CN115968214A - Hole transport film, preparation method thereof, photoelectric device and display device - Google Patents
Hole transport film, preparation method thereof, photoelectric device and display device Download PDFInfo
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- CN115968214A CN115968214A CN202111171832.6A CN202111171832A CN115968214A CN 115968214 A CN115968214 A CN 115968214A CN 202111171832 A CN202111171832 A CN 202111171832A CN 115968214 A CN115968214 A CN 115968214A
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- hole transport
- metal oxide
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- triazine
- transport film
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/15—Hole transporting layers
- H10K50/155—Hole transporting layers comprising dopants
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
- H10K71/15—Deposition of organic active material using liquid deposition, e.g. spin coating characterised by the solvent used
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The application discloses a hole transport film, a preparation method thereof, a photoelectric device and a display device. The hole transport film comprises a metal oxide nano material doped with a triazine framework material. The triazine framework material contains rich nitrogen elements, has polarity on the surface, and can induce to form strong molecular dipoles on the interface of the metal oxide nanometer material layer, so that the energy level position is adjusted, the energy levels of the hole transport film and the luminescent layer are more matched, and the electron-hole injection balance of the photoelectric device is facilitated. The triazine ring skeleton is of a layered porous structure, has a large specific surface area, can have a coating effect on metal oxide nanoparticles, can effectively control the nucleation rate of the nanoparticles, passivates the surface defects of the nanoparticles, increases the crystallinity and the conductivity of the material, and improves the hole transmission rate. The luminous efficiency of the photoelectric device is improved and the turn-on voltage of the photoelectric device is reduced by improving the electron-hole injection balance and the hole transmission rate.
Description
Technical Field
The application relates to the technical field of display, in particular to a hole transport film, a preparation method thereof, a photoelectric device and a display device.
Background
The photoelectric device refers to a device manufactured according to a photoelectric effect, and has wide applications in the fields of new energy, sensing, communication, display, illumination and the like, such as a solar cell, a photoelectric detector, an organic electroluminescent device (OLED) or a quantum dot electroluminescent device (QLED). The conventional optoelectronic device mainly includes an anode, a hole injection layer, a hole transport layer (i.e., a hole transport film), a light emitting layer, an electron transport layer, an electron injection layer, and a cathode. Under the action of an electric field, holes generated by an anode of the photoelectric device and electrons generated by a cathode move, are respectively injected into the hole transport layer and the electron transport layer and finally migrate to the light emitting layer, and when the holes and the electrons meet at the light emitting layer, energy excitons are generated, so that light emitting molecules are excited to finally generate visible light.
PSS is widely used in the fields of optoelectronic devices such as OPV, OFET, perovskite solar cells, OLED, QLED and the like, and achieves good effects. However, the PEDOT-PSS material is acidic and easy to corrode the ITO conductive glass surface, and is hygroscopic and easy to corrode by moisture in the air, thereby adversely affecting the stability of the device. Compared with organic hole transport materials, inorganic hole transport materials have more excellent stability, higher hole mobility and low cost, and can realize solution-soluble processing.
However, the hole transport layer prepared by the existing metal oxide nano material has the problems of poor energy level matching with the light emitting layer, poor conductivity and the like, so that the photoelectric device has low efficiency.
Disclosure of Invention
In view of this, the present application provides a hole transport film, a method for manufacturing the same, a photovoltaic device, and a display device, and aims to solve the problem of low efficiency of the photovoltaic device.
The embodiments of the present application are achieved by providing a hole transport film comprising a metal oxide nanomaterial doped with a triazine backbone material.
Optionally, in some embodiments of the present application, the hole transport thin film is composed of a metal oxide nanomaterial doped with a triazine backbone material.
Alternatively, in some embodiments of the present application, the triazine skeleton material is polymerized from a monomer, which is an aromatic group-containing nitrile compound.
Optionally, in some embodiments of the present application, the aromatic group-containing nitrile compound is selected from cyano-substituted benzene ring compounds, cyano-substituted pyridine compounds, cyano-substituted pyrimidine compounds, cyano-substituted biphenyl compounds, and cyano-substituted naphthalene ring compounds.
Optionally, in some embodiments of the present application, the aromatic group-containing nitrile compound includes at least two cyano groups, and the aromatic group-containing nitrile compound is selected from at least one of tricyanobenzene, p-cyanobenzene, biphenyl dinitrile, and pyridine dinitrile.
Optionally, in some embodiments of the present application, in the metal oxide nanomaterial doped with triazine skeleton material, the molar ratio of metal oxide to triazine skeleton material is in the range of 1 (1-1.5).
Optionally, in some embodiments herein, the metal oxide nanomaterial is selected from NiO x 、MoO x 、WO x 、CuO x At least one of
Correspondingly, the embodiment of the application also provides a preparation method of the hole transport film, which comprises the following steps: preparing a metal oxide precursor doped with a triazine framework material; providing a substrate, and arranging the triazine skeleton material-doped metal oxide precursor on the substrate to obtain the hole transport film of the triazine skeleton material-doped metal oxide nano material.
Alternatively, in some embodiments of the present application, the step of preparing a metal oxide precursor doped with a triazine framework material comprises: providing metal salt, a triazine framework material and a solvent, and mixing to obtain a metal salt mixture solution doped with the triazine framework material; and adding alkali into the metal salt mixture solution to obtain the metal oxide precursor doped with the triazine framework material.
Optionally, in some embodiments of the present application, the metal salt is selected from at least one of a metal chloride salt, a metal nitrate salt, a metal acetylacetonate salt; and/or the alkali is selected from at least one of sodium hydroxide, potassium hydroxide and tetramethyl ammonium hydroxide; and/or the solvent is selected from at least one of methanol, ethanol, glycol, glycerol, DMF and DMSO.
Optionally, in some embodiments of the present application, the step of providing a substrate, and disposing the triazine skeleton material-doped metal oxide precursor on the substrate to obtain a hole transport thin film comprising a triazine skeleton material-doped metal oxide nanomaterial includes: providing a substrate, and coating the metal oxide precursor doped with the triazine framework material on the substrate by adopting a solution method; and drying to obtain the hole transport film of the metal oxide nano material doped with the triazine framework material.
Correspondingly, the embodiment of the application also provides a photoelectric device, which comprises an anode, a light-emitting layer, a hole transport layer and a cathode which are arranged in a stacked manner, wherein the hole transport layer is the hole transport film, or the hole transport film is prepared by the preparation method of the hole transport film.
Optionally, in some embodiments of the present application, the light emitting layer is an organic light emitting layer or a quantum dot light emitting layer, and the material of the organic light emitting layer is selected from at least one of diarylanthracene derivatives, stilbene aromatic derivatives, pyrene derivatives or fluorene derivatives, blue light emitting TBPe fluorescent material, green light emitting TTPA fluorescent material, orange light emitting TBRb fluorescent material, and red light emitting DBP fluorescent material; the material of the quantum dot light-emitting layer comprises at least one of II-VI compound, III-V compound and I-III-VI compound; the II-VI compound is at least one selected from 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 InP, inAs, gaP, gaAs, gaSb, alN, alP, inAsP, inNP, inNSb, gaAlNP andand InAlNP; the group I-III-VI compound is selected from CuInS 2 、CuInSe 2 And AgInS 2 At least one of (1).
Correspondingly, the embodiment of the application also provides a display device which comprises the photoelectric device.
The hole transport thin film of the present application comprises a metal oxide nanomaterial doped with a triazine backbone material. The triazine skeleton material has good chemical stability and thermal stability, is a porous material, contains rich nitrogen elements, has polarity on the surface, and can induce the formation of strong molecular dipoles on the interface of a metal oxide nano material layer, so that the energy level position is adjusted, the energy levels of a hole transport layer and a light-emitting layer of the metal oxide nano material are matched, the injection and the transmission of holes are facilitated, and the electron-hole balance is promoted. Meanwhile, the covalent triazine ring skeleton has a layered structure and a high specific surface area, has a coating effect on the metal oxide nanoparticles, and can effectively control the nucleation rate of the metal oxide nanoparticles, passivate the surface defects of the metal oxide nanoparticles, reduce the surface energy of a polar surface, increase the crystallinity of the material, improve the conductivity of the metal oxide nanoparticles, improve the hole transmission rate, and further synergistically improve the performance and the efficiency of the device.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
Fig. 1 is a schematic structural diagram of an optoelectronic device provided in an embodiment of the present application;
FIG. 2 is a schematic flow chart of a method for preparing a hole transport film according to an embodiment of the present disclosure;
FIG. 3 is a flowchart illustrating an embodiment of step S10 in FIG. 2;
FIG. 4 is a flowchart illustrating an embodiment of step S20 of FIG. 2;
fig. 5 is a schematic flow chart of a method for fabricating a photovoltaic device provided by an embodiment of the present application;
fig. 6 is a schematic flow chart of another method for fabricating an optoelectronic device provided by an embodiment of the present application;
FIG. 7 is a schematic structural diagram of triazine framework materials CTF-1 and CTF-2 provided by the application.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application. Furthermore, it should be understood that the detailed description and specific examples, while indicating exemplary embodiments of the invention, are given by way of illustration and explanation only, and are not intended to limit the scope of the invention. In the present application, unless otherwise specified, the use of directional words such as "upper" and "lower" specifically refer to the orientation of the figures in the drawings. In addition, in the description of the present application, the term "including" means "including but not limited to". Various embodiments of the invention may exist in a range of forms; it is to be understood that the description in range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the invention; accordingly, the described range descriptions should be considered to have specifically disclosed all the possible sub-ranges as well as individual numerical values within that range. For example, it is contemplated that the 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 individual numbers within the stated range, such as 1, 2, 3, 4, 5, and 6, for example, as applicable regardless of the range. In addition, whenever a numerical range is indicated herein, it is meant to include any number (fractional or integer) recited within the range so indicated.
Referring to fig. 1, the present embodiment provides a hole transport film 10, which is mainly used in an optoelectronic device 100. The hole transport film 10 includes a triazine skeleton material-doped metal oxide nanomaterial, which may be abbreviated as MOx/CTF, where MOx is a metal oxide and CTF is a triazine skeleton material.
In this embodiment, in the metal oxide nanomaterial doped with the triazine framework material, since the triazine framework material contains abundant nitrogen elements and has polarity on the surface, a strong molecular dipole can be induced to form on the interface of the metal oxide nanomaterial layer, so as to adjust the energy level position, so that the energy levels of the metal oxide nanomaterial hole transport film 10 and the light emitting layer are more matched, which is beneficial to the electron-hole injection balance of the optoelectronic device 100 including the hole transport film 10. Meanwhile, the covalent triazine ring skeleton is of a layered porous structure, has a large specific surface area, can have a coating effect on the metal oxide nanoparticles, and the covalent triazine ring skeleton and the metal oxide nanoparticles are in close contact, so that the nucleation rate of the metal oxide nanoparticles can be effectively controlled, the surface defects of the metal oxide nanoparticles are passivated, the surface energy of a polar surface is reduced, the crystallinity of the material is increased, the conductivity of the metal oxide nanoparticles is improved, and the hole transmission rate is improved. The above two cooperate to improve the light emitting efficiency of the optoelectronic device 100 and reduce the turn-on voltage of the optoelectronic device 100. In addition, the triazine skeleton material has good chemical stability and thermal stability, and is doped in the metal oxide nano material to be used as a hole transport material, so that the chemical stability and the thermal stability of the hole transport film 10 and the photoelectric device 100 are not negatively influenced.
In this embodiment, the hole transport film may be composed of only the metal oxide nanomaterial doped with the triazine skeleton material, and may further include other materials than the metal oxide nanomaterial doped with the triazine skeleton material. For example, conventional organic hole transport materials such as PEDOT: PSS, or metal particles, etc., may also be included.
In this embodiment, the triazine skeleton material is formed by polymerizing a monomer, and the monomer is an aromatic nitrile compound. The nitrile compound containing an aromatic group may also be referred to as an aromatic nitrile compound, a cyano-substituted aromatic compound, or a cyano-substituted aromatic ring compound. Specifically, cyano groups in the nitrile compound containing the aromatic group are subjected to cyclization trimerization under certain conditions to form a triazine ring structure, and a plurality of triazine ring structures form a triazine framework material. It is understood that the triazine skeleton material of the present application can be obtained by other methods, and the triazine skeleton material of the present application is not limited to the polymerization of the aromatic group-containing nitrile compound, but also includes triazine skeleton materials prepared by other methods known in the art.
In some embodiments of the present application, the nitrile compound containing an aromatic group as a monomer may be selected from cyano-substituted benzene rings, cyano-substituted pyridines, cyano-substituted pyrimidines, cyano-substituted biphenyls, and cyano-substituted naphthalene rings. That is, the aromatic group in the nitrile compound containing aromatic group may be benzene ring, pyridine ring, pyrimidine ring, biphenyl or naphthalene ring, etc.
In some embodiments herein, the aromatic group-containing nitrile compound includes at least two cyano groups. Two and more cyano groups may add reactive sites to the monomer for cyclotrimerization to a triazine ring structure. Each cyano group may participate in the formation of the triazine ring structure, and then at least two cyano groups may support each monomer to participate in the formation of at least two triazine ring structures, and may be capable of linking a plurality of triazine ring structures to form a triazine skeleton material with a high degree of polymerization. Specifically, the aromatic group-containing nitrile compound may be p-cyanobenzene containing two cyano groups, biphenyl dinitrile or pyridine dinitrile, or tricyanobenzene containing three cyano groups. Wherein the tricyanobenzene can be 1, 3, 5-tricyano-substituted phenyl or 1, 3, 5-benzene tricyano.
It is understood that a triazine skeleton material in this embodiment may be polymerized from one monomer, or may be polymerized from two or more different monomers. For example, the triazine backbone material may be polymerized from two monomers, p-cyanobenzene and tricyanobenzene.
It is understood that the metal oxide nanomaterial in this embodiment may be doped with one triazine framework material, or may be doped with two or more triazine framework materials. For example, the metal oxide nano material can be doped with a triazine skeleton material formed by polymerizing p-cyanobenzene, and simultaneously doped with a triazine skeleton material formed by polymerizing tricyanobenzene.
In some embodiments of the present application, in the triazine backbone material doped metal oxide nanomaterial, the molar ratio of metal oxide to triazine backbone material is in the range of 1 (1-1.5). Specifically, the molar ratio of the metal oxide to the triazine skeleton material may be 1:1, 1.1, 1.2, 1.3, 1. The content of the triazine skeleton material is too low, so that the effect of improving the hole transmission rate of the hole transmission film 10 is difficult to achieve; if the content of the triazine skeleton material is too high, the charge transport property of the hole transport film 10 is lowered. The triazine skeleton material is a polymer, and the molar ratio can be calculated by the average molecular weight of the polymer. Wherein the average molecular weight can be obtained by multiplying the average degree of polymerization by the molecular weight of the monomer, and the average degree of polymerization can be obtained by a viscosity test. In this embodiment, the polymerization degree of the triazine ring skeleton material may be controlled to 900 to 3000.
In some embodiments of the present application, the metal oxide nanomaterial may be selected from inorganic materials having hole transport capability, including but not limited to at least one of doped or undoped NiOx, moOx, WOx, and CuOx. Specifically, the metal oxide nano material can be selected from NiO and WO 3 、MoO 3 And CuO.
An embodiment of the present application further provides a method for manufacturing a hole transport film 10, please refer to fig. 2, fig. 2 is a flowchart of the method for manufacturing a hole transport film according to the embodiment of the present application, including the following steps:
step S10: preparing a metal oxide precursor doped with the triazine framework material.
In this embodiment, the triazine skeleton material is formed by polymerizing a monomer, and the monomer is a nitrile compound containing an aromatic group. The nitrile compound containing an aromatic group may also be referred to as an aromatic nitrile compound, a cyano-substituted aromatic compound, or a cyano-substituted aromatic ring compound. Specifically, cyano groups in the nitrile compound containing the aromatic group are subjected to cyclization trimerization under certain conditions to form a triazine ring structure, and a plurality of triazine ring structures form a triazine framework material.
In some embodiments of the present application, the nitrile compound containing an aromatic group as a monomer may be selected from cyano-substituted benzene ring compounds, cyano-substituted pyridine compounds, cyano-substituted pyrimidine compounds, cyano-substituted biphenyl compounds, and cyano-substituted naphthalene ring compounds. That is, the aromatic group in the nitrile compound containing aromatic group can be benzene ring, pyridine ring, pyrimidine ring, biphenyl or naphthalene ring, etc.
In some embodiments herein, the aromatic group-containing nitrile compound includes at least two cyano groups. Two and more cyano groups may add reactive sites to the monomer for cyclotrimerization to a triazine ring structure. Each cyano group can participate in the formation of a triazine ring structure, and then at least two cyano groups can support each monomer to participate in the formation of at least two triazine ring structures, and can connect a plurality of triazine ring structures to form a triazine skeleton material with high polymerization degree. Specifically, the aromatic group-containing nitrile compound may be p-cyanobenzene containing two cyano groups, biphenyldinitrile or pyridinedicarbonitrile, or tricyanobenzene containing three cyano groups. Wherein the tricyanobenzene can be 1, 3, 5-tricyano-substituted phenyl or 1, 3, 5-benzene tricyano.
It is understood that a triazine skeleton material in this embodiment may be polymerized from one monomer, or may be polymerized from two or more different monomers. For example, the triazine backbone material may be polymerized from two monomers, p-cyanobenzene and tricyanobenzene.
It is understood that the metal oxide nanomaterial in this embodiment may be doped with one triazine skeleton material, or may be doped with two or more triazine skeleton materials. For example, the metal oxide nano material can be doped with a triazine skeleton material formed by polymerizing p-cyanobenzene, and simultaneously doped with a triazine skeleton material formed by polymerizing tricyanobenzene.
In an embodiment, referring to fig. 3, fig. 3 is a schematic flowchart of an embodiment of step S10 in fig. 2, where step S10 may specifically include:
step S11: providing metal salt, triazine framework material and solvent, and mixing to obtain the metal salt mixture solution doped with the triazine framework material.
In this step, the metal salt may be at least one selected from a metal chloride salt, a metal nitrate salt, and a metal acetylacetonate salt. For example, the nickel salt may be nickel chloride, nickel nitrate, nickel acetylacetonate, or the like.
In this step, the solvent used may be at least one selected from the group consisting of alcohol, DMF, and DMSO. Wherein the alcohol can be methanol, ethanol, ethylene glycol, propanol, glycerol, butanol, etc. The alcohol is used as a solvent, so that the formation of non-bridging hydroxyl on the surface of the metal oxide nano material can be avoided, and the occurrence of an agglomeration phenomenon is reduced. And because the precursor particles contain physically and chemically adsorbed alcohol, the particles can be further prevented from approaching, and the formation of agglomeration can be effectively reduced. In order to uniformly mix the triazine skeleton material and the metal salt in the metal salt mixture solution doped with the triazine skeleton material, stirring and mixing or ultrasonic treatment may be performed to sufficiently disperse and mix.
It is understood that at least one of the references in this application includes one, two, and more than two.
Step S12: and adding alkali into the metal salt mixture solution to obtain the metal oxide precursor doped with the triazine framework material.
The alkali may be at least one selected from sodium hydroxide, potassium hydroxide and tetramethylammonium hydroxide.
In the step, alkali is added into the metal salt mixture solution to obtain the metal oxide precursor doped with the triazine framework material with the pH value ranging from 8 to 14. Namely, the pH range of the metal oxide precursor doped with the triazine framework material is 8-14, the alkaline environment is favorable for the formation of the subsequent metal oxide nano material, and the pH value of the metal oxide precursor is too low, so that more hydroxyl ligands can be formed on the surface of the metal oxide nano material more easily, and the agglomeration phenomenon is caused; and too high pH value of the metal oxide precursor can result in too small particle size of the formed metal oxide nano material and more surface defects.
In order to reduce the occurrence of the phenomena of non-uniform size, agglomeration and the like of the nanoparticles, the base can be slowly added into the metal salt mixture solution, for example, a slow dripping mode can be adopted. The alkali can be dissolved in the alcohol to form an alcohol solution of the alkali, and the alcohol can be used as a solvent on one hand and can also be used as a diluent of the alkali on the other hand, so that the occurrence of subsequent agglomeration of the metal oxide nanoparticles is reduced.
After the alkali is added to adjust the pH value of the solution, the solution can be stirred for a certain time, such as 1 to 6 hours, so that the solution of the metal oxide precursor doped with the triazine framework material is uniformly mixed, the triazine framework material is fully contacted with the metal oxide precursor, the particle agglomeration phenomenon during the subsequent generation of the metal oxide nanoparticles is reduced, the triazine framework material wraps the metal oxide nanoparticles, the nucleation rate of the metal oxide nanoparticles is effectively controlled, and the surface defects of the metal oxide nanoparticles are passivated.
After the metal oxide precursor doped with the triazine skeleton material is prepared in the above step, step S20 is performed.
Step S20: providing a substrate, and arranging the triazine skeleton material-doped metal oxide precursor on the substrate to obtain the hole transport film of the triazine skeleton material-doped metal oxide nano material.
In some embodiments of the present application, the metal oxide nanomaterial may be selected from inorganic materials having hole transport capability, including but not limited to at least one of doped or undoped NiOx, moOx, WOx, and CuOx. Specifically, the metal oxide nano material can be selected from NiO and WO 3 、MoO 3 And CuO. In order to prepare a certain metal oxide nanomaterial, in step S10, a metal salt of the corresponding metal needs to be used. For example, if a nickel salt is used in step S10, the hole transport film 10 including the nickel oxide nanomaterial doped with the triazine skeleton material is obtained in this step.
In some embodiments of the present application, the molar ratio of the metal oxide to the triazine skeleton material in the hole transport film prepared in this step is in the range of 1 (1 to 1.5). Specifically, the molar ratio of the metal oxide to the triazine skeleton material may be 1:1, 1.1, 1.2, 1.3, 1. Accordingly, in order to make the molar ratio of the metal oxide to the triazine framework material in the hole transport film comprising the metal oxide nanomaterial doped with the triazine framework material obtained in step S20 be in the range of 1 (1-1.5), the molar ratio of the metal oxide precursor to the triazine framework material may be controlled in the preset range in the previous step S10, or the metal salt and the triazine framework material may be added in the preset ratio in step S11.
Specifically, referring to fig. 4, fig. 4 is a schematic flowchart of an embodiment of step S20 in fig. 2, where step S20 may specifically include:
step S21: providing a substrate, and arranging the metal oxide precursor doped with the triazine framework material on the substrate by adopting a solution method.
In this step, the triazine skeleton material-doped metal oxide precursor is in a solution state, and when the precursor is placed on a substrate, a wet film or a solution layer is formed on the substrate. Wherein the solution process includes, but is not limited to, spin coating, ink jet printing, blade coating, dip coating, dipping, spray coating, roll coating, or casting. In this step, the thickness of the finally formed hole transport film 10 can be controlled and adjusted by controlling and adjusting the conditions such as the concentration of the solution used in the solution method. The thickness of the hole transport film 10 may be 10 to 60nm, such as 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, etc. Taking spin coating as an example, the thickness can be controlled by adjusting the concentration of the solution, the spin coating speed and the spin coating time, for example, the spin coating speed can be 2000-6000rpm/min, and the spin coating time can be 30-90s.
Step S22: and drying to obtain the hole transport film of the metal oxide nano material doped with the triazine framework material.
In the previous step S21, after a wet film or solution layer is formed on the substrate, it is dried in this step, and the solvent is removed to obtain a dried hole transport film.
The drying treatment in this step may be an annealing treatment. The "annealing process" includes all treatment processes that can make the wet film obtain higher energy to change from the wet film state to the dry state, for example, the "annealing process" may refer to only a heat treatment process, that is, heating the wet film to a specific temperature and then maintaining the wet film for a specific time to sufficiently volatilize the solvent in the wet film; as another example, the "annealing process" may further include a heat treatment process and a cooling process sequentially performed, i.e., the wet film is heated to a specific temperature, then kept for a specific time to sufficiently volatilize the solvent in the first wet film, and then cooled at a suitable speed to eliminate the residual stress and reduce the risk of layer deformation and cracking of the dried hole transport film.
It is understood that the kind of the substrate is not limited. In one embodiment, the substrate is an anode substrate, and the hole transport film 10 comprising a triazine backbone material doped metal oxide nanomaterial is disposed on the anode 20. The substrate may be a conventionally used substrate, and may be, for example, a rigid substrate, the material of which is glass; the material of the flexible substrate can be polyimide. The material of the anode 20 may be, for example, one or more of a metal, a carbon material, and a metal oxide, and the metal may be, for example, one or more of Al, ag, cu, mo, au, ba, ca, and Mg; the carbon material may be, for example, one or more of graphite, carbon nanotubes, graphene, and carbon fibers; the metal oxide may be doped or undoped metal oxide, including one or more of ITO, FTO, ATO, AZO, GZO, IZO, MZO and AMO, and also includes a composite electrode sandwiching a metal between doped or undoped transparent metal oxides, including but not limited to AZO/Ag/AZO, AZO/Al/AZO, ITO/Ag/ITO, ITO/Al/ITO, znO/Ag/ZnO, znO/Al/ZnO, tiO/Al/ZnO 2 /Ag/TiO 2 、TiO 2 /Al/TiO 2 、ZnS/Ag/ZnS、ZnS/Al/ZnS、TiO 2 /Ag/TiO 2 And TiO 2 /Al/TiO 2 One or more of (a). In another embodiment, the substrate includes a cathode, an electron transport film, and a light emitting layer, which are stacked, and the hole transport film 10 including a metal oxide nanomaterial doped with a triazine skeleton material is disposed on the light emitting layer.
Referring to fig. 1, an optoelectronic device 100 is also provided in the embodiments of the present application, where the optoelectronic device 100 may be a solar cell, a photodetector, an organic electroluminescent device (OLED), or a quantum dot electroluminescent device (QLED). The photovoltaic device 100 includes an anode 20, a hole transport layer, a light-emitting layer 30, and a cathode 40, which are sequentially stacked.
The material of anode 20 is a material known in the art for anodes and the material of cathode 40 is a material known in the art for cathodes. The material of the anode 20 and the cathode 40 may be, for example, one or more of metal, carbon material, and metal oxide, and the metal may be, for example, one or more of Al, ag, cu, mo, au, ba, ca, and Mg; the carbon material may be, for example, one or more of graphite, carbon nanotubes, graphene, and carbon fibers; the metal oxide may be doped or undoped metal oxide, including one or more of ITO, FTO, ATO, AZO, GZO, IZO, MZO and AMO, and also includes a composite electrode sandwiching a metal between doped or undoped transparent metal oxides, including but not limited to AZO/Ag/AZO, AZO/Al/AZO, ITO/Ag/ITO, ITO/Al/ITO, znO/Ag/ZnO, znO/Al/ZnO, tiO/Al/ZnO 2 /Ag/TiO 2 、TiO 2 /Al/TiO 2 、ZnS/Ag/ZnS、ZnS/Al/ZnS、TiO 2 /Ag/TiO 2 And TiO 2 /Al/TiO 2 One or more of (a). The thickness of the anode 20 may be, for example, 10nm to 200nm, such as 40nm, 60nm, 80nm, etc.; the thickness of the cathode 40 may be, for example, 10nm to 200nm, such as 40nm, 60nm, 80nm, etc.
The hole transport layer is the hole transport film 10, and reference may be made to the above description, which is not repeated herein. The thickness of the hole transport film 10 may range from 10 to 60nm, such as 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, and the like.
The light emitting layer 30 may be an organic light emitting layer or a quantum dot light emitting layer. When the light emitting layer 30 is an organic light emitting layer, the optoelectronic device 100 may be an organic electroluminescent device. When the light emitting layer 30 is a quantum dot light emitting layer, the optoelectronic device 100 may be a quantum dot electroluminescent device. The thickness of the light emitting layer 30 may be, for example, 10nm to 60nm, such as 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, and the like.
Among them, the material of the organic light emitting layer is a material known in the art for the organic light emitting layer, and for example, may be selected from at least one of diarylanthracene derivatives, stilbene 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 material of the quantum dot light-emitting layer is quantum dots known in the art for use in quantum dot light-emitting layers, for example, one of red quantum dots, green quantum dots, and blue quantum dots. The quantum dots may be selected from, but not limited to, at least one of single-structure quantum dots and core-shell structure quantum dots. For example, the quantum dots may be selected from, but are not limited to, one or more of group II-VI compounds, group III-V compounds, and group I-III-VI compounds. By way of example, the group II-VI compound may be selected from, but not limited to, cdSe, cdS, cdTe, znSe, znS, cdTe, znTe, cdZnSe, cdZnTe, zneses, znete, cdSeS, cdSeTe, cdTeS; one or more of CdZnSeS, cdZnSeTe and CdZnSTe; the III-V compound may be selected from, but is not limited to, one or more of InP, inAs, gaP, gaAs, gaSb, alN, alP, inAsP, inNP, inNSb, gaAlNP, and InAlNP; the I-III-VI compound may be selected from, but is not limited to, cuInS 2 、CuInSe 2 And AgInS 2 One or more of (a). The particle size of the quantum dots may be, for example, 5nm to 20nm.
Referring to fig. 1, in an embodiment, the optoelectronic device 100 may further include an electron transport layer 50, wherein the electron transport layer 50 is located between the light-emitting layer 30 and the cathode 40. The material of the electron transport layer 50 may be a material known in the art for use in electron transport layers. For example, it may be selected from, but not limited to, one or more of inorganic nanocrystalline materials, doped inorganic nanocrystalline materials, organic materials. The inorganic nanocrystalline material may include: one or more of zinc oxide, titanium dioxide, tin dioxide, aluminum oxide, calcium oxide, silicon dioxide, gallium oxide and zirconium oxide, wherein the doped inorganic nanocrystalline material comprises one or more of zinc oxide doped impurities, titanium dioxide doped impurities and tin dioxide doped impurities, the doped inorganic nanocrystalline material is an inorganic material doped with other elements, the doped elements are selected from Mg, ca, li, ga, al, co, mn and the like, and the doping proportion can be 0-50%; the organic material may include one or both of polymethyl methacrylate and polyvinyl butyral. The thickness may be, for example, 10nm to 60nm, such as 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, and the like.
It is understood that, besides the above functional layers, some functional layers that are conventionally used in optoelectronic devices and contribute to the performance of optoelectronic devices, such as an electron blocking layer, a hole blocking layer, an electron injection layer, a hole injection layer, an interface modification layer, etc., may be added to the optoelectronic device 100.
It is understood that the materials of the various layers of the optoelectronic device 100 can be tailored to the lighting requirements of the optoelectronic device 100.
It is understood that the optoelectronic device 100 can be an upright optoelectronic device or an inverted optoelectronic device.
The embodiment of the application also provides a display device which comprises the photoelectric 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, an in-vehicle display, a television, or an electronic book reader, wherein the smart wearable device may be a smart bracelet, a smart watch, a Virtual Reality (VR) helmet, or the like.
The embodiment of the present application further provides a method for manufacturing the optoelectronic device 100, which includes a step of manufacturing a hole transport film, and the method for manufacturing the hole transport film is adopted in steps S10 and S20.
Referring to fig. 5, an embodiment of the present application provides a method for manufacturing an optoelectronic device 100, including the following steps:
step S31: providing an anode 20;
step S32: preparing a hole transport film 10 on an anode 20 by a method for preparing the hole transport film 10;
step S33: a light-emitting layer 30 and a cathode 40 are sequentially formed on the hole transport film 10.
It is understood that, when the optoelectronic device 100 further includes the electron transport layer 50, the step S33 is: an electron transport layer 50, a light-emitting layer 30, and a cathode 40 are sequentially formed on the hole transport film 10.
Referring to fig. 6, an embodiment of the present application further provides another method for manufacturing an optoelectronic device 100, including the following steps:
step S41: providing a cathode 40, and forming a light-emitting layer 30 on the cathode 40;
step S42: on the light-emitting layer 30, the hole transport film 10 is prepared by the preparation method of the hole transport film 10;
step S43: an anode 20 is formed on the hole transport film 10.
It is understood that, when the optoelectronic device 100 further includes the electron transport layer 50, the step S41 is: a cathode 40 is provided, and an electron transport layer 50 and a light-emitting layer 30 are sequentially formed on the cathode 40.
It should be noted that the anode 20, the hole transport film 10, the light emitting layer 30, the electron transport layer 50, the cathode 40 and other functional layers can be prepared by conventional techniques in the art, including but not limited to solution processes and deposition processes, wherein the solution processes include but are not limited to spin coating, ink jet printing, blade coating, dip coating, dipping, spray coating, roll coating or casting; deposition methods include chemical methods including, but not limited to, chemical vapor deposition, sequential ionic layer adsorption and reaction, anodization, electrodeposition, or coprecipitation methods, and physical methods including, but not limited to, thermal evaporation coating, electron beam evaporation coating, magnetron sputtering, multi-arc ion coating, physical vapor deposition, atomic layer deposition, or pulsed laser deposition. When the anode 20, the hole transport film 10, the light emitting layer 30, the electron transport layer 50, the cathode 40, and other functional layers are prepared by a solution method, a drying process is added.
It is understood that, when the optoelectronic device 100 further includes other functional layers such as an electron blocking layer, a hole blocking layer, an electron injection layer, a hole injection layer and/or an interface modification layer, the method for manufacturing the optoelectronic device 100 further includes the step of forming each functional layer.
It is understood that the method for manufacturing the optoelectronic device 100 may further include an encapsulation step, the encapsulation material may be acrylic resin or epoxy resin, the encapsulation may be machine encapsulation or manual encapsulation, and the concentration of oxygen and water in the environment where the encapsulation step is performed is lower than 0.1ppm, so as to ensure the stability of the optoelectronic device 100.
The technical solution and the technical effect of the present application will be described in detail by using a comparative example of nickel oxide nanomaterial as a hole transport material and a specific example of nickel oxide nanomaterial doped with triazine framework material, and the following examples are only some examples of the present application and are not intended to limit the present application.
Example 1
In the present embodiment, with reference to fig. 1, a quantum dot light emitting diode 1 of the present embodiment includes an anode 20, a hole transport film 10, a quantum dot light emitting layer 30, an electron transport layer 50, and a cathode 40, which are sequentially stacked, where the hole transport film 10 is composed of a nickel oxide nanomaterial including a triazine-doped framework material.
The quantum dot light-emitting diode comprises the following structures:
the anode 20 is made of ITO (indium tin oxide), the thickness of the anode 20 is 55nm, and one surface of the anode 20 is connected with a glass substrate.
The hole transport film 10 is made of a CTF-1 doped nickel oxide nano material, and the molar ratio of nickel oxide to CTF-1 is 1:1. the thickness of the hole transport film 10 was 60nm. Structure of triazine framework material CTF-1 referring to FIG. 7, CTF-1 is a triazine framework material polymerized by using 1, 3, 5-tricyanobenzene as a monomer, and the polymerization degree is 1200.
The material of the light-emitting layer 30 is Cd x Zn 1-x The thickness of the blue quantum dot with the Se/ZnS core-shell structure is 40nm.
The electron transport layer 50 is made of zinc oxide nano-material and has a thickness of 40nm.
The cathode 40 is made of aluminum and has a thickness of 70nm.
The preparation method of the quantum dot light-emitting diode in the embodiment comprises the following steps:
providing a glass substrate with an ITO anode 20, and pretreating the glass substrate;
providing nickel nitrate hexahydrate, CTF-1 and ethylene glycol, and mixing to obtain a nickel nitrate mixture solution doped with CTF-1, wherein the CTF-1 is a triazine framework material polymerized by taking 1, 3 and 5-tricyanobenzene as a monomer, and the molar ratio of the nickel nitrate hexahydrate to the CTF-1 is 1:1; dissolving sodium hydroxide in ethanol to form an alkali solution; dropwise adding an alkali solution into a CTF-1-doped nickel nitrate mixture solution, adjusting the pH to be =12, and stirring for 1 hour to obtain a CTF-1-doped nickel oxide precursor; spin-coating the precursor solution on the anode 20 to make the precursor completely cover the anode 20, and performing heat treatment on a heating table at 150 ℃ for 60min to obtain a NiOx/CTF-1 composite hole transport film 10 with the thickness of 60 nm; wherein the spin coating speed is 3000rpm/min.
Spin coating Cd onto hole transport layer 10 x Zn 1-x Blue quantum dots with Se/ZnS core-shell structure to obtain a light-emitting layer 30 with the thickness of 40 nm;
spin-coating zinc oxide nano material solution on the luminescent layer 30 to obtain an electron transport layer 50 with the thickness of 40 nm;
evaporating a layer of metal aluminum on the electron transport layer 50 to obtain a cathode 40 with the thickness of 70 nm;
and packaging to obtain the quantum dot light-emitting diode.
Example 2
Compared with the quantum dot light emitting diode of embodiment 1, the quantum dot light emitting diode of the embodiment differs only in that: the hole transport film 10 is made of different materials, the hole transport film 10 in this embodiment is made of a CTF-2 doped nickel oxide nanomaterial, and the molar ratio of nickel oxide to CTF-2 is 1:1.2. the structure of the triazine framework material CTF-2 can be seen from figure 7, wherein CTF-2 is a triazine framework material formed by polymerizing p-cyanobenzene as a monomer, and the polymerization degree is 1500.
Compared with the method for preparing the quantum dot light emitting diode in the embodiment 1, the method for preparing the quantum dot light emitting diode in the embodiment is different only in that: in this embodiment, nickel chloride, CTF-2, and ethylene glycol are provided and mixed to obtain a CTF-2-doped nickel nitrate mixture solution, where CTF-2 is a triazine skeleton material polymerized from p-cyanobenzene as a monomer, and a molar ratio of nickel chloride to CTF-2 is 1:1.2; dissolving potassium hydroxide in ethanol to form an alkali solution; dropwise adding the alkali solution into the CTF-2-doped nickel chloride mixture solution, adjusting the pH =10, and stirring for 1 hour to obtain a CTF-2-doped nickel oxide precursor; and spin-coating the precursor solution on the anode 20 to enable the precursor to completely cover the anode 20, and performing heat treatment on a heating table at 150 ℃ for 90min to obtain the NiOx/CTF-2 composite hole transport film 10 with the thickness of 60nm.
Comparative example
Compared with the quantum dot light-emitting diode in the embodiment 1, the quantum dot light-emitting diode in the embodiment is different only in that: the hole transport film 10 is different in material. The material of the hole transport film 10 of this comparative example is a nickel oxide nanomaterial, and the triazine skeleton material is not doped in the nickel oxide nanomaterial. In this comparative example, the triazine framework material was also added to the nickel oxide precursor solution without mixing.
The external quantum efficiency EQE and the turn-on voltage of the photoelectric devices 100 of examples 1-2 and the photoelectric devices of the comparative examples were tested. Wherein, the external quantum efficiency EQE and the starting voltage are measured by an EQE optical test instrument. The turn-on voltage is the voltage at which the device luminance is 1 nits. The test results are given in table one below.
Table one:
| EQE(％) | starting voltage (V) | |
| Comparative example | 4.5 | 3.53 |
| Example 1 | 8.5 | 2.44 |
| Example 2 | 7.3 | 2.41 |
As can be seen from table one, compared to the quantum dot light emitting diode in which the hole transport film material is the nickel oxide nanomaterial in the comparative example, the quantum dot light emitting diode in which the hole transport film 10 material is the metal oxide nanomaterial doped with the triazine skeleton material in examples 1 and 2 has higher light emitting efficiency and lower turn-on voltage.
In the embodiments 1 and 2, the hole transport film 10 is doped with the added triazine skeleton material, and a strong dipole is induced on the interface to increase the NiOx work function, so that the hole injection barrier is reduced, which is beneficial to the electron-hole injection balance of the quantum dot light emitting diode including the hole transport film 10, the light emitting efficiency of the photoelectric device 100 is improved, the crystallinity and the film forming uniformity of nickel oxide are improved, and the contact with the adjacent functional layer or light emitting layer is optimized, so that the conductivity is better, the carrier transport is more efficient, the leakage current is smaller, and the turn-on voltage is reduced.
The hole transport film and the optoelectronic device provided in the embodiments of the present application are described in detail above, and the principle and the implementation of the present application are explained in the present application by applying specific examples, and the description of the above embodiments is only used to help understanding the method and the core concept of the present application; meanwhile, for those skilled in the art, according to the idea of the present application, the specific implementation manner and the application scope may be changed, and in summary, the content of the present specification should not be construed as a limitation to the present application.
Claims (14)
1. A hole transport film comprising a metal oxide nanomaterial doped with a triazine backbone material.
2. The hole transport film of claim 1, wherein the hole transport film is comprised of a metal oxide nanomaterial doped with a triazine backbone material.
3. The hole-transporting film according to claim 1 or 2, wherein the triazine skeleton material is polymerized from a monomer which is an aromatic group-containing nitrile compound.
4. The hole-transporting film according to claim 3, wherein the aromatic group-containing nitrile compound is selected from the group consisting of cyano-substituted benzene ring compounds, cyano-substituted pyridine compounds, cyano-substituted pyrimidine compounds, cyano-substituted biphenyl compounds, and cyano-substituted naphthalene ring compounds.
5. The hole-transport film according to claim 3, wherein the aromatic group-containing nitrile compound includes at least two cyano groups, and the aromatic group-containing nitrile compound is at least one selected from the group consisting of tricyanobenzene, p-cyanobenzene, biphenyldinitrile, and pyridinedicarbonitrile.
6. The hole transport film according to claim 2, wherein the molar ratio of the metal oxide to the triazine skeleton material in the metal oxide nanomaterial doped with the triazine skeleton material is in the range of 1 (1-1.5).
7. Hole transport according to claim 1 or 2A film, wherein the metal oxide nanomaterial is selected from NiO x 、MoO x 、WO x And CuO x At least one of (a).
8. A method for preparing a hole transport film is characterized by comprising the following steps:
preparing a metal oxide precursor doped with a triazine framework material;
providing a substrate, and arranging the triazine skeleton material-doped metal oxide precursor on the substrate to obtain the hole transport film of the triazine skeleton material-doped metal oxide nano material.
9. The method according to claim 8, wherein the step of preparing the metal oxide precursor doped with the triazine skeleton material comprises:
providing metal salt, a triazine framework material and a solvent, and mixing to obtain a metal salt mixture solution doped with the triazine framework material;
and adding alkali into the metal salt mixture solution to obtain the metal oxide precursor doped with the triazine framework material.
10. The production method according to claim 9, wherein the metal salt is at least one selected from the group consisting of a metal chloride salt, a metal nitrate salt, and a metal acetylacetonate salt; and/or
The alkali is selected from at least one of sodium hydroxide, potassium hydroxide and tetramethyl ammonium hydroxide; and/or
The solvent is at least one selected from methanol, ethanol, glycol, glycerol, butanol, DMF and DMSO.
11. The method according to claim 8, wherein the step of providing a substrate, disposing the triazine skeleton material-doped metal oxide precursor on the substrate, and obtaining the hole transport thin film comprising the triazine skeleton material-doped metal oxide nanomaterial comprises:
providing a substrate, and arranging the metal oxide precursor doped with the triazine framework material on the substrate by adopting a solution method;
and drying to obtain the hole transport film of the metal oxide nano material doped with the triazine framework material.
12. A photoelectric device comprises an anode, a hole transport layer, a light-emitting layer and a cathode which are arranged in a stacking mode, and is characterized in that: the hole transport layer is the hole transport film according to any one of claims 1 to 7, or the hole transport layer is produced by the method for producing the hole transport film according to any one of claims 8 to 11.
13. The optoelectronic device according to claim 12,
the luminescent layer is an organic luminescent layer or a quantum dot luminescent layer, and the material of the organic luminescent layer is at least one of diaryl anthracene derivatives, stilbene aromatic derivatives, pyrene derivatives or fluorene derivatives, blue light-emitting TBPe fluorescent materials, green light-emitting TTPA fluorescent materials, orange light-emitting TBRb fluorescent materials and red light-emitting DBP fluorescent materials; the material of the quantum dot light-emitting layer comprises at least one of II-VI compound, III-V compound and I-III-VI compound; the II-VI compound is at least one selected from 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 InP, inAs, gaP, gaAs, gaSb, alN, alP, inAsP, inNP, inNSb, gaAlNP and InAlNP; the group I-III-VI compound is selected from CuInS 2 、CuInSe 2 And AgInS 2 At least one of (a).
14. A display device, characterized by: the display device comprises an optoelectronic device according to any one of claims 12 to 13.
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| CN202111171832.6A CN115968214A (en) | 2021-10-08 | 2021-10-08 | Hole transport film, preparation method thereof, photoelectric device and display device |
| PCT/CN2022/119697 WO2023056838A1 (en) | 2021-10-08 | 2022-09-19 | Thin film and preparation method therefor, photoelectric device |
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| CN104722212B (en) * | 2013-12-18 | 2017-03-29 | 中国科学院大连化学物理研究所 | A kind of preparation method of covalent triazine skeleton doping hybridized film |
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