Composite material, method for producing the same, thin film, and optoelectronic device

Abstract

This application discloses a composite material, its preparation method, a thin film, and an optoelectronic device. The composite material includes metal oxides and metal-organic cages. The composite material proposed in this application exhibits better dispersibility and better film-forming effect.

Description

Technical Field

[0001] This application relates to the field of semiconductor technology, and in particular to a composite material and its preparation method, thin film and optoelectronic device. Background Technology

[0002] Metal oxide nanoparticles, such as zinc oxide nanoparticles and tin oxide nanoparticles, are widely used in semiconductor devices due to their suitable energy levels, excellent carrier injection or transport, long lifespan, high transparency, and low cost.

[0003] However, the insufficient dispersibility of metal oxide nanoparticles in solvents can easily affect the uniformity of film formation. Summary of the Invention

[0004] In view of this, this application provides a composite material, a method for preparing the same, a thin film, and an optoelectronic device.

[0005] The embodiments of this application are implemented as follows:

[0006] In a first aspect, embodiments of this application provide a composite material, including a metal oxide and a metal-organic cage.

[0007] Secondly, embodiments of this application provide a method for preparing a composite material, comprising the following steps:

[0008] A metal oxide, a metal-organic cage, and a first solvent are provided; the metal oxide, the metal-organic cage, and the first solvent are mixed and a first reaction is carried out to obtain a composite material; or...

[0009] A metal salt, a metal-organic cage, an alkali, and a first solvent are provided; the metal salt, the metal-organic cage, the alkali, and the first solvent are mixed to carry out a second reaction to obtain a composite material.

[0010] Thirdly, embodiments of this application provide a thin film, the material of which includes metal oxides and metal-organic cages.

[0011] Fourthly, embodiments of this application provide an optoelectronic device, including a stacked anode, a charge carrier functional layer, and a cathode, wherein the charge carrier functional layer includes the thin film described above.

[0012] Fifthly, embodiments of this application provide a display device including the optoelectronic devices described above.

[0013] The composite material proposed in this application has better dispersibility and better film-forming effect. Attached Figure Description

[0014] To more clearly illustrate the technical solutions in the embodiments of this application, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0015] Figure 1 This is a schematic diagram of the structure of an optoelectronic device provided in an embodiment of this application;

[0016] Figure 2 This is a schematic diagram of the structure of an optoelectronic device provided in another embodiment of this application;

[0017] Reference numerals: Optoelectronic device 100; Anode 10; Cathode 20; Light-emitting layer 30; Hole transport layer 40; Hole injection layer 50; Electron functional layer 60; First film layer 61; Second film layer 62. Detailed Implementation

[0018] The technical solutions in the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this application, and not all embodiments. Based on the embodiments in this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application. In addition, it should be understood that the specific embodiments described herein are only for illustration and explanation of this application and are not intended to limit this application. In this application, unless otherwise stated, directional terms such as "upper" and "lower" specifically refer to the drawing directions in the accompanying drawings. In addition, in the description of this application, the term "including" means "including but not limited to". Various embodiments of this 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 conciseness and should not be construed as a hard limitation on the scope of this application; therefore, it should be considered that the range description has specifically disclosed all possible sub-ranges and single values ​​within that range. For example, it should be assumed that the description of a range from 1 to 6 specifically discloses subranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the range, such as 1, 2, 3, 4, 5, and 6, regardless of the range. Furthermore, whenever a numerical range is referred to herein, it means including any referenced number (fraction or integer) within the range referred to.

[0019] In this application, "and / or" describes the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A existing alone, A and B existing simultaneously, or B existing alone. A and B can be singular or plural.

[0020] In this application, "at least one" means one or more, and "more than one" means two or more. "At least one," "at least one of the following," or similar expressions refer to any combination of these items, including any combination of single or multiple items. For example, "at least one of a, b, or c," or "at least one of a, b, and c," can both mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can be single or multiple.

[0021] Terminology Explanation

[0022] In this application, "aryl" refers to an aromatic hydrocarbon group derived from an aromatic compound by removing one hydrogen atom. It can be a monocyclic aryl, fused-ring aryl, or polycyclic aryl, etc. For polycyclic rings, at least one ring is an aromatic ring system. For example, a C6-C18 aryl refers to an aryl containing 6 to 18 carbon atoms, preferably an aryl having 6 to 14 carbon atoms, particularly preferably an aryl having 6 to 10 carbon atoms, and optionally further substituted. Suitable examples include, but are not limited to: phenyl, biphenyl, terphenyl, naphthyl, anthracene, phenanthrene, fluoranyl, triphenylene, pyrene, perylene, tetraphenyl, fluorenyl, dinaphthylphenyl, acenaphthyl, and their derivatives. It is understood that multiple aryl groups can also be interrupted by short non-aromatic units (e.g., <10% non-H atoms, such as C, N, or O atoms), specifically acenaphthene, fluorene, or 9,9-diarylfluorene, triarylamine, and diaryl ether systems should also be included in the definition of aryl. It is understood that the aromatic ring or aromatic ring system in this application only indicates the structural features of an aromatic ring and does not limit the substituent sites on the ring. For example, it can specifically be aryl, arylene (aromatic hydrocarbon groups derived from aromatic compounds by removing two hydrogen atoms), tertiary aryl (aromatic hydrocarbon groups derived from aromatic compounds by removing three hydrogen atoms), etc.

[0023] In this application, "heteroaryl" refers to an aryl group in which at least one carbon atom on the ring is replaced by a non-carbon atom (heteroatom), which can be an N atom, O atom, S atom, etc. For example, a C5-C18 heterocyclic group refers to a heteroaryl group containing 5 to 18 carbon atoms, preferably a heteroaryl group having 5 to 14 carbon atoms, more preferably a heteroaryl group having 5 to 10 carbon atoms, and the heterocyclic group may optionally be further substituted. Suitable examples include, but are not limited to: thiophene, furanyl, pyrrole, imidazolyl, diazolyl, triazolyl, pyridyl, bipyridyl, pyrimidinyl, triazine, acridine, pyridazinyl, quinolinyl, isoquinolinyl, quinazole Linyl, quinoxalinyl, phthalazinyl, pyridinylpyrimidinyl, pyridinylpyrazinyl, benzothiopheneyl, benzofuranyl, indolyl, pyrroloimidazolyl, pyrrolopyrrolyl, thienopyrrolyl, thienopyrrolyl, furanolyl, furanolyl, thienofuranyl, benzoisoxazolyl, benzoisothiazolyl, benzoimidazolyl, o-diazonyl, phenanthrynyl, primidyl, quinazolinoneyl, dibenzothiopheneyl, dibenzofuranyl, carbazoleyl and their derivatives.

[0024] In this application, "alkyl" can mean straight-chain alkyl and / or branched alkyl. Cycloalkyl refers to a cyclic alkyl group. Phrases containing this term, such as "C1-C20 alkyl," refer to alkyl groups containing 1 to 20 carbon atoms, and each time it appears, it can independently be C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, C7 alkyl, C8 alkyl, C9 alkyl, C10 alkyl, C11 alkyl, C12 alkyl, C13 alkyl, C14 alkyl, C15 alkyl, C16 alkyl, C17 alkyl, C18 alkyl, C19 alkyl, C20 alkyl. Non-limiting examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, etc.

[0025] In this application, "alkoxy" refers to a group with the structure "-O-alkyl", that is, an alkyl group as defined above connected to other groups via an oxygen atom. Suitable examples of phrases containing this term include, but are not limited to: methoxy (-O-CH3 or -OMe), ethoxy (-O-CH2CH3 or -OEt), and tert-butoxy (-OC(CH3)3 or -OtBu). It is understood that "aryloxy" refers to a group with the structure "-O-aryl", and "heteroaryloxy" refers to a group with the structure "-O-heteroaryl".

[0026] In this application, "amino group" refers to an amine derivative having the structural feature of the formula -N(X)2, wherein each "X" is independently H, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted heterocyclic group, etc. Non-limiting types of amino groups include -NH2, -N(alkyl)2, -NH(alkyl), -N(cycloalkyl)2, -NH(cycloalkyl), -N(heterocyclic)2, -NH(heterocyclic), -N(aryl)2, -NH(aryl), -N(alkyl)(aryl), -N(alkyl)(heterocyclic), -N(cycloalkyl)(heterocyclic), -N(aryl)(heteroaryl), -N(alkyl)(heteroaryl), etc.

[0027] In this application, unless otherwise defined, halogen groups refer to -F, -Cl, -Br or -I, hydroxyl groups refer to -OH, carboxyl groups refer to -COOH, nitro groups refer to -NO2, sulfonic acid groups refer to "-SO3H", aldehyde groups refer to -CHO, mercapto groups refer to -SH, and cyano groups refer to -C≡N.

[0028] The terms “combinations thereof,” “any combination thereof,” and “any combination thereof” as used in this application include all suitable combinations of any two or more of the listed items.

[0029] This application provides a composite material comprising a metal oxide and a metal-organic cage.

[0030] Metal-organic cages (MOCs) are discrete supramolecular entities formed by metal clusters or metal ions containing metal elements linked to organic linkers via coordinate bonds. MOCs have a cage-like structure with an internal cavity. MOCs exhibit good solubility in solvents such as alcohols and chlorobenzene.

[0031] The composite material proposed in this application has better dispersibility and better film-forming effect.

[0032] In some embodiments, the metal oxides and metal-organic cages in the composite material are distributed independently and stacked in a disordered manner. Based on the good solubility of the metal-organic cages, the dispersibility of the metal oxides can be improved to a certain extent, thus giving it a better film-forming effect.

[0033] In other embodiments, the metal oxide is connected to the metal-organic cage. The combination of the metal-organic cage and the metal oxide further improves the dispersibility of the metal oxide in organic solvents, making it less prone to aggregation and exhibiting good dispersion stability. When this composite material is used to prepare thin films, it demonstrates good film-forming performance. Furthermore, due to the combination of the metal oxide and the metal-organic cage, defects on the surface of the metal oxide are passivated by the metal-organic cage, resulting in a composite material with fewer surface defects. When used as the charge carrier functional layer of optoelectronic device 100, this reduces non-radiative recombination of excitons caused by surface defects, effectively improving the device's luminescence performance and lifetime. In addition, the metal-containing cage molecules (i.e., the metal-organic cage) can also promote charge carrier transport and improve device performance.

[0034] In some embodiments, the metal-organic cage has active groups; the active groups include at least one of hydroxyl, primary amino, secondary amino, and thiol groups. The metal-organic cage can be connected to the metal oxide through the active groups. Specifically, the active groups can bind to uncoordinated metals on the surface of the metal oxide and surface groups such as hydroxyl groups present on the surface of the metal oxide through hydrogen bonding, electrostatic interactions, or other forces.

[0035] In some embodiments, the metal-organic cage is an A-based MOC, wherein A is a metallic element selected from one or more of Zr, Ti, Hf, Nb, Zn, Cu, and Fe. A-based metal-organic cages not only possess good electrical conductivity and solubility, but the corresponding products are also widely available and easy to prepare.

[0036] Furthermore, in some embodiments, the metal-organic cage has the structure shown in formula (I), which is a tetrahedral cage molecule with four vertices being metal clusters, and six organic linkers L connected one-to-one between two metal clusters, thereby forming a tetrahedral MOC with a conical structure.

[0037] Equation (Ⅰ):

[0038] In formula (Ⅰ):

[0039] It is a trinuclear A metal cluster composed of three A dicerocene salts, and * represents the connection site with L.

[0040]

[0041] A is a metallic element, which can be selected from Zr, Ti, Hf, and Nb.

[0042] X1, X2, and X3 are each independently selected from one or more combinations of hydrogen, deuterium, halogen, hydroxyl, carboxyl, nitro, sulfonic acid, aldehyde, mercapto, cyano, amino, C1-C20 alkyl, C3-C30 cycloalkyl, C1-C20 alkoxy, C6-C30 aryl, C5-C30 heteroaryl, C6-C30 aryloxy, and C5-C30 heteroaryloxy.

[0043] Wherein, the number of carbon atoms in ring B is 6 to 30, and ring B is selected from substituted or unsubstituted aromatic rings; when substituted, each substituent is independently selected from one or more combinations of deuterium, halogen, hydroxyl, carboxyl, nitro, sulfonic acid, aldehyde, mercapto, cyano, amino, C1 to C20 alkyl, C3 to C30 cycloalkyl, C1 to C20 alkoxy, C6 to C30 aryl, C5 to C30 heteroaryl, C6 to C30 aryloxy, and C5 to C30 heteroaryloxy.

[0044] Wherein, R1 represents an active group selected from at least one of -OH, -NH2, -NHR2 and -SH; R2 is selected from one or more combinations of alkyl groups from C1 to C20, cycloalkyl groups from C3 to C30, substituted or unsubstituted aryl groups from C6 to C30, and heteroaryl groups with substituted or unsubstituted ring atoms of 5 to 20.

[0045] The structural formula of L indicates that ring B is connected to a substituent R1. R1 can be connected to any atom on ring B. It can be understood that when ring B is a structure formed by multiple aromatic rings connected together, R1 can be connected to any atom on any aromatic ring.

[0046] The metal-organic cage based on the above structure exhibits better electrical conductivity and better compatibility with metal oxides. Furthermore, this type of metal-organic cage can be prepared by reacting a dihalocene salt of metal A with a compound exhibiting a COOH-L-COOH structure, making the preparation method simple.

[0047] Furthermore, in some embodiments, A is selected from Zr; L is selected from any of the following structures:

[0048]

[0049]

[0050] In some embodiments, the metal oxide may include an N-type metal oxide. Accordingly, the composite material based on the N-type metal oxide is named an N-type composite material. The thin film (named the first thin film) made from this material has good electron transport properties and can be used as the electronic functional layer 60 of the optoelectronic device 100. Specifically, the N-type metal oxide may include one or more of undoped oxides and doped oxides; the undoped oxide may include, but is not limited to, one or more of ZnO, SnO2, and TiO2; the doped oxide includes oxides doped with dopant elements, wherein the oxide includes one or more of ZnO, SnO2, and TiO2, and the dopant element includes one or more of Al, Mg, Li, In, Ga, Ti, Mn, Sn, Ag, and Cu. By incorporating dopant elements, the electron transport properties of the oxide can be modulated, making it more compatible with other film layers of the optoelectronic device 100. Furthermore, when the metal oxide is a doped metal oxide, the molar percentage of the dopant element in the doped metal oxide is greater than 0 and less than or equal to 20%; for example, it can be a value greater than 0 and less than 0.001%, 0.001%, 0.005%, 0.01%, 0.05%, 0.1%, 0.5%, 1%, 2%, 3%, 5%, 8%, 10%, 15%, 17%, 20%, or any two of the above values. By controlling it within this range, the electron transport properties of the doped metal oxide can be precisely controlled.

[0051] In other embodiments, the metal oxide may include a p-type metal oxide. Accordingly, the composite material based on the p-type metal oxide is named a p-type composite material. The thin film made using this material (named the second thin film) has good hole transport or injection properties and can be used as the hole functional layer of the optoelectronic device 100. Specifically, the p-type metal oxide includes one or more of molybdenum oxide, copper oxide, nickel oxide, tungsten oxide, and vanadium oxide.

[0052] In some embodiments, the molar ratio of the metal-organic cage to the metal oxide in the composite material is 1:1.3 to 5; for example, it can be 1:1.3, 1:1.5, 1:1.8, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, or any two of the above values. Controlling the molar ratio within this range can improve the carrier transport performance of the composite material while improving the dispersion and surface defects of the metal oxide.

[0053] This application also proposes a method for preparing a composite material, based on which the composite material described above can be obtained. In some embodiments, the preparation method includes the following steps:

[0054] S100a, providing a metal oxide, a metal-organic cage, and a first solvent, mixing the metal oxide, the metal-organic cage, and the first solvent, and carrying out a first reaction to obtain a composite material; or,

[0055] S100b provides a metal salt, a metal-organic cage, an alkali, and a first solvent; the metal salt, the metal-organic cage, the alkali, and the first solvent are mixed to carry out a second reaction to obtain a composite material.

[0056] In step S100a:

[0057] A composite material can be obtained by mixing a metal oxide with a metal-organic cage, the composite material comprising the metal oxide and the metal-organic cage exhibiting good film-forming properties. The preparation method is simple and easy to implement.

[0058] In some embodiments, in the composite material obtained based on step S100a, the metal oxide and the metal-organic cage are distributed independently and are in a disordered stacked state.

[0059] In some embodiments, the molar ratio of the metal-organic cage to the metal oxide is 1:3 to 8; for example, it can be 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, or any two of the above values. This allows for better control of the ratio of the two components in the reaction product-composite material.

[0060] In some embodiments, the temperature of the first reaction is 20 to 40°C; for example, it can be 20°C, 22°C, 24°C, 25°C, 28°C, 29°C, 30°C, 33°C, 35°C, 37°C, 40°C, or any two of the above values, which helps to provide a suitable temperature environment for the first reaction and promote the reaction to proceed.

[0061] In some embodiments, the time for the first reaction is 60 to 80 hours; for example, it can be 60 hours, 63 hours, 65 hours, 67 hours, 70 hours, 71 hours, 72 hours, 75 hours, 76 hours, 78 hours, 80 hours, or any two of the above values, which helps to promote the reaction to proceed fully and improve the conversion rate.

[0062] In some embodiments, the metal oxide includes an N-type metal oxide or a P-type metal oxide. The N-type metal oxide includes one or more of undoped oxides and doped oxides. The undoped oxide includes one or more of ZnO, SnO2, and TiO2. The doped oxide includes an oxide doped with a dopant element. The oxide includes one or more of ZnO, SnO2, and TiO2, and the dopant element includes one or more of Al, Mg, Li, In, Ga, Ti, Mn, Sn, Ag, and Cu. Optionally, in the doped metal oxide, the molar percentage of the dopant element is greater than 0 and less than or equal to 20%. The P-type metal oxide includes one or more of molybdenum oxide, copper oxide, nickel oxide, tungsten oxide, and vanadium oxide.

[0063] The metal oxide can be prepared in-house or purchased from the market through customization, purchase, or other means.

[0064] In step S100b, a metal-organic cage is added during the synthesis of the metal oxide. This allows the metal oxide and the metal-organic cage to combine simultaneously. Relatively speaking, the method of introducing the metal-organic cage during the synthesis process in step S100b is more conducive to the combination of the two, which helps to improve the bonding force and the stability and yield of the composite material.

[0065] In some embodiments, the metal salt includes a first metal salt or a second metal salt. The first metal salt includes one or more of zinc salt, titanium salt, and tin salt, and the second metal salt includes one or more of copper salt, nickel salt, tungsten salt, molybdenum salt, and vanadium salt. When the first metal salt is used, the resulting metal oxide is an N-type metal oxide; when the second metal salt is used, the resulting metal oxide is a P-type metal oxide. It is understood that in other embodiments, when the target metal oxide is an N-type metal oxide and specifically belongs to a doped state metal oxide, the metal salt includes not only the first metal salt but also a doped metal salt. The doped metal salt includes one or more of aluminum salt, magnesium salt, lithium salt, indium salt, gallium salt, titanium salt, manganese salt, tin salt, silver salt, and copper salt. The amounts of the first metal salt and the doped metal salt can be adjusted according to the expected molar percentage of the dopant element.

[0066] In some embodiments, the molar ratio of the metal element in the metal salt to the metal-organic cage is 4.5 to 12.5:1; for example, it can be 4.5:1, 5:1, 5.5:1, 6:1, 6.5:1, 7:1, 7.5:1, 8:1, 8.5:1, 9:1, 9.5:1, 10:1, 10.5:1, 11:1, 11.5:1, 12:1, 12.5:1, or any range between any two of the above values. In this way, the molar ratio of the metal oxide formed in the reaction to the metal-organic cage in the mixed system can be controlled, thereby better controlling the ratio of the two in the reaction product-composite material.

[0067] In some embodiments, the alkali comprises one or more alkali metal hydroxides; specifically, the alkali metal hydroxide may include, but is not limited to, one or more of potassium hydroxide, sodium hydroxide, and lithium hydroxide. In some embodiments, the molar ratio of the metal element in the metal salt to the alkali is 1:1.5 to 2.5; for example, it can be 1:1.5, 1:1.7, 1:1.8, 1:1.9, 1:2, 1:2.1, 1:2.2, 1:2.3, 1:2.4, 1:2.5, or any range between two of the above values.

[0068] In some embodiments, the first solvent includes one or more of dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), methanol, ethanol, isopropanol, n-butanol, pentanol, and hexanol.

[0069] In some embodiments, the temperature of the second reaction is 20 to 40°C; for example, it can be 20°C, 22°C, 24°C, 25°C, 28°C, 29°C, 30°C, 33°C, 35°C, 37°C, 40°C, and any two of the above values.

[0070] In some embodiments, the time for the second reaction is 10 to 72 hours; for example, it can be 10 hours, 12 hours, 14 hours, 16 hours, 18 hours, 20 hours, 22 hours, 24 hours, 26 hours, 28 hours, 30 hours, 33 hours, 35 hours, 36 hours, 40 hours, 45 hours, 50 hours, 60 hours, 65 hours, 70 hours, 71 hours, 72 hours, and any range between any two of the above values.

[0071] In some embodiments, the metal-organic cage has an active group, which includes at least one selected from hydroxyl, primary amino, secondary amino, and thiol groups. Further, the metal-organic cage is an A-based MOC, wherein A is a metallic element selected from one or more of Zr, Ti, Hf, Nb, Zn, Cu, and Fe; even further, the metal-organic cage has the structure shown in formula (I). For details, please refer to the foregoing description, which will not be repeated here.

[0072] The metal-organic cages mentioned above can be purchased commercially through customization or other means. For example, the Zr-MOCs (ZrT-1-NH2, ZrT-1-OH) provided in the literature "Efficient removal of dyes from water by zirconium-based metal-organic cages with varying functional groups; Xiao-Qing Wang, Man Zhang, Jiandong Yang, Jie Yang, Hongzhen Duan" have the structure shown in formula (Ⅰ), where A is Zr and L is... (i.e., the structure shown in equation (2-1)) or (Structure shown in Equation (1-1)); The Zr-MOCs (cage-2) provided in the literature “Artificial Biomolecular Channels: Enantioselective Transmembrane Transport of Amino Acids Mediated by Homochiral Zirconium Metal-Organic Cages; Yingguo Li, Jinqiao Dong, Wei Gong, Xianhui Tang, Yuhao Liu, Yong Cui, and Yan Liu” have the structure shown in Equation (Ⅰ), where A is Zr and L is the structure shown in Equation 13-2.

[0073] The metal-organic cage can also be prepared by itself. In some embodiments, when the metal-organic cage has the structural formula (I), the preparation method further includes the preparation of the metal-organic cage, which includes: S101, dispersing the dihalodicyclopentadiene salt and the first compound in a second solvent, and carrying out a third reaction at 40-80°C to obtain the metal-organic cage; wherein, the dihalodicyclopentadiene salt has the structure shown in formula (II), and the first compound has the structure shown in formula (III):

[0074] Formula (II):

[0075] Formula (Ⅲ): COOH-L-COOH;

[0076] Where X is selected from X1, X2 or X3; Y1 and Y2 are each independently selected from halogens.

[0077] In some embodiments, the dihalocene dichloride includes one of zirconium dichloride (Cp2ZrCl2, CAS: 1291-32-3), 1,1'-dibutylzirconium dichloride (n-Bu-Cp2ZrCl2, CAS: 73364-10-0), titanium dichloride (CAS: 1271-19-8), hafnium dichloride (CAS: 12116-66-4), and niobium dichloride (CAS: 12793-14-5).

[0078] In some embodiments, the first compound comprises one of the following compounds: 2-hydroxyterephthalic acid (CAS: 636-94-2), 2-aminoterephthalic acid (CAS: 10312-55-7), p-mercaptoterephthalic acid (CAS: 25906-66-5), 2,3-dimercaptoterephthalic acid (CAS: 174577-68-5), 2,5-difluoro-3,6-dimercaptoterephthalic acid (CAS: 2089430-11-3), 2,6-dihydroxyterephthalic acid (CAS: 69660-39-5), and 2,5-dihydroxyterephthalic acid (CAS: 610-92-4). ), 2,3-dihydroxy-1,4-phthalic acid (CAS: 19829-72-2), 2,5-diphenylaminoterephthalic acid (CB61161834), 2-(aniline)terephthalic acid (CAS: 566155-75-7), 2,5-bis(2-chloroaniline)terephthalic acid (CAS: 10291-27-7), 4,8-diamino-2,6-naphthalenedicarboxylic acid (CAS: 2226204-96-0), 4,4'-(6,6'-dichloro-2,2'-diethoxy-[1,1'-bidinaphthalic]-4,4'-substituted)dibenzoic acid (see reference "Homochiral") BINAPDA-Zr-MOF for Heterogeneous Asymmetric Cyanosilylation of Aldehydes (prepared by Fa-ZhengJin, Chen-Chen Zhao, Hui-Chao Ma, Gong-Jun Chen, *and Yu-Bin Dong*). The above compound has the following structural formula:

[0079]

[0080] In some embodiments, the second solvent includes one or more of dimethylformamide (DMF), dimethylacetamide (DMA), dimethyl sulfoxide (DMSO), methanol, acetone, and acetonitrile.

[0081] In some embodiments, the molar ratio of the dihalocene salt to the first compound is 1:1.8 to 3; for example, it can be 1:1.8, 1:1.9, 1:2.0, 1:2.1, 1:2.2, 1:2.3, 1:2.4, 1:2.5, 1:3, and any two of the above values.

[0082] Furthermore, embodiments of this application also propose a thin film, the material of which includes metal oxides and metal-organic cages.

[0083] The specific materials and preparation methods of the metal oxide and the metal-organic cage can be referred to the above content, and will not be repeated here.

[0084] In the thin film, the metal-organic cage can combine with the metal oxide to passivate surface defects of the metal oxide and improve the performance of the thin film.

[0085] Metal oxides and metal-organic cages can be distributed in various ways in thin films. For example:

[0086] In some embodiments, metal oxides are bonded together to form a thin film material. Specifically, the thin film is a single-layer film, and the material of the single-layer film includes the composite material described above. The resulting thin film not only has passivated surface defects but also exhibits fewer overall defects and better film formation performance.

[0087] It should be noted that when a single-layer film is used as the carrier functional layer of optoelectronic device 100, the thickness of the film can be adjusted to further improve device performance and achieve better matching between the film layers. Specifically, in some embodiments, when the metal oxide in the single-layer film is an N-type metal oxide, the single-layer film can be used as the electronic functional layer 60, and the thickness of the single-layer film is 25–50 nm; for example, it can be 25 nm, 26 nm, 28 nm, 30 nm, 35 nm, 40 nm, 45 nm, 50 nm, or any two of the above values. When the metal oxide in the single-layer film is a P-type metal oxide, the single-layer film can be used as the hole functional layer, and the thickness of the single-layer film is 42–66 nm; for example, it can be 42 nm, 45 nm, 50 nm, 52 nm, 55 nm, 58 nm, 60 nm, 66 nm, or any two of the above values.

[0088] In other embodiments, the thin film includes a first film layer 61 and a second film layer 62 disposed on one side of the first film layer 61. The material of the first film layer 61 includes the metal oxide, and the material of the second film layer 62 includes the metal-organic cage. The metal oxide and the metal-organic cage located at the interface between the first film layer 61 and the second film layer 62 can bond together to passivate the metal oxide.

[0089] It should be noted that when the thin film based on the aforementioned stacked structure composed of the first film layer 61 and the second film layer 62 is used as the carrier functional layer of the optoelectronic device 100, the thickness of the thin film can be adjusted to further improve device performance and achieve better matching between the film layers. For details, please refer to [link to relevant documentation]. Figure 2 In some embodiments, when the metal oxide in the thin film is an N-type metal oxide, the thin film can be used as the electronic functional layer 60. The thickness of the first film layer 61 is 25–50 nm; for example, it can be 25 nm, 26 nm, 28 nm, 30 nm, 35 nm, 40 nm, 45 nm, 50 nm, or any two of the above values. The thickness of the second film layer 62 is 26–55 nm; for example, it can be 26 nm, 28 nm, 30 nm, 35 nm, 40 nm, 45 nm, 50 nm, 52 nm, 55 nm, or any two of the above values. Furthermore, the second film layer 62 can be disposed between the first film layer 61 and the anode 10, which helps to improve non-radiative recombination caused by defects. When the metal oxide in the monolayer is a p-type metal oxide, the monolayer can be used as a hole functional layer, and the thickness of the monolayer is 42–66 nm; for example, it can be 42 nm, 45 nm, 50 nm, 52 nm, 55 nm, 58 nm, 60 nm, 66 nm, or any two of the above values. When the metal oxide in the thin film is a p-type metal oxide, the thin film can be used as a hole functional layer, and the thickness of the first film layer 61 is 42–66 nm; for example, it can be 42 nm, 45 nm, 50 nm, 52 nm, 55 nm, 58 nm, 60 nm, 66 nm, or any two of the above values; the thickness of the second film layer 62 is 42–70 nm, for example, it can be 42 nm, 45 nm, 50 nm, 52 nm, 55 nm, 58 nm, 60 nm, 66 nm, 70 nm, or any two of the above values. Furthermore, the second film layer 62 can be disposed between the first film layer 61 and the cathode 20, which helps to improve non-radiative recombination caused by defects.

[0090] In some embodiments, the material of the first film layer 61 may further include the metal-organic cage, and the molar ratio of the metal-organic cage to the metal oxide in the first film layer 61 is 1:1.3 to 5; for example, it can be 1:1.3, 1:1.5, 1:1.8, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, and any two of the above values. This helps to further passivate the metal oxide in the first film layer 61. In other embodiments, the material of the first film layer 61 may be a composite material, which not only further passivates defects but also improves the film formation uniformity of the first film layer 61.

[0091] Furthermore, this application also proposes an optoelectronic device 100, please refer to [link to relevant documentation]. Figure 1 The optoelectronic device 100 includes a stacked anode 10, a carrier functional layer, and a cathode 20, wherein the carrier functional layer includes the thin film described above.

[0092] Using thin films with fewer defects in the carrier functional layer helps reduce nonradiative recombination of excitons and improve device performance, such as increasing the external quantum efficiency and extending the device lifetime. In some cases, when the material of the thin film used in the carrier functional layer is a composite material, it also helps to improve the uniformity of the carrier functional layer, making the film surface smoother, improving the interfacial contact between adjacent film layers, and further improving device performance.

[0093] When the metal oxide in the thin film is an N-type metal oxide, the thin film is a first thin film; when the metal oxide in the thin film is a P-type metal oxide, the thin film is a second thin film.

[0094] In some embodiments, the charge carrier functional layer includes a hole functional layer, which includes a second thin film. Further, the hole functional layer may include one or both of a hole transport layer 40 and a hole injection layer 50, wherein the second thin film can serve as either the hole transport layer 40 or the hole injection layer 50. When the hole functional layer includes both the hole transport layer 40 and the hole injection layer 50, the hole injection layer 50 is located between the hole transport layer 40 and the anode 10. One of the hole transport layer 40 and the hole injection layer 50 may be a second thin film, while the other may be a hole transport material or a hole injection material commonly used in the art; alternatively, both layers may be a second thin film.

[0095] Commonly used hole transport materials can be selected from organic materials with hole transport capabilities, including but not limited to 4,4'-N,N'-dicarbazolyl-biphenyl (CBP), poly[(9,9'-dioctylfluorene-2,7-diyl)-co-(4,4'-(N-(4-sec-butylphenyl)diphenylamine))](TFB), and N,N'-diphenyl-N,N'-bis(1-naphthyl)-1,1'-biphenyl- 4,4”-Diamine (α-NPD), N,N'-diphenyl-N,N'-bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine (TPD), N,N'-bis(3-methylphenyl)-N,N'-bis(phenyl)-spiro(spiro-TPD), N,N'-bis(4-(N,N'-diphenyl-amino)phenyl)-N,N'-diphenylbenzidine (DNTPD), 4, 4',4”-Tris(N-3-methylphenyl-N-phenylamino)triphenylamine (m-MTDATA), poly(p-)phenylenevinylene (PPV), poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV), poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylenevinylene] (MOMO-PPV), PEDOT:PSS, poly(N-vinylcarbazole) (PVK), polymethacrylate, poly(9,9-octylfluorene), N,N'-di(naphthyl-1-yl)-N,N'-diphenylbenzidine (NPB), spiroNPB, doped graphene, undoped graphene, and one or more transition metal oxides, wherein the transition metal oxides include one or more of NiO, MoO2, WO3, and CuO.

[0096] Commonly used hole injection materials refer to materials known in the art that have hole injection capabilities, including but not limited to poly(3,4-ethylenedioxythiophene) (PEDOT), poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid (PEDOT:PSS), 2,3,5,6-tetrafluoro-7,7',8,8'-tetracyanoquinone-dimethylethane (F4-TCNQ), 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazabenzophenanthrene (HATCN), copper polyester carbonate (CuPc), transition metal oxides, and metal chalcogenides; wherein the transition metal oxides include one or more of NiO, MoO2, WO3, and CuO; and the metal chalcogenides include one or more of MoS2, MoSe2, WS3, WSe3, and CuS.

[0097] In other embodiments, the carrier functional layer includes an electronic functional layer 60, which includes a first thin film.

[0098] In some other embodiments, the carrier functional layer may also include an electronic functional layer 60 and a hole functional layer, with the electronic functional layer 60 including a first thin film and the hole functional layer including a second thin film. That is, both the electronic functional layer 60 and the hole functional layer of the device use the above-mentioned thin film, which helps to further improve the device performance.

[0099] In some embodiments, the optoelectronic device 100 further includes a light-emitting layer 30, which is disposed between the carrier functional layer and the anode 10 or between the carrier functional layer and the cathode 20; specifically, the light-emitting layer 30 is disposed between the electron functional layer 60 and the hole functional layer, that is, between the hole functional layer and the cathode 20 or between the electron functional layer 60 and the anode 10. In a specific embodiment, the optoelectronic device 100 includes an anode 10, a hole injection layer 50, a hole transport layer 40, a light-emitting layer 30, an electron functional layer 60, and a cathode 20 stacked sequentially.

[0100] The material of the light-emitting layer 30 may include organic light-emitting materials or quantum dots.

[0101] The organic light-emitting material includes at least one of the following: diaromatic anthracene derivative, stilbene aromatic derivative, pyrene derivative or fluorene derivative, TBPe fluorescent material emitting blue light, TTPA fluorescent material emitting green light, TBRb fluorescent material emitting orange light, and DBP fluorescent material emitting red light.

[0102] The quantum dots include at least one of single-structure quantum dots, core-shell quantum dots, and perovskite semiconductor materials. The shell of the core-shell quantum dots comprises one or more layers. The material of the single-structure quantum dots, the core material of the core-shell quantum dots, and the shell material of the core-shell quantum dots respectively include at least one of group II-VI compounds, group IV-VI compounds, group III-V compounds, and group I-III-VI compounds. The group II-VI compounds include CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, and Zn. At least one of the following: SeS, 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 include SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, SnSeTe, SnS At least one of Te, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, SnPbSeTe, and SnPbSTe; the III-V compounds include 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, and GaAlNP. At least one of GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, and InAlPSb; the I-III-VI group compounds include at least one of CuInS2, CuInSe2, and AgInS2; the perovskite semiconductor material includes 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+ Cu2+ Ni 2+ Cd 2+ Cr 2+ Mn 2+ Co 2+ Fe 2+ 、Ge 2+ Yb 2+ Eu 2+ At least one of them, where X is a halide anion selected from Cl. - ,Br - I - At least one of the following; the general structural formula of the organic-inorganic hybrid perovskite semiconductor is BMX3, wherein B is an organic amine cation selected from CH3(CH2). n-2 NH3 + Or [NH3(CH2)] n NH3] 2+ Where n≥2, M is a divalent metal cation selected from Pb 2+ Sn 2+ Cu 2+ Ni 2+ Cd 2+ Cr 2+ Mn 2+ Co 2+ Fe 2+ 、Ge 2+ Yb 2+ Eu 2+ At least one of them, where X is a halide anion selected from Cl. - ,Br - I - At least one of them.

[0103] As an example, the core-shell structured quantum dots may be selected from, but are 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 aforementioned materials consisting of single-structure quantum dots, or core-shell structure quantum dots, or shell-structure quantum dots, the provided chemical formulas only indicate the elemental composition, not the content of each element. For example, CdZnSe only indicates that it is composed of three elements: Cd, Zn, and Se. If the content of each element were specified, it would correspond to Cd... xZn 1-x Se, where 0 < x < 1. It can be understood that the core material of the core-shell structured quantum dots and the materials of each shell layer are expressed by connecting with " / ", and the order from left to right is the types of materials of the quantum dots from inside to outside: core material / first shell layer material / Nth shell layer material, where N is an integer greater than or equal to 1; for example, CdSe / CdZnSeS / ZnS represents a core-shell structured quantum dot with two shell layers, its core material is CdSe, the material of the first shell layer coated on the core is CdZnSeS, and the material of the second shell layer coated outside the first shell layer is ZnS.

[0104] The anode 10 and the cathode 20 each independently include a doped metal oxide particle electrode, a composite electrode of metal and metal oxide, a graphene electrode, a carbon nanotube electrode or a metal electrode. 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. Here, " / " 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.

[0105] It can be understood that the optoelectronic device 100 can also add some functional layers that are commonly used in optoelectronic devices 100 and are helpful to improve the device performance, such as an electron blocking layer, a hole blocking layer, an interface modification layer, etc.

[0106] It can be understood that the materials of each layer of the optoelectronic device 100 can be adjusted according to the optoelectronic requirements of the optoelectronic device 100.

[0107] Furthermore, this application also proposes a method for fabricating an optoelectronic device 100, which can produce the optoelectronic device 100 described above. The fabrication method includes sequentially fabricating multiple film layers according to a film layer stacking order to obtain the optoelectronic device 100. The film layer stacking order refers to the order in which the multiple film layers of the intended optoelectronic device 100 are stacked. For example, in some embodiments, the optoelectronic device 100 includes an anode 10, a hole injection layer 50, a hole transport layer 40, a light-emitting layer 30, an electronic functional layer 60, and a cathode 20 stacked sequentially. In this case, the anode 10, hole injection layer 50, hole transport layer 40, light-emitting layer 30, electronic functional layer 60, and cathode 20 are fabricated sequentially, with each subsequent film layer formed on the surface of the previous film layer. In other embodiments, when the optoelectronic device 100 includes a cathode 20, electronic functional layer 60, light-emitting layer 30, hole transport layer 40, hole injection layer 50, and anode 10 stacked sequentially, the cathode 20, electronic functional layer 60, light-emitting layer 30, hole transport layer 40, hole injection layer 50, and anode 10 are fabricated sequentially.

[0108] It is understood that when one or more of the hole injection layer 50, hole transport layer 40 and electronic functional layer 60 are prepared using the composite material described above or using the thin film described above as the film layer, the film layer can be prepared by referring to the thin film preparation method described above.

[0109] Other film layers besides the aforementioned film layer, such as the anode 10, cathode 20, and light-emitting layer 30, can be formed using chemical or physical methods. Chemical methods include chemical vapor deposition, continuous ion layer adsorption and reaction, anodic oxidation, electrolytic deposition, and co-precipitation. Physical methods include physical deposition or solution processing. Physical deposition methods include thermal evaporation deposition (CVD), electron beam evaporation deposition, magnetron sputtering, multi-arc ion deposition, physical vapor deposition (PVD), atomic layer deposition, and pulsed laser deposition. Solution processing methods include spin coating, printing, inkjet printing, blade coating, dip coating, immersion coating, spraying, roller coating, casting, slot coating, and strip coating. Those skilled in the art can prepare the various film layers of the optoelectronic device 100 of this application embodiment using methods known in the art, which will not be elaborated further here.

[0110] Furthermore, embodiments of this application also relate to a display device, which includes the optoelectronic device 100 provided in this application, or the optoelectronic device 100 prepared by the method described above. The display device can be any electronic product with display functionality, including but not limited to smartphones, tablets, laptops, digital cameras, digital camcorders, smart wearable devices, smart weighing scales, in-vehicle displays, televisions, or e-book readers. Smart wearable devices can be, for example, smart bracelets, smartwatches, virtual reality (VR) headsets, etc.

[0111] The present application will be specifically described below through specific embodiments. These embodiments are only some embodiments of the present application and are not intended to limit the present application. Unless otherwise specified, the raw materials used in the following embodiments are all commercially available products.

[0112] Thin Film Example 1

[0113] (1) Dissolve the metal-organic cage ZrT-1-OH in DMSO; then follow the steps of dissolving the metal-organic cage and Zn 2+ The molar ratio is 1:6. An ethanol solution of zinc acetate dihydrate is added, and after stirring until homogeneous, KOH and Zn are added according to... 2+ The molar ratio of Zr to ZnO was 1.5:1. An ethanol solution of KOH was added dropwise, and the mixture was stirred at room temperature (approximately 24°C) for 12 hours to obtain the reaction product. The reaction product was washed with ethanol and n-heptane, respectively, and then dried under vacuum to obtain the composite material—MOC powder loaded with ZnO. The prepared composite material was analyzed by ICP-OES, and the results showed that the material contained Zr and Zn, with a molar ratio close to 2:1 (Zr:Zn), indicating that ZnO was successfully loaded into ZrT-1-OH.

[0114] ZrT-1-OH has the following structure:

[0115]

[0116] in:

[0117] (2) The composite material was dispersed in ethanol to prepare a composite material solution with a concentration of about 30 mg / mL.

[0118] (3) Using the above composite material solution, a film layer with a thickness of about 40 nm was printed on a glass substrate using a Dimatix Materials Printer DMP-2831 inkjet printer, and then annealed at 120°C for 15 min to obtain a thin film.

[0119] Thin Film Example 2

[0120] This embodiment is basically the same as thin film embodiment 1, except that in this embodiment, the metal organic cage is replaced with ZrT-1-NH2, that is, L is replaced with The prepared composite material was tested by ICP-OES and it was found that the material contained Zr and Zn, and the molar ratio was close to 2:1 (Zr:Zn), indicating that ZnO was successfully loaded into ZrT-1-NH2.

[0121] Thin Film Example 3

[0122] This embodiment is basically the same as thin film embodiment 1, except that in this embodiment, the metal organic cage is replaced with M1, which has a structure similar to ZrT-1-OH.

[0123]

[0124] L changed to:

[0125]

[0126] Accordingly, M1 is prepared by the following method:

[0127] 0.1 mmol of compound 1 and 0.2 mmol of n-Bu-Cp2ZrCl2 were dissolved in 15 mL of dimethylacetamide (DEA) and 15 mL of CH3CN. The mixture was heated at 50 °C for 24 h. After cooling, the product was centrifuged and washed with DMF, CH2Cl2, and Et2O, respectively. Finally, it was dried under vacuum to obtain a tetrahedral metal-organic cage M1. The structural formula of compound 1 is as follows:

[0128]

[0129] The prepared composite material was tested by ICP-OES and it was found that the material contained Zr and Zn in a molar ratio close to 1:1, indicating that compound 1 successfully chelated with n-Bu-Cp2ZrCl2 to form a cage molecule and that ZnO was successfully loaded into M1.

[0130] Thin Film Example 4

[0131] This embodiment is basically the same as thin film embodiment 3, except that in this embodiment, the metal organic cage is replaced with M2, and in M2, L is replaced with: Accordingly, in the preparation method, compound 1 is replaced with a compound having the following structural formula:

[0132] The prepared composite material was tested by ICP-OES and it was found that the material contained Zr and Zn in a molar ratio close to 1:1, indicating that compound 1 successfully chelated with n-Bu-Cp2ZrCl2 to form a cage molecule, and ZnO was successfully loaded into M2.

[0133] Thin Film Example 5

[0134] This embodiment is basically the same as thin film embodiment 3, except that in this embodiment, the metal organic cage is replaced with M3, and in M3, L is replaced with: Accordingly, in the preparation method, compound 1 is replaced with a compound having the following structural formula:

[0135] The prepared composite material was tested by ICP-OES and it was found that the material contained Zr and Zn in a molar ratio close to 1:1, indicating that compound 1 successfully chelated with n-Bu-Cp2ZrCl2 to form a cage molecule and that ZnO was successfully loaded into M3.

[0136] Thin Film Example 6

[0137] This embodiment is basically the same as thin film embodiment 3, except that in this embodiment, the metal organic cage is replaced with M4, which has a structure similar to ZrT-1-OH. The only difference is:

[0138]

[0139] Accordingly, in the preparation method, n-Bu-Cp2ZrCl2 is replaced with hafnium dichloroethylene, and compound 1 is replaced with a compound having the following structural formula:

[0140] The prepared composite material was tested by ICP-OES and found to contain Hf and Zn in a molar ratio close to 2:1, indicating that compound 1 successfully chelated with hafnium dichlorocerocene to form a cage molecule and that ZnO was successfully loaded into M4.

[0141] Thin Film Example 7

[0142] This embodiment is basically the same as thin film embodiment 1, except that in this embodiment, the metal-organic cage is replaced with a copper-based metal-organic cage - MOP1, derived from the literature "Surface functionalization of metalorganic polyhedron for homogeneous cyclopropanation catalysis; Weigang Lu, Daqiang Yuan, Andrey Yakovenko and Hong-Cai Zhou". It has the following structure:

[0143]

[0144] in:

[0145] The prepared composite material was tested by ICP-OES and it was found that the material contained Cu and Zn in a molar ratio close to 1:1, indicating that ZnO was successfully loaded into the copper-based metal organic cage-MOP1.

[0146] Thin Film Example 8

[0147] This embodiment is basically the same as thin film embodiment 1, except that in this embodiment, the metal organic cage and Zn 2+ The molar ratio was changed to 1:4.5.

[0148] Thin Film Example 9

[0149] This embodiment is basically the same as thin film embodiment 1, except that in this embodiment, the metal organic cage and Zn 2+ The molar ratio was changed to 1:12.5.

[0150] Thin Film Example 10

[0151] This embodiment is basically the same as thin film embodiment 1, except that in this embodiment, the metal organic cage and Zn 2+ The molar ratio was changed to 1:14.

[0152] Thin Film Example 11

[0153] This embodiment is basically the same as thin film embodiment 1, except that in step (1) of this embodiment, zinc oxide is directly mixed with the metal organic cage. Specifically, step (1) is changed to:

[0154] According to KOH and Zn 2+ The molar ratio of zinc acetate dihydrate to zinc acetate was 2:1. An ethanol solution of KOH was added dropwise to the zinc acetate dihydrate solution, and the mixture was stirred at room temperature (approximately 24°C) for 12 hours to obtain ZnO nanoparticles. After washing repeatedly with ethanol, the nanoparticles were dispersed in ethanol to obtain an ethanol solution of ZnO.

[0155] The metal-organic cage (ZrT-1-OH) was dissolved in DMSO to obtain a cage molecule solution; then, the metal-organic cage and Zn were reacted... 2+ The molar ratio of the cage molecules was 1:6. The ethanol solution of ZnO was mixed and stirred at room temperature (about 24°C) for 72 hours to obtain the reaction product. The reaction product was washed with ethanol several times and dried under vacuum to obtain the composite material.

[0156] Thin Film Example 12

[0157] This embodiment is basically the same as thin film embodiment 1, except that in this embodiment, ZnO is replaced with SnO2, and correspondingly, zinc acetate dihydrate in step (1) is replaced with tin acetate.

[0158] Thin Film Example 13

[0159] This embodiment is basically the same as thin film embodiment 1, except that in this embodiment, ZnO is replaced with nickel oxide, and correspondingly, zinc acetate dihydrate in step (1) is replaced with nickel acetate.

[0160] Thin Film Comparative Example 1

[0161] This comparative example is basically the same as the thin film example 1, except that the zinc oxide nanoparticles and the thin film based on the zinc oxide nanoparticles are prepared in this example. Accordingly, in step (1), no metal organic cage is added.

[0162] Thin Film Comparative Example 2

[0163] This comparative example is basically the same as that of the thin film example 1, except that in this example, the metal organic cage is replaced with a metal organic framework (MOF) material -- UiO-66(Zr), CAS:1072413-89-8.

[0164] Thin Film Comparative Example 3

[0165] This comparative example is basically the same as that of thin film example 1, except that in this example, the metal organic cage is replaced with an organic cage molecule cube 4a (refer to cube 4a in the literature: Chem. Commun., 2014, 50, 12454-12457).

[0166] Thin film comparative example 4

[0167] This comparative example is basically the same as thin film example 12, except that the tin oxide nanoparticles and thin films based on tin oxide nanoparticles are prepared in this example. Accordingly, in step (1), no metal organic cage is added.

[0168] Thin film comparative example 5

[0169] This comparative example is basically the same as thin film example 13, except that the nickel oxide nanoparticles and thin films based on nickel oxide nanoparticles are prepared in this example. Accordingly, in step (1), no metal organic cage is added.

[0170] (i) Dispersion test: Take the composite material solutions prepared in step (2) of each film example and comparative example, and after standing for 30 minutes, take each sample for dynamic light scattering (DLS) test to detect the particle size distribution. If the test result shows a single value, it indicates that the particle size is basically the same and the particles are relatively uniformly distributed in the solvent. If the test result shows a value that fluctuates within a certain range, it indicates that agglomeration may have occurred. The test results are recorded in Table 1.

[0171] (II) Film Uniformity Testing: The thickness of the films prepared in each thin film example and comparative example was measured using a white light interferometer, and the average film thickness was calculated. A film region with a certain thickness (average film thickness ± 10 nm) was selected and denoted as the uniform film region. The film uniformity was calculated according to the following formula, and the results were recorded in Table 1.

[0172] Film uniformity = Total film surface area of ​​the uniform film region / Total film area of ​​the entire film × 100%.

[0173] Table 1

[0174]

[0175]

[0176] As shown in the table above:

[0177] Compared with film comparative example 1, the films prepared in film examples 1 to 11 all have better film uniformity. Compared with film comparative example 4, film example 12 has better film uniformity. Compared with film comparative example 5, film example 13 has better film uniformity, indicating that the film prepared from the composite material proposed in this application has a better film forming effect.

[0178] Furthermore, comparing the thin film examples 1 to 13, it can be seen that the thin film examples 1 to 10, as well as 12 and 13, not only showed a significant improvement in film uniformity, but also exhibited good dispersibility and no agglomeration. This indicates that by combining the metal-organic cage with the metal oxide, the dispersibility of the composite material can be further improved, the agglomeration problem can be mitigated, and the film formation effect can be further enhanced.

[0179] Furthermore, a comparison of Thin Film Example 1 and Thin Film Comparative Examples 1 to 3 shows that Thin Film Example 1 has a more significant improvement in film uniformity compared to Comparative Examples 2 and 3, indicating that compared to metal-organic frameworks and organic cage molecules, the use of metal-organic cages can better improve the film-forming performance of metal oxides.

[0180] Device Example 1

[0181] This embodiment provides a QLED device with a structure of ITO (75nm) / PEDOT:PSS (80nm) / TFB (60nm) / QD (30nm) / ETL (40nm) / Ag (100nm), and the fabrication method is as follows:

[0182] An inkjet printer was used to sequentially deposit a hole injection layer, a hole transport layer, a quantum dot luminescent layer, an electronic functional layer, and a cathode on a bottom-emitting substrate (as the anode). The printer used was a Dimatix Materials Printer DMP-2831.

[0183] The substrate is a glass substrate; the bottom electrode is ITO with a thickness of 75 nm; the hole injection layer is PEDOT:PSS with a thickness of 80 nm; the hole transport layer is TFB with a thickness of 60 nm; the quantum dot emitting layer is CdSe / ZnS core-shell quantum dots (fluorescence at 620 nm) with a thickness of 30 nm; the electronic functional layer is the synthesized ZnO@MOC with a thickness of 40 nm; and the top electrode is Ag with a thickness of 100 nm. After the device fabrication is completed, performance testing is performed, with the device heated at 130°C for 20 minutes before the performance testing.

[0184] Device Examples 2 to 12

[0185] Example n is essentially the same as device example 1, except that in example n, the material of the electronic functional layer is the composite material solution used in thin film example n. n is any integer from 2 to 12.

[0186] Device Example 13

[0187] This embodiment is basically the same as Device Embodiment 1, except that in this embodiment, the electronic functional layer is prepared using an ethanol solution of ZnO obtained in Thin Film Embodiment 11; and the hole transport layer is prepared using a composite material solution obtained in Thin Film Embodiment 13 instead of TFB.

[0188] Device Example 14

[0189] This embodiment is basically the same as device embodiment 1, except that the fabrication of the electronic functional layer is changed in this embodiment:

[0190] Take the cage molecular solution prepared in Thin Film Example 11 and the ethanol solution of ZnO.

[0191] An ethanol solution of ZnO was inkjet printed onto the light-emitting layer to obtain a first film layer with a thickness of approximately 27 nm.

[0192] A cage molecule solution was inkjet printed onto the first film layer to obtain a second film layer with a thickness of approximately 26 nm. The first and second film layers together serve as an electronic functional layer.

[0193] Device Example 15

[0194] This embodiment is basically the same as device embodiment 1, except that the fabrication of the electronic functional layer is changed in this embodiment:

[0195] Take the composite material solution prepared in Thin Film Example 1 and the cage molecule solution prepared in Thin Film Example 11 for later use.

[0196] A composite material solution was inkjet printed onto the light-emitting layer to obtain a first film layer with a thickness of approximately 27 nm.

[0197] A cage molecule solution was inkjet printed onto the first film layer to obtain a second film layer with a thickness of approximately 26 nm.

[0198] The first and second films together serve as electronic functional layers.

[0199] Device Example 16

[0200] This embodiment is basically the same as device embodiment 1, except that the fabrication of the electronic functional layer is changed in this embodiment:

[0201] Take the cage molecular solution prepared in Thin Film Example 11 and the ethanol solution of ZnO.

[0202] A cage molecule solution was inkjet printed onto the light-emitting layer to obtain a second film layer with a thickness of approximately 15 nm.

[0203] An ethanol solution of ZnO was inkjet printed onto the third film layer to obtain a first film layer with a thickness of approximately 27 nm.

[0204] A cage molecule solution was inkjet printed onto the first film layer to obtain a second film layer with a thickness of approximately 11 nm.

[0205] The first film layer and the two second film layers together serve as the electronic functional layer.

[0206] Device Example 17

[0207] This embodiment is basically the same as device embodiment 13, except that the fabrication of the electronic functional layer is changed in this embodiment:

[0208] Take the cage molecule solution prepared in Thin Film Example 11 and set it aside.

[0209] Nickel oxide nanoparticles were dispersed in ethanol to obtain an ethanol solution of nickel oxide.

[0210] An ethanol solution of nickel oxide was inkjet printed onto the light-emitting layer to obtain a first film layer with a thickness of approximately 27 nm.

[0211] A cage molecule solution was inkjet printed onto the first film layer to obtain a second film layer with a thickness of approximately 26 nm. The first and second film layers together serve as an electronic functional layer.

[0212] Device Example 18

[0213] This embodiment is basically the same as device embodiment 13, except that the fabrication of the electronic functional layer is changed in this embodiment:

[0214] Take the composite material solution prepared in Thin Film Example 13 and the cage molecule solution prepared in Thin Film Example 11 for later use.

[0215] A composite material solution was inkjet printed onto the light-emitting layer to obtain a first film layer with a thickness of approximately 27 nm.

[0216] A cage molecule solution was inkjet printed onto the first film layer to obtain a second film layer with a thickness of approximately 26 nm.

[0217] The first and second films together serve as electronic functional layers.

[0218] Device Example 19

[0219] This embodiment is basically the same as device embodiment 13, except that the fabrication of the electronic functional layer is changed in this embodiment:

[0220] Take the cage molecule solution prepared in Thin Film Example 11 and set it aside.

[0221] Nickel oxide nanoparticles were dispersed in ethanol to obtain an ethanol solution of nickel oxide.

[0222] A cage molecule solution was inkjet printed onto the light-emitting layer to obtain a third film layer with a thickness of approximately 15 nm.

[0223] An ethanol solution of nickel oxide was inkjet printed onto the third film layer to obtain a first film layer with a thickness of approximately 27 nm.

[0224] A cage molecule solution was inkjet printed onto the first film layer to obtain a second film layer with a thickness of approximately 11 nm.

[0225] The first film layer and the two second film layers together serve as the electronic functional layer.

[0226] Device Comparison Examples 1 to 4

[0227] Comparative Example m is basically the same as Device Example 1, except that in Comparative Example m, the material of the electronic functional layer is a composite material solution prepared in Thin Film Comparative Example m. m is any integer from 1 to 4.

[0228] Device Comparison Example 5

[0229] This comparative example is basically the same as the device example 13, except that in this comparative example, the hole transport layer is prepared by replacing TFB with nickel oxide solution prepared in thin film comparative example 5.

[0230] (III) Performance tests were conducted on the QLED devices prepared in the above embodiments and comparative examples. The results are shown in Table 2. The testing methods are as follows:

[0231] (1) External quantum dot efficiency:

[0232] The ratio of electron-hole pairs injected into a quantum dot to emitted photons, expressed as a percentage (%), is an important parameter for evaluating the quality of electroluminescent devices. It can be measured using an EQE optical testing instrument. The specific calculation formula is as follows:

[0233]

[0234] Where ηe is the optical output coupling efficiency, ηr is the ratio of recombination carriers to injected carriers, χ is the ratio of the number of excitons generating photons to the total number of excitons, and K R K is the radiation process rate. NR This represents the rate of a non-radiative process.

[0235] Test conditions: Conducted at room temperature with an air humidity of 30-60%.

[0236] (2) Lifetime: The time required for the brightness of a device to decrease to a certain percentage of its maximum brightness under constant current or voltage driving. The time for the brightness to decrease to 95% of the maximum brightness is defined as T95, and this lifetime is the measured lifetime. To shorten the testing cycle, device lifetime testing is usually performed by accelerating device aging under high brightness, referencing OLED device testing, and the lifetime under high brightness is obtained by fitting the extended exponential decay brightness decay fitting formula. For example, the lifetime at 1000 nits is measured as T95. 1000nit The specific calculation formula is as follows:

[0237]

[0238] In the formula, T95 L For longer lifespan at low brightness, T95 H For the measured lifetime under high brightness, L H To accelerate the device to its maximum brightness, L L The value is 1000 nits, and A is the acceleration factor. For OLEDs, this value is usually 1.6 to 2. In this experiment, the lifetime of several groups of QLED devices under rated brightness was measured, and the value of A was found to be 1.7.

[0239] The life test system was used to test the life of the corresponding devices. The test conditions were: room temperature and air humidity of 30-60%.

[0240] Table 2

[0241]

[0242]

[0243] As can be seen from the table above:

[0244] Compared to Comparative Example 1, the devices fabricated in Examples 1 to 11 and 14-16 all exhibit better EQE and T95. 1000nit Compared to Comparative Example 4, Device Example 12 exhibits superior EQE and T95. 1000nit Compared to Comparative Example 5, Device Examples 13 and 17-19 exhibit better EQE and T95. 1000nit This demonstrates that the device prepared from the composite material proposed in this application has better luminescence performance and lifetime. Furthermore, comparing device example 1 with device comparative examples 1 to 3 shows that device example 1 exhibits a more significant improvement in performance compared to device comparative examples 2 and 3. This indicates that compared to metal-organic frameworks and organic cage molecules, using metal-organic cages can better improve device performance. This may be because, compared to crystalline metal-organic frameworks, supramolecular metal-organic cages have better solubility and can combine with metal oxides, thus better improving the material's dispersibility and film-forming properties. Moreover, the metal-organic cage contains metal atoms, which, compared to organic cage molecules, are more conducive to carrier transport, further contributing to improved device performance.

[0245] The technical solutions provided by the embodiments of this application have been described in detail above. Specific examples have been used to illustrate the principles and implementation methods of this application. The description of the above embodiments is only for the purpose of helping to understand the method and core ideas of this application. At the same time, for those skilled in the art, there will be changes in the specific implementation methods and application scope based on the ideas of this application. Therefore, the content of this specification should not be construed as a limitation of this application.

Claims

1. A composite material, characterized in that, This includes metal oxides and metal-organic cages.

2. The composite material according to claim 1, characterized in that, The metal-organic cage is connected to the metal oxide; optionally, the metal-organic cage has an active group, the active group including at least one of hydroxyl, primary amino, secondary amino and thiol groups; the metal-organic cage is connected to the metal oxide through the active group.

3. The composite material according to claim 1, characterized in that, The metal oxide includes N-type metal oxides, which include one or more of undoped oxides and doped oxides; the undoped oxides include one or more of ZnO, SnO2, and TiO2; the doped oxides include oxides doped with a dopant element, which includes one or more of ZnO, SnO2, and TiO2, and the dopant element includes one or more of Al, Mg, Li, In, Ga, Ti, Mn, Sn, Ag, and Cu; optionally, in the doped metal oxide, the molar percentage of the dopant element is greater than 0 and less than or equal to 20%, or the metal oxide includes P-type metal oxides, which include one or more of molybdenum oxide, copper oxide, nickel oxide, tungsten oxide, and vanadium oxide; And / or, the molar ratio of the metal organic cage to the metal oxide is 1:1.3 to 5; And / or, the metal organic cage is an A-based MOC, wherein A is a metallic element selected from one or more of Zr, Ti, Hf, Nb, Zn, Cu, and Fe; Optionally, the metal organic cage has the structure shown in formula (I): Equation (Ⅰ): in: A is selected from one of Zr, Ti, Hf, and Nb; X1, X2, and X3 are each independently selected from one or more combinations of hydrogen, deuterium, halogen, hydroxyl, carboxyl, nitro, sulfonic acid, aldehyde, mercapto, cyano, amino, C1-C20 alkyl, C3-C30 cycloalkyl, C1-C20 alkoxy, C6-C30 aryl, C5-C30 heteroaryl, C6-C30 aryloxy, and C5-C30 heteroaryloxy. R1 is selected from at least one of -OH, -NH2, -NHR2 and -SH; R2 is selected from one or more combinations of C1 to C20 alkyl, C3 to C30 cycloalkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted heteroaryl with 5 to 20 ring atoms. Ring B is selected from substituted or unsubstituted aromatic rings of C6 to C30; When substituted, each substituent is independently selected from one or more combinations of deuterium, halogen, hydroxyl, carboxyl, nitro, sulfonic acid, aldehyde, mercapto, cyano, amino, C1-C20 alkyl, C3-C30 cycloalkyl, C1-C20 alkoxy, C6-C30 aryl, C5-C30 heteroaryl, C6-C30 aryloxy, and C5-C30 heteroaryloxy.

4. The composite material according to claim 3, characterized in that, A is selected from Zr; And / or, L is selected from any of the following structures:

5. A method for preparing a composite material, characterized in that, Includes the following steps: A metal oxide, a metal-organic cage, and a first solvent are provided; the metal oxide, the metal-organic cage, and the first solvent are mixed and a first reaction is carried out to obtain a composite material; or... A metal salt, a metal-organic cage, an alkali, and a first solvent are provided; the metal salt, the metal-organic cage, the alkali, and the first solvent are mixed to carry out a second reaction to obtain a composite material.

6. The preparation method according to claim 5, characterized in that, Includes at least one of the following features (1) to (12): (1) The molar ratio of the metal organic cage to the metal oxide is 1:3 to 8; (2) The metal oxide includes N-type metal oxide or P-type metal oxide. The N-type metal oxide includes one or more of undoped oxide and doped oxide. The undoped oxide includes one or more of ZnO, SnO2, and TiO2. The doped oxide includes oxide doped with a dopant element. The oxide includes one or more of ZnO, SnO2, and TiO2. The dopant element includes one or more of Al, Mg, Li, In, Ga, Ti, Mn, Sn, Ag, and Cu. Optionally, in the doped metal oxide, the molar percentage of the dopant element is greater than 0 and less than or equal to 20%. The P-type metal oxide includes one or more of molybdenum oxide, copper oxide, nickel oxide, tungsten oxide, and vanadium oxide. (3) The metal-organic cage is an A-based MOC, wherein A is a metallic element selected from one or more of Zr, Ti, Hf, Nb, Zn, Cu, and Fe; optionally, the metal-organic cage has the structure shown in formula (I): Equation (Ⅰ): in: A is selected from Zr, Ti, Hf, and Nb; X1, X2, and X3 are each independently selected from one or more combinations of hydrogen, deuterium, halogen, hydroxyl, carboxyl, nitro, sulfonic acid, aldehyde, mercapto, cyano, amino, C1-C20 alkyl, C3-C30 cycloalkyl, C1-C20 alkoxy, C6-C30 aryl, C5-C30 heteroaryl, C6-C30 aryloxy, and C5-C30 heteroaryloxy; R1 is selected from at least one of -OH, -NH2, -NHR2, and -SH; R2 is selected from C1-C20 alkyl, C3-C30 cycloalkyl, substituted or The ring B is selected from one or more combinations of unsubstituted C6-C30 aryl groups and substituted or unsubstituted heteroaryl groups having 5-20 ring atoms; when substituted, each substituent is independently selected from one or more combinations of deuterium, halogen, hydroxyl, carboxyl, nitro, sulfonic acid, aldehyde, mercapto, cyano, amino, C1-C20 alkyl, C3-C30 cycloalkyl, C1-C20 alkoxy, C6-C30 aryl, C5-C30 heteroaryl, C6-C30 aryloxy, and C5-C30 heteroaryloxy. (4) The temperature of the first reaction is 20-40℃; (5) The reaction time for the first reaction is 60-80 hours; (6) The metal salt includes a first metal salt or a second metal salt, wherein the first metal salt includes one or more of zinc salt, titanium salt, and tin salt, and the second metal salt includes one or more of copper salt, nickel salt, tungsten salt, molybdenum salt, and vanadium salt; optionally, when the metal salt includes the first metal salt, the metal salt further includes a doped metal salt, wherein the doped metal salt includes one or more of aluminum salt, magnesium salt, lithium salt, indium salt, gallium salt, titanium salt, manganese salt, tin salt, silver salt, and copper salt; (7) The base includes one or more alkali metal hydroxides; (8) The first solvent includes one or more of dimethyl sulfoxide, N,N-dimethylformamide, methanol, ethanol, isopropanol, n-butanol, pentanol, and hexanol; (9) The molar ratio of the metal element in the metal salt to the metal organic cage is 4.5 to 12.5:1; (10) The molar ratio of the metal element in the metal salt to the alkali is 1:1.5 to 2.5; (11) The temperature of the second reaction is 20–40 °C; (12) The second reaction takes 10 to 72 hours.

7. The preparation method according to claim 6, characterized in that, When the metal-organic cage has the structural formula (I), the preparation method further includes the preparation of the metal-organic cage, which includes: dispersing a dihalodicyclopentadiene salt and a first compound in a second solvent, and carrying out a third reaction at 40-80°C to obtain the metal-organic cage; wherein the dihalodicyclopentadiene salt has the structure shown in formula (II), and the first compound has the structure shown in formula (III): Formula (II): Formula (Ⅲ): COOH-L-COOH; Wherein, X is selected from X1, X2 or X3; Y1 and Y2 are each independently selected from halogens; Optionally, the dihalocene dichloride includes one of zirconium dichloride, 1,1'-dibutylzirconium dichloride, titanium dichloride, hafnium dichloride, and niobium dichloride. Optionally, the molar ratio of the dihalocene salt to the first compound is 1:1.8 to 3; Optionally, the second solvent includes one or more of dimethylformamide, dimethylacetamide, dimethyl sulfoxide, methanol, acetone, and acetonitrile; Optionally, the first compound includes one of the following compounds:

8. A thin film, characterized in that, The materials of the thin film include metal oxides and metal-organic cages.

9. The thin film according to claim 8, characterized in that, The film is a single-layer film, and the material of the single-layer film includes the composite material according to any one of claims 1 to 4, or the composite material prepared by the preparation method according to any one of claims 5 to 7; or, The thin film includes a first film layer and a second film layer disposed on one side of the first film layer. The material of the first film layer includes the metal oxide, and the material of the second film layer includes the metal-organic cage. Further, the material of the first film layer also includes the metal-organic cage. In the first film layer, the molar ratio of the metal-organic cage to the metal oxide is 1:1.3 to 5.

10. An optoelectronic device, characterized in that, It includes a stacked anode, a carrier functional layer, and a cathode, wherein the carrier functional layer includes the thin film as described in claim 9 or 10.

11. The optoelectronic device according to claim 10, characterized in that, When the metal oxide in the thin film is an N-type metal oxide, the thin film is a first thin film; when the metal oxide in the thin film is a P-type metal oxide, the thin film is a second thin film. The carrier functional layer includes a hole functional layer and / or an electron functional layer, wherein the electron functional layer includes the first thin film and the hole functional layer includes the second thin film.

12. The optoelectronic device according to claim 11, characterized in that, The optoelectronic device further includes a light-emitting layer, which is disposed between the charge carrier functional layer and the anode or between the charge carrier functional layer and the cathode; the material of the light-emitting layer includes organic light-emitting materials or quantum dots, wherein the organic light-emitting material includes at least one of diaromatic anthracene derivatives, stilbene aromatic derivatives, pyrene derivatives or fluorene derivatives, blue-emitting TBPe fluorescent materials, green-emitting TTPA fluorescent materials, orange-emitting TBRb fluorescent materials, and red-emitting DBP fluorescent materials; the quantum dots include at least one of single-structure quantum dots, core-shell structure quantum dots, and perovskite semiconductor materials, wherein the shell of the core-shell structure quantum dots comprises one or more layers; the material of the single-structure quantum dots... The core material and shell material of the core-shell structured quantum dots respectively include at least one of group II-VI compounds, group IV-VI compounds, group III-V compounds, and group I-III-VI compounds; the group II-VI compounds include 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, HgZn At least one of Se, HgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, and HgZnSTe; the IV-VI group compounds include 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 group compounds include GaN, GaP, GaAs, and Ga Sb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPS b. At least one of GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs and InAlPSb;The group I-III-VI compounds include at least one of CuInS2, CuInSe2, and AgInS2; the perovskite semiconductor material includes 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, where X is a halide anion selected from Cl. - ,Br - I - At least one of the following; the general structural formula of the organic-inorganic hybrid perovskite semiconductor is BMX3, wherein B is an organic amine cation selected from CH3(CH2). n-2 NH3 + Or [NH3(CH2)] n NH3] 2+ Where n≥2, M is a divalent metal cation selected from Pb 2+ Sn 2+ Cu 2+ Ni 2+ Cd 2+ Cr 2+ Mn 2+ Co 2+ Fe 2+ 、Ge 2+ Yb 2+ Eu 2+ At least one of them, where X is a halide anion selected from Cl. - ,Br - I - At least one of them; and / or, The anode and the cathode each independently include a doped metal oxide particle electrode, a metal and metal oxide composite electrode, a graphene electrode, a carbon nanotube electrode, or a metal electrode. 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 metal and metal oxide composite electrode is selected from AZO / Ag / AZO, AZO / Al / AZO, ITO / Ag / ITO, ITO / Al / ITO, ZnO / Ag / ZnO, ZnO / Al / ZnO, TiO2 / Ag / TiO2, TiO2 / Al / TiO2, ZnS / Ag / ZnS, and ZnS / Al / ZnS. The material of the metal electrode is selected from one or more of Ag, Al, Cu, Mo, Au, Pt, Si, Ca, Mg, and Ba.

Images