Thin film, photoelectric device and display device

Abstract

The invention discloses a thin film, a photoelectric device and a display device. Materials of the thin film comprise an N-type semiconductor material and a two-dimensional material, and the two-dimensional material comprises one or more of graphene oxide and an MXene material. In the thin film provided by the invention, the two-dimensional material and the surface of the N-type semiconductor material form the hydrogen bond through the surface functional group, and due to the reversibility characteristic of the hydrogen bond, the thin film has self-repairing performance and can realize self-repairing through hydrogen bond rearrangement when the thin film generates microcracks.

Description

Technical Field

[0001] The present application relates to the field of semiconductor materials, and particularly to a thin film, an optoelectronic device, and a display device. Background Art

[0002] N-type semiconductor materials refer to semiconductor materials with electron transport or electron injection properties. For example, they can be zinc oxide nanoparticles, titanium dioxide nanoparticles, tin oxide nanoparticles, etc. However, when such materials are made into thin films, cracks or fractures are likely to occur due to scratching or bending, thus affecting their performance. Summary of the Invention

[0003] In view of this, the present application provides a thin film, an optoelectronic device, and a display device.

[0004] The embodiments of the present application are implemented as follows:

[0005] In a first aspect, the present application proposes a thin film. The material of the thin film includes an N-type semiconductor material and a two-dimensional material, and the two-dimensional material includes one or more of graphene oxide and MXene materials.

[0006] In a second aspect, the present application proposes an optoelectronic device, including an anode, an electron functional layer, and a cathode. The material of the electron functional layer includes the thin film as described above, or the electron functional layer includes the thin film as described above.

[0007] In a third aspect, the present application further proposes a display device, and the display device includes the optoelectronic device as described above.

[0008] The technical solution provided by the present application adds a two-dimensional material with surface functional groups to the N-type semiconductor material. The two-dimensional material forms hydrogen bonds with the surface of the N-type semiconductor material through surface functional groups, so that the thin film has self-healing performance and can achieve self-healing through hydrogen bond rearrangement when microcracks occur. Brief Description of the Drawings

[0009] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the following will briefly introduce the drawings required for the description of the embodiments. Obviously, the following drawings are only some embodiments of the present application. For those skilled in the art, other drawings can be obtained based on these drawings without creative efforts.

[0010] Figure 1 is a schematic structural diagram of an optoelectronic device proposed in an embodiment of the present application;

[0011] Reference Signs:

[0012] 100 - Optoelectronic device; 10 - Anode; 20 - Light - emitting layer; 30 - Electron - transporting layer; 40 - Cathode; 50 - Hole - transporting layer; 60 - Hole - injecting layer. Detailed implementation manners

[0013] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments of the present application, all other embodiments obtained by those skilled in the art without creative efforts belong to the scope of protection of the present application. In addition, it should be understood that the specific implementation manners described herein are only for explaining and understanding the present application, and are not used to limit the present application.

[0014] In the present application, unless otherwise stated, the orientation terms such as "upper" and "lower" specifically refer to the drawing directions in the accompanying drawings. In addition, in the description of the specification of the present application, the term "including" means "including but not limited to".

[0015] The various embodiments of the present application may exist in the form of a range; it should be understood that the description in the form of a range is only for convenience and brevity, and should not be construed as a rigid limitation on the scope of the present application; therefore, it should be considered that the described range description has specifically disclosed all possible sub - ranges and single values within that range. For example, it should be considered that the range description from 1 to 6 has specifically disclosed sub - ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., and single numbers within that range, such as 1, 2, 3, 4, 5, and 6, regardless of the range. In addition, whenever a numerical range is indicated herein, it means including any cited number (fraction or integer) within the indicated range.

[0016] In the present application, "and / or" describes the association relationship of associated objects, indicating that there can be three relationships. For example, A and / or B can represent: A exists alone, A and B exist simultaneously, and B exists alone. Wherein A and B can be singular or plural.

[0017] In the present application, "at least one" means one or more, and "a plurality" means two or more. "At least one kind", "at least one of the following items (pieces)" or similar expressions refer to any combination of these items, including any combination of single item (piece) or plural items (pieces). For example, "at least one of (a, b, or c)", or, "at least one of (a, b, and c)" can both represent: a, b, c, a - b (that is, a and b), a - c, b - c, or a - b - c, where a, b, and c can be single or multiple respectively.

[0018] The technical solution of this application is implemented as follows:

[0019] In a first aspect, this application provides a thin film. The material of the thin film includes an N-type semiconductor material and a two-dimensional material with surface functional groups. The two-dimensional material includes one or more of graphene oxide and MXene materials.

[0020] Graphene oxide is an oxide of graphene, generally denoted as GO. Graphene oxide is a sheet-like two-dimensional material, and its surface contains a large number of functional groups, including but not limited to hydroxyl groups, epoxy groups, carboxyl groups, etc. The Mxene material presents a sheet-like morphology and is also a two-dimensional material. Its surface has a large number of functional groups. Specifically, the chemical general formula of the Mxene material is M n+ 1X n T x , M is selected from at least one of transition metals, X is selected from C or N, the value of n is 1 to 3, and T x includes O 2- 、OH - 、F - any one or several of them; among them, the transition metal can be selected from one or more of any transition metal elements known in the art. For example, Ti, Zr, Hf, V, Nb, Ta, Cr, Sc, etc.; T x refers to the group on the surface of the two-dimensional material.

[0021] The N-type semiconductor material refers to an N-type metal oxide and / or doped N-type metal oxide with electron transport or injection performance. The N-type semiconductor material is usually prepared by a sol-gel method or a hydrothermal method, and hydroxyl groups are often connected to its surface.

[0022] In the technical solution provided by this application, a two-dimensional material with surface functional groups is added to the N-type semiconductor material. The two-dimensional material forms a dynamic reversible hydrogen bond with the hydroxyl groups existing on the surface of the N-type semiconductor material through the surface functional groups. Due to the reversibility of the hydrogen bond, the thin film has self-healing performance, enabling the thin film to achieve self-healing through hydrogen bond rearrangement when microcracks occur.

[0023] In addition, graphene oxide and MXene materials have electron transport and injection performance. Adding them to the N-type semiconductor material helps improve the charge transport ability of the thin film.

[0024] In some specific embodiments, the Mxene material includes Ti2CT x 、TiNbCT x 、Ti3CN x T x 、Ta4C3T x 、Nb2CT x 、V2CT x, Nb4C3T x , Mo2CT x , Ti4N3T x At least one of them, where T x includes O 2- , OH - , F - At least one of them.

[0025] In some embodiments, in the thin film, the mass ratio of the two-dimensional material to the N-type semiconductor material is 1:(2 - 20); for example, it can be 1:5, 1:8, 1:10, 1:12, 1:15, 1:18, 1:20, and values between any two of the above; controlling the mass ratio of the two-dimensional material to the N-type semiconductor material within this range helps to improve the self-healing performance of the material while ensuring that the material has a high charge transport ability.

[0026] In some embodiments, the material of the thin film further includes a complexing agent, which refers to a compound that can complex with metal cations in the N-type semiconductor material. The complexing agent further enhances the self-healing performance of the thin film by forming dynamic reversible coordination bonds with the N-type semiconductor material. The complexing agent can be a common complexing agent with coordinating atoms capable of chelating metal ions. For example, it can include, but is not limited to, one or more of ethylenediaminetetraacetic acid, dimercaptopropanol, dimercaptopropanesulfonic acid, mercaptoethylamine, and mercaptoacetic acid.

[0027] Furthermore, in some embodiments, in the thin film, the mass ratio of the complexing agent to the N-type semiconductor material is 1:(8 - 12); for example, it can be 1:8, 1:9, 1:10, 1:11, 1:12, and values between any two of the above; controlling the mass ratio of the complexing agent to the N-type semiconductor material within this range helps to improve the self-healing performance of the thin film while avoiding interference of the complexing agent with the charge transport ability of the material.

[0028] In some other embodiments, the material of the thin film further includes a first compound, and the first compound includes one or more of the compounds having the structure of formula (1):

[0029] Formula (1): R 1 -L-R 2 ;

[0030] Wherein, R 1 , R 2 are each independently selected from any one of hydroxyl, carboxyl, and amino; L is selected from substituted or unsubstituted C2 - C20 straight-chain alkylene groups; the substituents include one or more of hydroxyl, carboxyl, amino, C1 - C10 alkyl groups, C1 - C10 alkoxy groups, and C1 - C10 alkyl carbonyl groups.

[0031] The first compound has hydroxyl, carboxyl, and amino active groups. On the one hand, these groups can form multiple hydrogen bonds with two-dimensional materials and N-type semiconductor materials. On the other hand, they can also crosslink with oxygen-containing groups in two-dimensional materials and N-type semiconductor materials, such as hydroxyl and carboxyl groups, thereby greatly enhancing the self-healing property of the material. In some other embodiments, the material of the thin film includes two-dimensional materials, complexing agents, the first compound, and N-type semiconductor materials. In the material, hydrogen bonds are formed between two-dimensional materials and N-type semiconductor materials, coordination bonds are formed between complexing agents and N-type semiconductor materials, and at the same time, multiple hydrogen bonds are formed between the first compound and two-dimensional materials, complexing agents, and N-type semiconductor materials, greatly enhancing the self-healing performance of the thin film.

[0032] In some embodiments, the number of active groups (total number of hydroxyl, carboxyl, and amino groups) contained in the structural formula of the first compound is 2 to 6, such as 2, 3, 4, 5, 6 active groups, which helps to form multiple hydrogen bonds and enhance the self-healing property of the material.

[0033] In some embodiments, in the thin film, the mass ratio of the first compound to the N-type semiconductor material is 1:(5 to 10); for example, it can be 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, and values between any two of the above; controlling the mass ratio of the first compound to the N-type semiconductor material within this range helps to ensure good film-forming property of the thin film while enhancing the self-healing performance of the material.

[0034] In some embodiments, the boiling point of the first compound is greater than or equal to 80 °C. In this way, the first compound is not easily volatile, and during the preparation of the thin film, the heat treatment process during the preparation can be avoided from destroying the multiple hydrogen bonds between the first compound and other materials.

[0035] In some embodiments, the first compound includes one or more of C2-C10 polyols, C2-C10 polyamines, and C2-C10 amino alcohol compounds. C2-C10 means containing 2 to 10 carbon atoms. Specifically, in some embodiments, the C2-C10 polyols include one or more of ethylene glycol, glycerol, and butanediol; the C2-C10 polyamines include one or more of ethylenediamine, methyl triamine, ethyl triamine, propyl triamine, and dimethyl triamine; the C2-C10 amino alcohol compounds include one or more of methylethanolamine, ethylethanolamine, 2-dibutylaminoethanol, and 2-diethylaminoethanol.

[0036] In some other embodiments, the first compound includes one or more of C2-C10 polyacids. Specifically, the C2-C10 polyacids include one or more of oxalic acid, malonic acid, and succinic acid.

[0037] In some embodiments, the N-type semiconductor material includes one or more of N-type metal oxides or doped N-type metal oxides. The N-type metal oxides include one or more of ZnO, TiO2, SnO2, and ZrO2. The N-type metal oxides in the doped N-type metal oxides include one or more of ZnO, TiO2, SnO2, and ZrO2, and the doping elements include one or more of Al, Mg, Li, In, and Ga. When the N-type semiconductor material is selected from the above N-type semiconductor particles, the corresponding thin film can have electron transport or injection properties. Specifically, it can be used to prepare the electron functional layer of the optoelectronic device 100.

[0038] Based on the above embodiments of the thin film, a method for preparing the thin film is further proposed. The preparation method includes: dispersing the material of the thin film in a solvent to form a mixed solution; providing a substrate, depositing the mixed solution on the substrate, and then removing the solvent to form a thin film. Among them, the material of the thin film refers to N-type semiconductor material and two-dimensional material in some embodiments; in other embodiments, it refers to N-type semiconductor material, two-dimensional material, and complexing agent, or N-type semiconductor material, two-dimensional material, and a first compound; in still other embodiments, it refers to N-type semiconductor material, two-dimensional material, complexing agent, and a first compound. Among them, the solvent refers to C1-C6 alcohol solvents, such as methanol, ethanol, isopropanol, n-butanol, pentanol, n-hexanol, etc.; the substrate can be a common substrate such as a glass substrate or a flexible substrate, or a certain film layer of a prefabricated semi-finished device. For example, it can be the light-emitting layer 20 of a prefabricated device (including an anode 10, a hole injection layer 60, a hole transport layer 50, and a light-emitting layer 20 stacked in sequence from bottom to top). The step of removing the solvent can be achieved by vacuum pumping or thermal annealing. Specifically, the step of vacuum pumping includes: standing for 15-25 min in an environment of 10 -1 ~10 -2 mTorr; the step of thermal annealing includes: baking at 75-85 °C for 8-12 min.

[0039] In a second aspect, the present application also proposes an optoelectronic device 100. The optoelectronic device 100 can be an organic light-emitting diode (OLED), a quantum dot light-emitting diode (QLED), a solar cell, etc. For ease of description, the structure of the optoelectronic device 100 will be specifically described below by taking a light-emitting diode as an example. Please refer to Figure 1 , which includes an anode 10, an electron functional layer, and a cathode 40. The material of the electron functional layer includes a composition; or the electron functional layer includes a thin film, and the material of the thin film includes an N-type semiconductor material and a two-dimensional material with surface functional groups. The two-dimensional material includes one or more of graphene oxide and MXene materials.

[0040] The technical solution provided by this application uses the thin film preparation of the electronic functional layer described above, so that the electronic functional layer has self-healing performance and can self-heal when cracks appear in the electronic functional layer, thereby effectively reducing the leakage problem of the device caused by cracks, helping to improve the yield of the device, and ensuring the light emission uniformity of the device. In addition, graphene oxide and MXene materials have electron transport and injection properties. Adding them to the N-type semiconductor material helps to improve the charge transport ability of the material, and further helps to improve the light emission performance of the device.

[0041] It can be understood that the electronic functional layer includes one or both of an electron transport layer 30 and an electron injection layer. When the hole functional layer includes an electron transport layer 30 and an electron injection layer, the electron transport layer 30 and the electron injection layer are stacked, and the electron injection layer is located between the electron transport layer 30 and the cathode 40.

[0042] In some embodiments, the anode 10 can be an anode 10 known in the art for use in the optoelectronic device 100. For example, it can be selected from, but not limited to, doped metal oxide particle electrodes, composite electrodes of metals and metal oxides, graphene electrodes, carbon nanotube electrodes, metal electrodes or alloy electrodes. The material of the doped metal oxide particle electrode is selected from one or more of indium-doped tin oxide, fluorine-doped tin oxide, antimony-doped tin oxide, aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, magnesium-doped zinc oxide, and aluminum-doped magnesium oxide. The composite electrode of metals and metal oxides is selected from AZO / Ag / AZO, AZO / Al / AZO, ITO / Ag / ITO, ITO / Al / ITO, ZnO / Ag / ZnO, ZnO / Al / ZnO, TiO2 / Ag / TiO2, TiO2 / Al / TiO2, ZnS / Ag / ZnS, ZnS / Al / ZnS. The material of the metal electrode is selected from one or more of Ag, Al, Cu, Mo, Au, Pt, Si, Ca, Mg, and Ba. Among them, " / " represents a stacked structure. For example, the composite electrode AZO / Ag / AZO represents an electrode with a three-layer stacked composite structure composed of an AZO layer, an Ag layer, and an AZO layer.

[0043] In some embodiments, the cathode 40 can be a cathode 40 known in the art for optoelectronic devices 100. For example, it can be selected from, but not limited to, doped metal oxide particle electrodes, composite electrodes of metal and metal oxide, graphene electrodes, carbon nanotube electrodes, metal electrodes or alloy electrodes. The material of the doped metal oxide particle electrode is selected from one or more of indium-doped tin oxide, fluorine-doped tin oxide, antimony-doped tin oxide, aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, magnesium-doped zinc oxide and aluminum-doped magnesium oxide. The composite electrode of metal and metal oxide is selected from AZO / Ag / AZO, AZO / Al / AZO, ITO / Ag / ITO, ITO / Al / ITO, ZnO / Ag / ZnO, ZnO / Al / ZnO, TiO2 / Ag / TiO2, TiO2 / Al / TiO2, ZnS / Ag / ZnS, ZnS / Al / ZnS. The material of the metal electrode is selected from one or more of Ag, Al, Cu, Mo, Au, Pt, Si, Ca, Mg and Ba. Among them, " / " represents a laminated structure. For example, the composite electrode AZO / Ag / AZO represents an electrode with a three-layer laminated composite structure composed of an AZO layer, an Ag layer and an AZO layer.

[0044] In some embodiments, the optoelectronic device 100 may further include a light-emitting layer 20, and the light-emitting layer 20 is disposed between the electronic functional layer and the anode 10. The material of the light-emitting layer 20 may adopt common light-emitting materials in the art, for example, it may include one or more of organic light-emitting materials and quantum dot light-emitting materials. The organic light-emitting materials are selected from one or more of 4,4'-bis(N-carbazolyl)-1,1'-biphenyl: tris[2-(p-tolyl)pyridine iridium(III)], 4,4',4”-tris(carbazol-9-yl)triphenylamine: tris[2-(p-tolyl)pyridine iridium, poly[(9,9-dioctylfluorene-2,7-diyl)-alternating-(2,1,3-benzothiadiazole-4,7-diyl)], diarylanthracene derivatives, stilbene aromatic derivatives, pyrene derivatives, fluorene derivatives, TBPe fluorescent materials, TTPX fluorescent materials, TBRb fluorescent materials, DBP fluorescent materials, delayed fluorescence materials, TTA materials, thermally activated delayed materials, polymers containing B-N covalent bonds, hybrid local charge transfer excited state materials, exciplex light-emitting materials; the quantum dot light-emitting materials are selected from at least one of single-structure quantum dots, core-shell structure quantum dots, and perovskite semiconductor materials; the materials of the single-structure quantum dots, the core materials of the core-shell structure quantum dots, and the shell materials of the core-shell structure quantum dots are respectively selected from at least one of II-VI group compounds, IV-VI group compounds, III-V group compounds, and I-III-VI group compounds; the II-VI group compounds are selected from at least one of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, and HgZnSTe; the IV-VI group compounds are selected from at least one of SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, SnPbSeTe, and SnPbSTe;The group III-V compound is selected from at least one of GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs and InAlPSb; the group I-III-VI compound is selected from at least one of CuInS2, CuInSe2 and AgInS2. As an example, the quantum dots of the core-shell structure can be selected from but not limited to at least one of CdZnSe / CdZnSe / ZnSe / CdZnS / ZnS, CdZnSe / CdZnSe / CdZnS / ZnS CdSe / CdSeS / CdS, InP / ZnSeS / ZnS, CdZnSe / ZnSe / ZnS, CdSeS / ZnSeS / ZnS, CdSe / ZnS, CdSe / ZnSe / ZnS, ZnSe / ZnS, ZnSeTe / ZnS, CdSe / CdZnSeS / ZnS and InP / ZnSe / ZnS. It should be noted that for the materials of the aforementioned single-structure quantum dots, or the core materials of the core-shell structure quantum dots, or the shell materials of the core-shell structure quantum dots, the chemical formulas provided only indicate the elemental composition and do not indicate the content of each element. For example, CdZnSe only represents being composed of three elements, Cd, Zn and Se. If the content of each element is to be represented, it corresponds to Cd; x Zn 1-x Se, 0 < x < 1.

[0045] The perovskite semiconductor material is selected from doped or undoped inorganic perovskite semiconductors, or organic-inorganic hybrid perovskite semiconductors; the general structural formula of the inorganic perovskite semiconductor is AMX3, where 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 them, X is a halogen anion, selected from Cl - , Br - , I - At least one of them; the structural general formula of the organic-inorganic hybrid perovskite semiconductor is BMX3, where B is an organic amine cation, selected from CH3(CH2) n-2 NH 3+ or [NH3(CH2) n NH3] 2+ , where n≥2, M is a divalent metal cation, selected from Pb 2+ , Sn 2+ , Cu 2+ , Ni 2+ , Cd 2+ , Cr 2+ , Mn 2+ , Co 2+ , Fe 2+ , Ge 2+ , Yb 2+ , Eu 2+ At least one of them, X is a halogen anion, selected from Cl - , Br - , I - At least one of them.

[0046] In some embodiments, the optoelectronic device 100 further includes a hole functional layer disposed between the electronic functional layer and the anode 10; when the optoelectronic device 100 further includes a light-emitting layer 20, the hole functional layer is disposed between the light-emitting layer 20 and the anode 10. The hole functional layer includes one or both of a hole transport layer 50 and a hole injection layer 60. When the hole functional layer includes the hole transport layer 50 and the hole injection layer 60, the hole transport layer 50 and the hole injection layer 60 are stacked, and the hole injection layer 60 is located between the hole transport layer 50 and the anode 10. The hole functional layer can be prepared from hole functional materials known in the art for the optoelectronic device 100 and having hole transport performance or hole injection performance. Specifically, the material of the hole transport layer 50 may include, but is not limited to, poly(9,9-dioctylfluorene-co-N-(4-butylphenyl)diphenylamine) (TFB), polyvinylcarbazole (PVK), poly(N,N'-bis(4-butylphenyl)-N,N'-bis(phenyl)benzidine) (poly-TPD), poly(9,9-dioctylfluorene-co-bis-N,N-phenyl-1,4-phenylenediamine) (PFB), 4,4',4''-tris(carbazol-9-yl)triphenylamine (TCATA), 4,4'-bis(9-carbazolyl)biphenyl (CBP), N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine (TPD), N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine (NPB), poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonic acid) (PEDOT:PSS), Spiro-NPB, Spiro-TPD, doped graphene, undoped graphene, C60, doped or undoped NiO, doped or undoped MoO3, doped or undoped WO3, doped or undoped V2O5, p-type gallium nitride, doped or undoped CrO3, doped or undoped CuO; the material of the hole injection layer 60 may include, but is not limited to, PEDOT:PSS (poly(3,4-ethylenedioxythiophene)-polystyrenesulfonic acid), CuPc, TiOPc (phthalocyanine oxotitanium), mMTDATA (CAS: 124729-98-2), 2-TNATA (4,4',4''-tris(2-naphthylphenylamino)triphenylamine), transition metal oxides, one or more of transition metal chalcogenides. Among them, the transition metal oxides include NiO x , MoO x , WO x , CrO x , CuO; one or more of the metal chalcogenides include MoS x , MoSe x , WS x , WSe x, one or more of CuS.

[0047] It can be understood that the optoelectronic device 100 can also be provided with some functional layers that are commonly used in optoelectronic devices 100 and are helpful for improving the performance of the optoelectronic device 100, such as an electron blocking layer, a hole blocking layer, etc.

[0048] It can be understood that the materials of the respective layers of the optoelectronic device 100 can be adjusted according to the actual requirements of the optoelectronic device 100.

[0049] It can be understood that the optoelectronic device 100 can be a normal structure device or an inverted structure device.

[0050] When there are multiple film layers provided between the anode 10 and the cathode 40, and the multiple film layers are selected from the light-emitting layer 20, the electron transport layer 30, the hole transport layer 50, and the hole injection layer 60, the film layer stacking order of the optoelectronic device 100 is the anode 10, the hole injection layer 60, the hole transport layer 50, the light-emitting layer 20, the electron transport layer 30, and the cathode 40; it can be understood that the optoelectronic device 100 can be a normal structure device or an inverted structure device. In some embodiments, the optoelectronic device 100 is a normal structure device. Correspondingly, the optoelectronic device 100 includes, from bottom to top in sequence, the anode 10, the hole injection layer 60, the hole transport layer 50, the light-emitting layer 20, the electron transport layer 30, and the cathode 40; in other embodiments, the optoelectronic device 100 is an inverted structure device. Correspondingly, the optoelectronic device 100 includes, from bottom to top in sequence, the cathode 40, the electron transport layer 30, the light-emitting layer 20, the hole transport layer 50, the hole injection layer 60, and the anode 10.

[0051] Based on the above embodiments of the optoelectronic device 100, the present application also proposes a method for manufacturing an optoelectronic device 100. The manufacturing method includes the following steps: sequentially manufacturing multiple film layers according to a preset film layer order to obtain the optoelectronic device 100; wherein, the multiple film layers include the anode 10, the cathode 40, and at least one functional layer provided between the anode 10 and the cathode 40. The at least one functional layer includes at least one of the light-emitting layer 20, the hole transport layer 50, and the hole injection layer 60, and the electron transport layer 30. Among them, the preset film layer order refers to the order in which the optoelectronic device 100 is stacked from bottom to top.

[0052] In the optoelectronic device 100 provided by the present application, for the functional layer, the anode 10, and the cathode 40, conventional preparation methods can also be used for preparation. Specifically, the conventional preparation methods can be chemical methods or physical methods. Among them, the chemical methods include chemical vapor deposition, sequential ionic layer adsorption and reaction, anodic oxidation, electrodeposition, and coprecipitation. The physical methods include physical coating methods and solution methods. Among them, the physical coating methods include: thermal evaporation coating, electron beam evaporation coating, magnetron sputtering, multi-arc ion coating, physical vapor deposition, atomic layer deposition, pulsed laser deposition, etc.; the solution method can be spin coating, printing, inkjet printing, blade coating, printing, dip coating, immersion, spraying, roll coating, casting, slot die coating, and bar coating, etc.

[0053] In some embodiments, after the optoelectronic device 100 is prepared, it further includes the step of encapsulating the optoelectronic device 100. The encapsulation process can use common machine encapsulation or manual encapsulation. Preferably, in the environment of the encapsulation process, both the oxygen content and the water content are lower than 0.1 ppm to ensure the stability of the optoelectronic device 100.

[0054] In addition, the present application also relates to a display device, and the display device includes the optoelectronic device 100 described above. The display device can be any electronic product with a display function. The electronic products include but are not limited to smartphones, tablet computers, laptop computers, digital cameras, digital video cameras, smart wearable devices, smart weighing electronic scales, in-vehicle displays, televisions, or e-book readers. Among them, the smart wearable devices can be, for example, smart bracelets, smart watches, virtual reality (VR) helmets, etc.

[0055] Hereinafter, the technical solutions and technical effects of the present application will be described in detail through specific examples and comparative examples. The following examples are only partial examples of the present application and do not specifically limit the present application.

[0056] Film Example 1

[0057] (1) According to the mass ratio of the N-type semiconductor material to the two-dimensional material of 5:1, the N-type semiconductor material and the two-dimensional material are dispersed in ethanol to form a mixed solution. In the solution, the concentration of the N-type semiconductor material is 30 mg / ml. Among them, the N-type semiconductor material is Mg-doped ZnO nanoparticles (abbreviated as ZMO, with an average particle size of 4 nm), and among them, the doping concentration of Mg is 10 wt%; the two-dimensional material is Mxene material Ti3C2T x .

[0058] (2) Spin-coat the mixed solution on a polyethylene naphthalate (PEN) substrate at a spin-coating speed of 3000 rpm for 30 s, and then bake it at 80 °C for 10 min to form a film with a thickness of 50 nm.

[0059] Film Example 2

[0060] This film example is basically the same as Film Example 1, except that in this film example, in step (1), the two-dimensional material is changed to graphene oxide.

[0061] Film Example 3

[0062] This film example is basically the same as Film Example 1, except that in this film example, the composition further includes a first compound. Correspondingly, step (1) is changed to:

[0063] Disperse the N-type semiconductor material, two-dimensional material, and first compound in ethanol according to the mass ratio of 10:1:1 of the N-type semiconductor material, two-dimensional material, and first compound to form a mixed solution. In the solution, the concentration of the N-type semiconductor material is 30 mg / ml. Among them, the N-type semiconductor material is Mg-doped ZnO nanoparticles (abbreviated as ZMO, with an average particle size of 4 nm), and among them, the doping concentration of Mg is 10 wt%; the two-dimensional material is Mxene material Ti3C2T x ; the first compound is glycerol.

[0064] Film Example 4

[0065] This film example is basically the same as Film Example 3, except that in this film example, in step (1), the first compound is changed to succinic acid.

[0066] Film Example 5

[0067] This film example is basically the same as Film Example 3, except that in this film example, in step (1), the first compound is changed to ethylenediamine.

[0068] Film Example 6

[0069] This film example is basically the same as Film Example 3, except that in this film example, in step (1), the first compound is changed to methylethanolamine.

[0070] Film Example 7

[0071] This film example is basically the same as Film Example 3, except that in this film example, the composition further includes a complexing agent. Correspondingly, step (1) is changed to:

[0072] Disperse the N-type semiconductor material, two-dimensional material, first compound, and complexing agent in ethanol at a mass ratio of 10:1:1:1 to prepare a mixed solution. In the solution, the concentration of the N-type semiconductor material is 30 mg / ml.

[0073] Among them, the N-type semiconductor material is Mg-doped ZnO nanoparticles (abbreviated as ZMO, with an average particle size of 4 nm), and the doping concentration of Mg is 10 wt%; the two-dimensional material is Mxene material Ti3C2T x ; the first compound is glycerol; the complexing agent is ethylenediaminetetraacetic acid.

[0074] Film Example 8

[0075] This material example is basically the same as Material Example 1, except that in this material example, the composite material also includes a complexing agent. Correspondingly, step (1) is changed to:

[0076] Disperse the N-type semiconductor material, two-dimensional material, and complexing agent in ethanol at a mass ratio of 10:1:1 to prepare a composite material solution. In the solution, the concentration of the N-type semiconductor material is 30 mg / ml.

[0077] Among them, the N-type semiconductor material is Mg-doped ZnO nanoparticles (abbreviated as ZMO, with an average particle size of 4 nm), and the doping concentration of Mg is 10 wt%; the two-dimensional material is Mxene material Ti3C2T x ; the complexing agent is ethylenediaminetetraacetic acid.

[0078] Film Comparative Example 1

[0079] This film comparative example is basically the same as Film Example 1, except that in this film comparative example, the composition is ZMO nanoparticles; correspondingly, the mixed solution is an ethanol solution of ZMO, and the concentration of ZMO is 30 mg / ml.

[0080] Device Example 1

[0081] (1) Use a flexible substrate with an ITO electrode structure as the anode, with a thickness of 75 nm. After cleaning, perform ultraviolet-ozone treatment for 15 min to improve the surface performance of the substrate;

[0082] (2) Spin-coat PEDOT:PPS on the treated ITO anode, and then bake it at 150 °C for 15 min to obtain a hole injection layer with a thickness of 40 nm.

[0083] (3) Spin-coat a chlorobenzene solution of TFB on the hole injection layer, and then bake it at 150 °C for 20 min to obtain a hole transport layer with a thickness of 40 nm.

[0084] (4) Spin-coat 25 nm thick green light quantum dots CdZnSe / CdS on the hole transport layer, and then bake it at 100 °C for 5 min to obtain a light-emitting layer.

[0085] (5) Spin-coat the mixed solution prepared in step (1) of Film Example 1 on the light-emitting layer, and then bake it at 80 °C for 10 min to obtain an electron transport layer with a thickness of 50 nm.

[0086] (6) Vacuum deposit 100 nm thick Ag on the electron transport layer to obtain a cathode, and then encapsulate it to obtain an optoelectronic device.

[0087] Device Examples 2 to 8

[0088] The scheme of Device Example n is basically the same as that of Device Example 1, except that in Device Example n, in step (5), the spin-coated solution is changed to the mixed solution prepared in Film Example n, where n is from 2 to 8.

[0089] Device Comparative Example 1

[0090] The scheme of this device comparative example is basically the same as that of Device Example 1, except that in step (5) of this device comparative example, the spin-coated solution is changed to the mixed solution prepared in Film Comparative Example 1.

[0091] Experimental Example

[0092] (1) Take the films prepared in the above Film Examples and Film Comparative Examples for testing. The results are shown in Table 1.

[0093] The detection method is as follows: Cut the film into a width of 2 cm and a length of 10 cm, and conduct a bending experiment on a universal testing machine for 10,000 cycles; Use an atomic force microscope to measure its roughness to characterize the morphology before and after bending.

[0094] Roughness growth rate (%) = (Roughness after bending test - Roughness before bending test) / Roughness before bending test * 100%.

[0095] Table 1

[0096]

[0097] After testing, cracks appeared in the film of Comparative Example 1 of the film after 10,000 bends, while the films of each film example had a better film-forming effect; it can also be seen from the detection data in the above table that compared with Comparative Example 1 of the film, each film example had a lower roughness growth rate, indicating that the increase in surface roughness of the film of the film example after 10,000 cycles of bending was smaller than that of Comparative Example 1 of the material, indicating that the film proposed in this application had strong self-healing performance and could still ensure a good microscopic morphology after multiple bends;

[0098] Furthermore, among the film examples, Film Examples 7 and 8 had the smallest roughness growth rate, followed by Film Examples 3 to 6, and the largest were Film Examples 1 to 2, indicating that adding a complexing agent and a first compound helped to further enhance the self-healing performance of the material and improve the cracking situation of the film after multiple bends.

[0099] (2) Test the devices prepared in the above device examples and device comparative examples. The detection method refers to the conventional methods in the art, and the results are recorded in Table 2.

[0100] The detection method is as follows:

[0101] Use a photometer to detect the initial brightness L0; then use a universal testing machine to perform cyclic bending on the device. After 10,000 bends, detect its brightness L1 again, and calculate its brightness change rate (%) = (L0 - L1) / L0 * 100%.

[0102] Table 2

[0103] <![CDATA[L0(cd / cm 2 )]]> <![CDATA[L1 (cd / cm 2 )]]> Rate of change (%) Device Example 1 18500 14500 21.6％ Device Example 2 20000 15000 25.0％ Device Example 3 19500 16500 15.4％ Device Example 4 18200 15000 17.6％ Device Example 5 17500 14200 18.9％ Device Example 6 17000 14000 17.6％ Device Example 7 20000 18500 7.5％ Device Example 8 19000 17000 10.5％ Device Comparative Example 1 15000 5000 66.7％

[0104] It can be seen from the above table that:

[0105] Compared with Device Comparative Example 1, each device example had a lower brightness change rate, indicating that the brightness decrease of the device of the device example after 10,000 cycles of bending was smaller than that of Device Comparative Example 1, indicating that the optoelectronic device proposed in this application had strong self-healing performance and could still ensure good luminescence performance after multiple bends;

[0106] Furthermore, among the device examples, Device Examples 7 and 8 had the smallest brightness change rate, followed by Device Examples 3 to 6, and the largest were Device Examples 1 to 2, indicating that adding a complexing agent and a first compound helped to further enhance the self-healing performance of the material, thereby improving the yield of the device and ensuring that the device still had good luminescence performance after multiple bends.

[0107] The above has introduced in detail the thin film, optoelectronic device and display device provided by the embodiments of the present application. Specific examples are used in this article to elaborate on the principle and implementation manner of the present application. The description of the above embodiments is only used to help understand the method and its core idea of the present application; at the same time, for those skilled in the art, according to the idea of the present application, there will be changes in the specific implementation manner and application scope. In summary, the content of this specification should not be construed as a limitation to the present application.

Claims

1. A thin film, characterized in that, The material of the thin film includes an N-type semiconductor material and a two-dimensional material, and the two-dimensional material includes one or more of graphene oxide and MXene material.

2. The thin film according to claim 1, wherein The Mxene material includes Ti2CT x , TiNbCT x , Ti3CN x T x , Ta4C3T x , Nb2CT x , V2CT x , Nb4C3T x , Mo2CT x , Ti4N3T x and at least one of the following, where T x includes at least one of O 2- , OH - , F - .

3. The thin film according to claim 1, characterized in that, In the thin film, the mass ratio of the two-dimensional material to the N-type semiconductor material is 1:(2-20); and / or, The two-dimensional material and the N-type semiconductor material are connected by hydrogen bonds.

4. The thin film according to claim 1, wherein The material of the thin film further includes a complexing agent, and the complexing agent includes one or more of ethylenediaminetetraacetic acid, dimercaptopropanol, dimercaptopropanesulfonic acid, mercaptoethylamine, and mercaptoacetic acid; and / or, The material of the thin film further includes a first compound, and the first compound includes one or more of the compounds having the structure of formula (1): Formula (1): R 1 -L-R 2 ; Among them, R 1 and R 2 are each independently selected from any one of hydroxyl, carboxyl, and amino; L is selected from substituted or unsubstituted C2-C20 straight-chain alkylene groups; The substituents include one or more of hydroxyl, carboxyl, amino, C1-C10 alkyl, C1-C10 alkoxy, and C1-C10 alkylcarbonyl.

5. The thin film according to claim 4, wherein In the thin film, the mass ratio of the complexing agent to the N-type semiconductor material is 1:(8-12); and / or, In the thin film, the mass ratio of the first compound to the N-type semiconductor material is 1:(5-10); and / or, The boiling point of the first compound is greater than or equal to 80 °C; and / or, The complexing agent is coordinately connected to the N-type semiconductor material; and / or, The first compound is connected to the N-type semiconductor material by hydrogen bonds.

6. The thin film according to claim 5, characterized in that, The first compound includes one or more of C2-C10 polyols, C2-C10 polyamines, and C2-C10 alkanolamines; or, The first compound includes one or more of C2-C10 polyacids.

7. The thin film according to claim 6, wherein The C2-C10 polyols include one or more of ethylene glycol, glycerol, and butanediol; and / or, The C2-C10 polyacids include one or more of oxalic acid, malonic acid, and succinic acid; and / or, The C2-C10 polyamines include one or more of ethylenediamine, methyltriamine, ethyltriamine, propyltriamine, and dimethyltriamine; and / or, The C2-C10 alkanolamines include one or more of methylethanolamine, ethylethanolamine, 2-dibutylaminoethanol, and 2-diethylaminoethanol; and / or, The material of the thin film includes the N-type semiconductor material, the two-dimensional material, the first compound, and the complexing agent. The two-dimensional material and the N-type semiconductor material are connected by hydrogen bonds. The complexing agent is coordinately connected to the N-type semiconductor material. Multiple hydrogen bonds are formed between the first compound and the two-dimensional material, the complexing agent, and the N-type semiconductor material.

8. The thin film according to claim 1, characterized in that, The N-type semiconductor material includes one or more of N-type metal oxides or doped N-type metal oxides. The N-type metal oxides include one or more of ZnO, TiO2, SnO2, and ZrO2. The N-type metal oxides in the doped N-type metal oxides include one or more of ZnO, TiO2, SnO2, and ZrO2, and the doping elements include one or more of Al, Mg, Li, In, and Ga.

9. An optoelectronic device, characterized in that, It includes an anode, an electron functional layer, and a cathode, and the material of the electron functional layer includes the thin film described in any one of claims 1 to 8.

10. The optoelectronic device according to claim 9, characterized in that, The anode and the cathode are each independently selected from doped metal oxide particle electrodes, composite electrodes of metal and metal oxide, graphene electrodes, carbon nanotube electrodes, metal electrodes or alloy electrodes. The material of the doped metal oxide particle electrode is selected from one or more of indium-doped tin oxide, fluorine-doped tin oxide, antimony-doped tin oxide, aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, magnesium-doped zinc oxide, and aluminum-doped magnesium oxide. The composite electrode of metal and metal oxide is selected from AZO / Ag / AZO, AZO / Al / AZO, ITO / Ag / ITO, ITO / Al / ITO, ZnO / Ag / ZnO, ZnO / Al / ZnO, TiO2 / Ag / TiO2, TiO2 / Al / TiO2, ZnS / Ag / ZnS, ZnS / Al / ZnS. The material of the metal electrode is selected from one or more of Ag, Al, Cu, Mo, Au, Pt, Si, Ca, Mg, and Ba; and / or The optoelectronic device further includes a light-emitting layer disposed between the electronic functional layer and the anode. The material of the light-emitting layer includes one or more of an organic light-emitting material and a quantum dot light-emitting material. The organic light-emitting material is selected from one or more of 4,4'-bis(N-carbazolyl)-1,1'-biphenyl: tris[2-(p-tolyl)pyridineiridium(III)], 4,4',4''-tris(carbazol-9-yl)triphenylamine: tris[2-(p-tolyl)pyridineiridium, poly[(9,9-dioctylfluorene-2,7-diyl)-alternating-(2,1,3-benzothiadiazole-4,7-diyl)], diarylanthracene derivatives, stilbene aromatic derivatives, pyrene derivatives, fluorene derivatives, TBPe fluorescent material, TTPX fluorescent material, TBRb fluorescent material, DBP fluorescent material, delayed fluorescence material, TTA material, thermally activated delayed material, a polymer containing B-N covalent bonding, a hybrid local charge transfer excited state material, and an exciplex light-emitting material. The quantum dot light-emitting material is selected from at least one of a single-structure quantum dot, a core-shell structure quantum dot, and a perovskite-type semiconductor material. The material of the single-structure quantum dot, the core material of the core-shell structure quantum dot, and the shell material of the core-shell structure quantum dot are each selected from at least one of II-VI group compounds, IV-VI group compounds, III-V group compounds, and I-III-VI group compounds. The shell layer of the core-shell structure quantum dot includes one or more layers. Among them, the II-VI group compounds are selected from at least one of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, and HgZnSTe; The IV-VI group compounds are selected from at least one of SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, SnPbSeTe, and SnPbSTe;The III-V compound is selected from at least one of GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, and InAlPSb; the I-III-VI compound is selected from at least one of CuInS2, CuInSe2, and AgInS2; the perovskite semiconductor material is selected from doped or undoped inorganic perovskite semiconductors, or organic-inorganic hybrid perovskite semiconductors; the structural general formula of the inorganic perovskite semiconductor is AMX3, where A is Cs; + ion, M is a divalent metal cation selected from 2+ 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 them, and X is a halogen anion selected from - Cl - Br - I - at least one of them; the structural general formula of the organic-inorganic hybrid perovskite semiconductor is BMX3, where B is an organic amine cation selected from CH3(CH2) n-2 NH 3+ or [NH3(CH2) n NH3] 2+ , where n≥2, M is a divalent metal cation selected from 2+ 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 them, X is a halogen anion, selected from Cl - , Br - , I - at least one of them.

11. A display device, characterized in that, The display device includes the optoelectronic device described in claim 9 or 10.

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