of the infrared radiation in step 3 is 1300nm.

Example 6

This embodiment is substantially the same as embodiment 1 except that: after the infrared irradiation treatment in the step 3, adopting electron beam scanning to carry out electron beam irradiation annealing treatment, wherein the average power of the electron beam spots is 2 multiplied by 10 ³ W/cm ² The energy density of the electron beam was 0.825J/cm ² Time is 1×10 ^-2 Second.

Example 7

This embodiment is substantially the same as embodiment 6 except that: in step 3, the energy density of the electron beam was 1J/cm ² 。

Example 8

This embodiment is substantially the same as embodiment 6 except that: in step 3, the energy density of the electron beam was 0.5J/cm ² 。

Example 9

This embodiment is substantially the same as embodiment 6 except that: in step 3, the energy density of the electron beam was 3J/cm ² 。

Example 10

This embodiment is substantially the same as embodiment 6 except that: in step 3, the energy density of the electron beam was 0.2J/cm ² 。

Comparative example 1:

this comparative example is substantially the same as example 1 except that after spin coating a CdZnSe quantum material on the hole transport layer in step 3, it is heated at 120 ℃ for 5 minutes.

Comparative example 2:

this comparative example is substantially the same as example 1, except that after spin coating a CdZnSe quantum material on the hole-transporting layer in step 3, it is performed at 1X 10 ^-2 Standing for 15min under the MPa environment.

Comparative example 3

This comparative example is substantially the same as example 1 except that the infrared irradiation treatment was not performed in step 3.

Experimental example 1

Light-emitting layer films were prepared on glass substrates according to the methods for preparing light-emitting layers in example 1, example 6 and comparative examples 1 to 2, respectively. The electroluminescent patterns of the corresponding luminescent layer films are shown in figures 3 a-3 d.

Compared with fig. 3c and 3d, the uniformity of the film in fig. 3a and 3b is obviously improved, which indicates that the film formed by combining the supercritical fluid treatment with the infrared irradiation treatment in the application has better film forming property and obviously improves the film forming quality.

Experimental example 2

For the photoelectric devices of examples 1 to 10 and comparative examples 1 to 3, the luminance L, lifetime T95, lifetime t95—1knit, and current efficiency C.E were measured, respectively. Wherein, each parameter is measured under the drive of a constant current (2 mA current), the brightness change of each light emitting device is tested by adopting a silicon optical system, the time required for the brightness to decay from 100% to 95% is recorded, the time required for the brightness of each light emitting device to decay from 100% to 95% under the brightness of 1000nit (T95_1k nit, h) is calculated, and the experimental result is shown in the following table 1:

table 1 results of performance test of light emitting devices of examples 1 to 10 and comparative examples 1 to 3

From Table one can see:

comparative example 3 has improved luminescence properties (L and C.E) and lifetime (t95 and t95_1knit) as compared to comparative examples 1 and 2, i.e., the luminescence properties and lifetime of the photovoltaic device can be improved as compared to conventional heating and vacuum drying treatments only by using supercritical fluid treatment.

Examples 1 to 3 significantly improved the luminescence properties (L and C.E) and lifetime (T95 and t95—1knit) of the photovoltaic devices corresponding to examples 1 to 3, compared to comparative example 3, indicating that the supercritical fluid treatment of the quantum dot solution in combination with the infrared irradiation treatment having a wavelength in the range of 900nm to 1100nm can improve the luminescence properties, lifetime, and other properties of the photovoltaic devices. Whereas the 800nm wavelength infrared radiation used in example 4, the photon energy is more likely to oversubscribe the quantum dot damage to the light emitting layer, resulting in the photovoltaic device exhibiting lower brightness (L), resulting in a decrease in t95—1knit. In example 5, the luminescence properties (L and C.E) were significantly improved, and the lifetime T95 and the lifetime t95_1knit were reduced to some extent, probably due to the use of 1300nm wavelength infrared irradiation, the photon energy was smaller and the solvent could not be effectively removed, which is manifested as a problem in film formation, and the abnormal electrical properties resulted in the reduction of the measured data of the device T95, resulting in the reduction of t95_1knit.

Examples 6 to 8 are improved to some extent in both L and C.E and lifetime (T95 and T95_1k nit) as compared with example 1, demonstrating that the light emission performance and lifetime of the photovoltaic device can be improved by combining the electron beam irradiation annealing treatment. Example 9 reduced luminance L and lifetime T95_1k nit compared to example 6, probably due to 3J/cm ² The energy density is too high, and the quantum dots are damaged, so that the performance of the light-emitting layer and the performance of the photoelectric device are affected. Example 10 may be due to 0.2J/cm compared to example 6 ² The energy density of (2) is too small to effectively remove the solvent, a tableAt present, problems occur in film formation, and abnormal electrical properties lead to reduction of measured data of a device T95, and lead to reduction of T95_1Knit.

The preparation method, the photoelectric device and the display device of the thin film provided by the embodiment of the application are described in detail, and specific examples are applied to the description of the principle and the implementation of the application, and the description of the above examples is only used for helping to understand the method and the core idea of the application; meanwhile, those skilled in the art will have variations in the specific embodiments and application scope in light of the ideas of the present application, and the present description should not be construed as limiting the present application in view of the above.

Claims

1. A method of producing a film comprising:

providing a substrate and a quantum dot solution, and arranging the quantum dot solution on the substrate to obtain a quantum dot wet film;

treating the quantum dot wet film by using a supercritical fluid to obtain an initial film;

And carrying out infrared irradiation on the initial film to obtain the film.

2. The method of claim 1, wherein the infrared radiation has a wavelength of 900-1100 nm, preferably 1000-1100 nm.

3. The method of claim 2, wherein the pulse width of the infrared irradiation is 100-120 fs, the repetition frequency is 1-1.5 kHz, the beam quality factor is 1-1.2, and the irradiation time of the infrared irradiation is 1X 10 ^-2 ～1×10 ^-1 s。

4. A method of producing a film according to any one of claims 1 to 3, wherein said subjecting said initial film to infrared radiation gives said film comprising:

an annealing treatment is further included after the infrared irradiation treatment is performed on the initial film and before the film is obtained.

5. The method according to claim 4, wherein the annealing treatment is an electron beam irradiation annealing treatment or a thermal annealing treatment.

6. The method according to claim 5, wherein the electron beam spot of the electron beam irradiation annealing treatment has an average power of 1X 10 ³ ～1×10 ⁴ W/cm ² The energy density of the electron beam is 0.5-1J/cm ² Annealing time is 1×10 ^-2 ～1×10 ^-1 s。

7. The method according to claim 5, wherein the temperature of the thermal annealing treatment is 80 to 100℃for 3 to 5 hours.

8. The preparation method according to claim 1, characterized in that the critical temperature of the supercritical fluid is 5-100 ℃, preferably 30-100 ℃.

9. The method according to any one of claims 1 to 8, wherein the supercritical fluid is at least one selected from the group consisting of supercritical carbon dioxide, supercritical ethylene, supercritical ethane, supercritical propane, and supercritical propylene.

10. The method of any one of claims 1 to 9, wherein the treating the quantum dot wet film with a supercritical fluid to obtain an initial film comprises:

and placing the substrate with the quantum dot wet film in an environment with critical temperature and/or critical pressure, spraying a supercritical fluid precursor into the environment to form a supercritical fluid, and processing the quantum dot wet film by the supercritical fluid to obtain the initial film.

11. The process according to any one of claims 1 to 10, which is characterized in thatCharacterized in that the quantum dot solution comprises quantum dots and a solvent, wherein the quantum dots are selected from at least one of single-structure quantum dots, core-shell structure quantum dots, doped or undoped inorganic perovskite type quantum dots or organic-inorganic hybrid perovskite type quantum dots, the single-structure quantum dots are selected from at least one of II-VI compound, III-V compound, II-V compound, III-VI compound, IV-VI compound, I-III-VI compound, II-IV-VI compound and IV simple substance, the II-VI compound is selected from at least one of CdSe, cdS, cdTe, znSe, znS, cdTe, znTe, cdZnS, cdZnSe, cdZnTe, znSeS, znSeTe, znTeS, cdSeS, cdSeTe, cdTeS, cdZnSeS, cdZnSeTe and CdZnSTe, the III-V compound is selected from at least one of InP, inAs, gaP, gaAs, gaSb, alN, alP, inAsP, inNP, inNSb, gaAlNP and InAlNP, and the I-III-VI compound is selected from CuInS ₂ 、CuInSe ₂ AgInS ₂ At least one of (a) and (b); the core of the quantum dot with the core-shell structure is selected from any one of the quantum dots with the single structure, and the shell material of the quantum dot with the core-shell structure is selected from at least one of CdS, cdTe, cdSeTe, cdZnSe, cdZnS, cdSeS, znSe, znSeS and ZnS; the structural general formula of the inorganic perovskite type quantum dot is AMX ₃ 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 halogen anion selected from Cl ^- 、Br ^- 、I ^- At least one of (a) and (b); the organic-inorganic hybridization perovskite type quantum dot has a structural general formula of BMX ₃ Wherein B is an organic amine cation selected from CH ₃ (CH ₂ ) _n-2 NH ₃ ⁺ Or [ NH ] ₃ (CH ₂ ) _n NH ₃ ] ²⁺ Wherein n is greater than or equal to 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 halogen anion selected from Cl ^- 、Br ^- 、I ^- At least one of (a) and (b);

the average particle size of the quantum dots is 2-20 nm;

the solvent is at least one selected from alkane with eighteen carbon atoms, alkene with eighteen carbon atoms, and olefine acid with eighteen carbon atoms.

12. An optoelectronic device comprising a cathode, a light-emitting layer and an anode, which are arranged in a stack, wherein the light-emitting layer is produced by the method for producing a film according to any one of claims 1 to 11.

13. The optoelectronic device of claim 12, wherein,

the cathode and the anode are each independently selected from one or more of a metal electrode, a carbon electrode, a doped or undoped metal oxide electrode, and a composite electrode; wherein the material of the metal electrode is at least one selected from Al, ag, cu, mo, au, ba, ca and Mg; the material of the carbon electrode is at least one selected from graphite, carbon nano tube, graphene and carbon fiber; the material of the doped or undoped metal oxide electrode is at least one selected from ITO, FTO, ATO, AZO, GZO, IZO, MZO and AMO; the composite electrode is selected from AZO/Ag/AZO, AZO/Al/AZO, ITO/Ag/ITO, ITO/Al/ITO, znO/Ag/ZnO, znO/Al/ZnO, and TiO ₂ /Ag/TiO ₂ 、TiO ₂ /Al/TiO ₂ 、ZnS/Ag/ZnS、ZnS/Al/ZnS、TiO ₂ /Ag/TiO ₂ TiO ₂ /Al/TiO ₂ At least one of them.

14. The optoelectronic device of claim 12 or 13, further comprising an electron transport layer disposed between the cathode and the light emitting layer and a hole functional layer disposed between the light emitting layer and the anode;

the material of the electron transport layer is one or more selected from inorganic nanocrystalline materials, doped inorganic nanocrystalline materials and organic materials; the inorganic nanocrystalline material is selected from one or more of zinc oxide, titanium dioxide, tin dioxide, aluminum oxide, calcium oxide, silicon dioxide, gallium oxide, zirconium oxide, nickel oxide and zirconium oxide; the doped inorganic nanocrystalline material is one or more of zinc oxide dopant, titanium dioxide dopant and tin dioxide dopant, wherein the doped inorganic nanocrystalline material is an inorganic material doped with other elements, and the doping elements are at least one of Mg, ca, li, ga, al, co, mn; the organic material is selected from one or two of polymethyl methacrylate and polyvinyl butyral;

When the hole functional layer comprises a hole transport layer and/or a hole injection layer, the hole transport layer is arranged close to one side of the light-emitting layer, and the hole injection layer is arranged close to one side of the anode;

wherein the material of the hole transport layer is selected from poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine), polyvinylcarbazole, poly (N, N '-bis (4-butylphenyl) -N, N' -bis (phenyl) benzidine), poly (9, 9-dioctylfluorene-CO-bis-N, N-phenyl-1, 4-phenylenediamine), 4 '-tris (carbazole-9-yl) triphenylamine, 4' -bis (9-carbazole) biphenyl, N, N '-diphenyl-N, N' -bis (3-methylphenyl) -1,1 '-biphenyl-4, 4' -diamine, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine, poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid), spiro-NPB, spiro-TPD, doped or undoped graphene, C ₆₀ 、NiO、MoO ₃ 、WO ₃ 、V ₂ O ₅ P-type gallium nitride, crO ₃ 、CuO、MoS _x 、MoSe _x 、WSx、WSe _x And one or more of CuS, cuSCN; the material of the hole injection layer is selected from poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid, 2,3,5, 6-tetrafluoro-7, 7', 8' -tetracyanoquinone-dimethane, 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazabenzophenanthrene, copper phthalocyanine and transition metal oxidation One or more of a compound, a transition metal chalcogenide; wherein the transition metal oxide is selected from one or more of NiOx, moOx, WOx, crOx, cuO and the transition metal chalcogenide is selected from one or more of MoSx, moSex, WSx, WSex, cuS.

15. A display device comprising an optoelectronic device according to any one of claims 12 to 14.