Method for producing metal oxides, metal oxides, thin films and optoelectronic devices

Abstract

This application provides a method for preparing a metal oxide, a metal oxide, a thin film, and an optoelectronic device. The method for preparing the metal oxide includes the steps of: mixing a metal precursor and an alkaline solution to obtain a first mixture; and mixing the first mixture with an amine compound to obtain the metal oxide, which can improve the performance stability of the metal oxide.

Description

Technical Field

[0001] This application relates to the field of optoelectronic materials technology, specifically to a method for preparing a metal oxide, the metal oxide, the thin film, and optoelectronic devices. Background Technology

[0002] Metal oxides are compounds formed by the combination of metal elements and oxygen elements. When metal oxides are nanoscaled, they exhibit small size effect, surface and interface effect, quantum dot size effect and macroscopic quantum tunneling effect due to their small size, large specific surface area and many surface active centers. As a result, they are widely used in batteries, optoelectronic devices, supercapacitors, energy storage devices and magnetic devices.

[0003] Metal oxides generally have a large number of defect states, such as oxygen vacancy defect states and metal vacancy defect states, and the number of defect states can vary with environmental conditions, resulting in poor performance stability of metal oxides, which in turn negatively affects the performance of devices containing metal oxides. Summary of the Invention

[0004] This application provides a method for preparing a metal oxide, the metal oxide, the thin film, and an optoelectronic device, to reduce the number of defect states in the metal oxide.

[0005] The technical solution of this application is as follows:

[0006] In a first aspect, embodiments of this application provide a method for preparing a metal oxide, comprising the steps of:

[0007] The metal precursor and the alkali were mixed in solution to obtain a first mixture; and

[0008] The first mixture is mixed with an amine compound to obtain the metal oxide;

[0009] The amine compounds have the structure shown in general formula (Ⅰ):

[0010]

[0011] In general formula (Ⅰ), R1, R2, and R3 are independently selected from hydrogen, deuterium, and *-NR, respectively. a R b Unreplaced or replaced by at least one R c Substituted C1–C30 aliphatic chain hydrocarbon groups, unsubstituted or with at least one R c Substituted C1–C30 aliphatic chain hydroxyl groups, unsubstituted or with at least one R c Substituted C3–C30 aliphatic cyclic hydrocarbon groups, unsubstituted or with at least one R cSubstituted C3–C30 aliphatic heterocyclic hydrocarbon groups, unsubstituted or with at least one R c The substituted aryl group has 6 to 30 cyclic atoms, is unsubstituted, or is substituted with at least one R. c The substituted aryloxy group has 6 to 30 cyclic atoms, and is either unsubstituted or substituted with at least one R. c The substituted heteroaryl group has 5 to 30 cyclic atoms, is unsubstituted, or is substituted with at least one R c The substituted ring atoms are 5 to 30 heteroaryloxy groups, or combinations of these groups;

[0012] R1 to R3 are not simultaneously selected from hydrogen, deuterium, *-NH2 or *-ND2;

[0013] R c Each occurrence is independently selected from deuterium and *-NR. a R b Halogen groups, hydroxyl groups, carboxyl groups, nitro groups, sulfonic acid groups, aldehyde groups, mercapto groups, cyano groups, C1-C20 aliphatic chain hydrocarbon groups, C1-C20 aliphatic chain alkyloxy groups, aliphatic cyclic hydrocarbon groups with 3-20 ring atoms, aliphatic heterocyclic hydrocarbon groups with 3-20 ring atoms, aryl groups with 6-20 ring atoms, aryloxy groups with 6-20 ring atoms, heteroaryl groups with 5-20 ring atoms, heteroaryloxy groups with 5-20 ring atoms, or combinations of these groups;

[0014] Among them, R a and R b Each time it appears, it is independently selected from hydrogen, deuterium, C1-C20 aliphatic chain hydrocarbon group, C1-C20 aliphatic chain hydrocarbon oxygen group, aliphatic cyclic hydrocarbon group with 3-20 ring atoms, aliphatic heterocyclic hydrocarbon group with 3-20 ring atoms, aryl group with 6-20 ring atoms, aryloxy group with 6-20 ring atoms, heteroaryl group with 5-20 ring atoms, heteroaryloxy group with 5-20 ring atoms, or a combination of these groups;

[0015] * indicates a connection point.

[0016] Secondly, this application provides a metal oxide whose surface is attached with a ligand having the structure shown in general formula (II):

[0017]

[0018] In general formula (II), & represents the connection site between the ligand and the metal oxide; R1 is selected from R1 as described in the first aspect, R2 is selected from R2 as described in the first aspect, and R3 is selected from R3 as described in the first aspect.

[0019] Thirdly, this application provides a thin film comprising a metal oxide prepared by the method for preparing metal oxides as described in the first aspect, and / or the thin film comprising a metal oxide as described in the second aspect.

[0020] Fourthly, this application provides an optoelectronic device, comprising:

[0021] The anode and cathode are arranged opposite each other; and

[0022] Multiple functional layers are disposed between the anode and the cathode;

[0023] Wherein, at least one of the plurality of functional layers is made of a metal oxide prepared by the method for preparing metal oxides as described in the first aspect, or a metal oxide as described in the second aspect, and / or at least one of the plurality of functional layers is made of a thin film as described in the third aspect.

[0024] This application provides a method for preparing a metal oxide, the metal oxide, the thin film, and the optoelectronic device, which has the following technical advantages:

[0025] In the preparation method of the metal oxide, the metal precursor and the alkaline solution are first mixed, and then an amine compound is added. This can improve the aggregation phenomenon of the colloidal dispersion during the nucleation and crystal growth stages of the metal oxide, and passivate the grain boundaries to reduce the number of defect states in the metal oxide, thereby improving the performance stability of the metal oxide. Attached Figure Description

[0026] 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.

[0027] Figure 1 This is a schematic flowchart of a method for preparing a metal oxide provided in an embodiment of this application.

[0028] Figure 2 This is a schematic diagram of the structure of an optoelectronic device provided in an embodiment of this application. Detailed Implementation

[0029] The technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of this application, and not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of this application without creative effort are within the scope of protection of this application.

[0030] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those familiar to those skilled in the art. Furthermore, any methods and materials similar to or equivalent to those described herein may be applied to this invention. The preferred embodiments and materials described herein are for illustrative purposes only and do not limit the scope of this application.

[0031] It should be noted that the order of description of the following embodiments is not intended to limit the preferred order of embodiments. The various embodiments of this application may exist in a range format. It should be understood that the description in a range format is merely for convenience and simplicity and should not be construed as a rigid limitation on the scope of the invention. Therefore, it should be considered that the range description has specifically disclosed all possible sub-ranges and single numerical 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 the range, such as 1, 2, 3, 4, 5, and 6, regardless of the range. Furthermore, whenever a numerical range is indicated herein, it means including any referenced number (fraction or integer) within the indicated range.

[0032] In this application, unless otherwise stated, directional terms such as "upper" and "lower" generally refer to the upper and lower positions of the optoelectronic device in its actual use or operating state, specifically the orientation shown in the accompanying drawings; while "inner" and "outer" refer to the outline of the optoelectronic device. The terms "first," "second," "third," etc., are used merely as indications and do not impose numerical requirements or establish a sequence.

[0033] In this application, descriptions such as "layer A is formed on one side of layer B," "layer A is formed on the side of layer B away from layer C," or similar expressions can mean that layer A is directly formed on one side of layer B or on the side of layer B away from layer C, i.e., layer A and layer B are in direct contact; or they can mean that layer A is indirectly formed on one side of layer B or on the side of layer B away from layer C, i.e., other spacer structures can be formed between layer A and layer B. Similarly, "layer A is disposed on one side of layer B" or "layer A is disposed on the side of layer B away from layer C" can mean that layer A and layer B are in direct contact, or that other spacer structures are provided between layer A and layer B; "layer A is disposed between layer B and layer C" can mean that layer A and layer B are in direct contact and layer A and layer C are in direct contact, or layer A and layer B are in direct contact and one or more spacer structures are provided between layer A and layer C, or layer A and layer B are provided and one or more spacer structures are provided between layer A and layer C, or layer A and layer B are provided and layer A and layer C are in direct contact.

[0034] In this application, the thickness of the thin film refers to the average thickness of the thin film, and the thickness of a certain functional layer refers to the average thickness of the functional layer. The thickness is obtained by measuring a step tester.

[0035] The term "including" means "including but not limited to". The term "and / or" describes the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A alone, A and B simultaneously, or B alone. A and B can be singular or plural. The term "at least one" means one or more, and "more than one" means two or more. The terms "at least one", "at least one of the following", or similar expressions refer to any combination of these items, including any combination of a single or plural type. For example, "at least one of a, b, or c" or "at least one of a, b, and c" can be expressed as: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can each be a single or multiple type.

[0036] The term "average particle size" refers to the area-average particle size of a particle swarm. Area-average particle size is calculated by dividing the total volume of the particle swarm by its total area, which is the reciprocal of the surface area per unit volume. If an imaginary swarm of particles with uniform size is used to replace the original swarm, and the total volume and area of ​​this imaginary swarm are identical to the original swarm, then the diameter of this imaginary swarm is the area-average particle size of the original swarm. Area-average particle size can be obtained through statistical analysis, using transmission electron microscopy to statistically analyze the particle size of each particle in the swarm.

[0037] The term "aliphatic chain hydrocarbon group" refers to a group obtained by removing a hydrogen atom from an aliphatic hydrocarbon (saturated or unsaturated aliphatic hydrocarbon). It can be an aliphatic straight-chain alkyl group, an aliphatic straight-chain alkenyl group, an aliphatic straight-chain alkynyl group, an aliphatic branched alkyl group, an aliphatic branched alkenyl group, or an aliphatic branched alkynyl group. "C1-C30 aliphatic chain hydrocarbon group" can be, for example, aliphatic chain hydrocarbon groups of C1-C20, C1-C18, C1-C15, C1-C12, C1-C10, C1-C8, C1-C6, or C1-C3. Aliphatic chain hydrocarbon groups can be, for example, C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, C7 alkyl, C8 alkyl, C9 alkyl, or C10 alkyl. Suitable examples of "aliphatic chain hydrocarbon groups" include, but are not limited to, methyl, ethyl, vinyl, ethynyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, etc.

[0038] The term "aliphatic chain alkyl group" refers to a group with the general formula *-O-aliphatic chain hydrocarbon group, where * indicates a linking site and O represents an oxygen atom. The number of carbon atoms in a "C1-C30 aliphatic chain alkyl group" can be, for example, 1 to 20, 1 to 18, 1 to 15, 1 to 10, 1 to 8, 1 to 5, or 1 to 3. For example, a "C1-C30 aliphatic chain alkyl group" can be an alkoxy group of C1-C20, C1-C18, C1-C15, C1-C12, C1-C10, C1-C8, C1-C6, or C1-C3. Suitable examples include, but are not limited to, methoxy (-O-CH3 or -OMe), ethoxy (-O-CH2CH3 or -OEt), tert-butoxy (-OC(CH3)3 or -OtBu), and n-hexyloxy (-O-C6H). 13 ), n-decanoyloxy (-OC) 10 H 21 ), or n-dodecyloxy (-OC) 12 H 25 ).

[0039] The term "aliphatic cyclic hydrocarbon group" refers to an aliphatic cyclic hydrocarbon group. "Aliphatic cyclic hydrocarbon groups with 3 to 30 ring atoms" can be, for example, aliphatic cyclic hydrocarbon groups with 3 to 20 ring atoms, 3 to 18 ring atoms, 3 to 16 ring atoms, 3 to 14 ring atoms, 3 to 12 ring atoms, 3 to 10 ring atoms, 3 to 8 ring atoms, 3 to 6 ring atoms, or 3 to 5 ring atoms. The number of ring atoms in an aliphatic cyclic hydrocarbon group can be, for example, 3 to 20, 3 to 18, 3 to 16, 3 to 14, 3 to 10, 3 to 8, or 3 to 5. More specifically, the aliphatic cycloalkyl group can be, for example, a C3-C20 cycloalkyl, C3-C18 cycloalkyl, C3-C16 cycloalkyl, C3-C14 cycloalkyl, C3-C10 cycloalkyl, C3-C8 cycloalkyl, or C3-C5 cycloalkyl. Suitable examples include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, or adamantyl.

[0040] The term "aliphatic heterocyclic hydrocarbon group" refers to an aliphatic cyclic hydrocarbon group in which at least one carbon atom is replaced by a non-carbon atom. The non-carbon atom can be one or more of N, O, S, Si, and P atoms. The number of heteroatoms in the aliphatic heterocyclic hydrocarbon group is independently between 1 and 20. "Aliphatic heterocyclic hydrocarbon group with 3 to 30 ring atoms" can be, for example, an aliphatic heterocyclic hydrocarbon group with 3 to 20 ring atoms, an aliphatic heterocyclic hydrocarbon group with 3 to 18 ring atoms, an aliphatic heterocyclic hydrocarbon group with 3 to 16 ring atoms, an aliphatic heterocyclic hydrocarbon group with 3 to 14 ring atoms, an aliphatic heterocyclic hydrocarbon group with 3 to 12 ring atoms, an aliphatic heterocyclic hydrocarbon group with 3 to 10 ring atoms, an aliphatic heterocyclic hydrocarbon group with 3 to 8 ring atoms, an aliphatic heterocyclic hydrocarbon group with 3 to 6 ring atoms, or an aliphatic heterocyclic hydrocarbon group with 3 to 5 ring atoms. The number of carbon atoms in an aliphatic heterocyclic hydrocarbon group can be, for example, 3 to 20, 3 to 18, 3 to 16, 3 to 14, 3 to 10, 3 to 8, or 3 to 5. Suitable examples of aliphatic heterocyclic hydrocarbon groups include, but are not limited to, cyclothioethyl, acridine, or ethylene oxide.

[0041] The term "aryl" refers to a group obtained by removing a hydrogen atom from an aromatic ring compound. It can be a monocyclic aryl, a fused-ring aryl, or a polycyclic aryl, and in the case of a polycyclic ring, at least one of the rings must be an aromatic ring system. "Aryl with 6 to 30 ring atoms" can be, for example, an aryl with 6 to 24 ring atoms, an aryl with 6 to 20 ring atoms, an aryl with 6 to 18 ring atoms, an aryl with 6 to 16 ring atoms, an aryl with 6 to 14 ring atoms, or an aryl with 6 to 10 ring atoms. Suitable examples include, but are not limited to, phenyl, biphenyl, terphenyl, naphthyl, anthracene, phenanthryl, fluoranyl, triphenylene, pyrene, perylene, tetraphenyl, fluorenyl, dinaphthylphenyl, acenaphthyl, and their derivatives. Understandably, 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.

[0042] The term "aryloxy group" refers to a group with the general formula *-O-aryl, where * indicates a linking site and O indicates an oxygen atom. "Aryloxy group with 6 to 30 ring atoms" can be, for example, an aryloxy group with 6 to 24 ring atoms, an aryloxy group with 6 to 20 ring atoms, an aryloxy group with 6 to 18 ring atoms, an aryloxy group with 6 to 16 ring atoms, an aryloxy group with 6 to 14 ring atoms, or an aryloxy group with 6 to 10 ring atoms. Suitable examples include, but are not limited to, phenoxy, naphthoxy, or biphenyloxy.

[0043] The term "heteroaryl" refers to an aryl group in which at least one carbon atom is replaced by a non-carbon atom. The non-carbon atom can be one or more of N, O, S, Si, and P atoms, and the number of heteroatoms can be, for example, 1 to 20. "Heteroaryl with 5 to 30 ring atoms" can be, for example, a heteroaryl with 5 to 24 ring atoms, a heteroaryl with 5 to 20 ring atoms, a heteroaryl with 5 to 18 ring atoms, a heteroaryl with 5 to 16 ring atoms, a heteroaryl with 5 to 14 ring atoms, or a heteroaryl with 5 to 10 ring atoms. Suitable examples include, but are not limited to, thiophene, furanyl, pyrrolyl, diazolyl, triazolyl, imidazole, pyridyl, bipyridyl, pyrimidinyl, triazinyl, acridineyl, pyridazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, benzothiophene, benzofuranyl, indolyl, pyrroloimidazolyl, pyrrolopyrrolyl, thienopyrrolyl, thienopyrrolyl, furanolyl, furanolyl, thienofuranyl, benzoisoxazolyl, benzoisothiazolyl, benzoimidazolyl, o-diazonyl, phenanthridine, primidyl, quinazolinone, dibenzothiophene, dibenzofuranyl, or carbazolyl.

[0044] The term "heteroaryl group" refers to a group with the general formula *-O-heteroaryl, where * represents the linking site and O represents an oxygen atom. "Heteroaryl group with 5 to 30 ring atoms" can be, for example, a heteroaryl group with 5 to 24 ring atoms, a heteroaryl group with 5 to 20 ring atoms, a heteroaryl group with 5 to 18 ring atoms, a heteroaryl group with 5 to 16 ring atoms, a heteroaryl group with 5 to 14 ring atoms, or a heteroaryl group with 5 to 10 ring atoms.

[0045] In this application, the single bonds connecting the substituents extend through the corresponding ring, indicating that the substituent can be connected to any position on the ring.

[0046] In this application, "halogen group" or "halogen" represents -Cl, -Br, -F or -I; hydroxyl group represents -OH; carboxyl group represents -COOH; nitro group represents -NO2; sulfonic acid group represents -SO3H; mercapto group represents -SH; cyano group represents *-C≡N.

[0047] 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.

[0048] Firstly, embodiments of this application provide a method for preparing a metal oxide, such as... Figure 1 As shown, it includes the following steps:

[0049] S1. Mix the metal precursor and the alkali in the solution to obtain the first mixture;

[0050] S2. Mix the first mixture with an amine compound to obtain a metal oxide.

[0051] Among them, amine compounds have the structure shown in the general formula (Ⅰ):

[0052]

[0053] In general formula (Ⅰ), R1, R2, and R3 are independently selected from hydrogen, deuterium, and *-NR, respectively. a R b Unreplaced or replaced by at least one R c Substituted C1–C30 aliphatic chain hydrocarbon groups, unsubstituted or with at least one R c Substituted C1–C30 aliphatic chain hydroxyl groups, unsubstituted or with at least one R c Substituted C3–C30 aliphatic cyclic hydrocarbon groups, unsubstituted or with at least one R c Substituted C3–C30 aliphatic heterocyclic hydrocarbon groups, unsubstituted or with at least one R c The substituted aryl group has 6 to 30 cyclic atoms, is unsubstituted, or is substituted with at least one R. c The substituted aryloxy group has 6 to 30 cyclic atoms, and is either unsubstituted or substituted with at least one R. c The substituted heteroaryl group has 5 to 30 cyclic atoms, is unsubstituted, or is substituted with at least one R c The substituted ring atoms are 5 to 30 heteroaryloxy groups, or combinations of these groups;

[0054] R1 to R3 are not simultaneously selected from hydrogen, deuterium, *-NH2 or *-ND2;

[0055] R c Each occurrence is independently selected from deuterium and *-NR. a R b Halogen groups, hydroxyl groups, carboxyl groups, nitro groups, sulfonic acid groups, aldehyde groups, mercapto groups, cyano groups, C1-C20 aliphatic chain hydrocarbon groups, C1-C20 aliphatic chain alkyloxy groups, aliphatic cyclic hydrocarbon groups with 3-20 ring atoms, aliphatic heterocyclic hydrocarbon groups with 3-20 ring atoms, aryl groups with 6-20 ring atoms, aryloxy groups with 6-20 ring atoms, heteroaryl groups with 5-20 ring atoms, heteroaryloxy groups with 5-20 ring atoms, or combinations of these groups;

[0056] Among them, R a and R bEach time it appears, it is independently selected from hydrogen, deuterium, C1-C20 aliphatic chain hydrocarbon group, C1-C20 aliphatic chain hydrocarbon oxygen group, aliphatic cyclic hydrocarbon group with 3-20 ring atoms, aliphatic heterocyclic hydrocarbon group with 3-20 ring atoms, aryl group with 6-20 ring atoms, aryloxy group with 6-20 ring atoms, heteroaryl group with 5-20 ring atoms, heteroaryloxy group with 5-20 ring atoms, or a combination of these groups.

[0057] * indicates a connection point.

[0058] In the above-mentioned method for preparing metal oxides, the metal precursor and the alkaline solution are first mixed, and then an amine compound is added. This can improve the aggregation of colloidal dispersions during the nucleation and crystal growth stages of metal oxides, and passivate grain boundaries to reduce the number of defect states in metal oxides, thereby improving the performance stability of metal oxides.

[0059] It should be noted that, compared to mixing the metal precursor, base, and amine compound together in solution, the above-mentioned method for preparing metal oxides has the following advantages: First, the stepwise addition of raw materials allows for more precise control of the nucleation and crystal growth stages, resulting in more uniform metal oxides with a narrower size distribution; second, the stepwise addition of raw materials reduces particle agglomeration during the reaction process; third, the stepwise addition of raw materials reduces the occurrence of side reactions, thereby improving the purity of the metal oxides; and fourth, the timely addition of amine compounds during the nucleation and growth stages can more effectively passivate grain boundaries and reduce defect states.

[0060] Compared to mixing the metal precursor and amine compound first, and then adding a base for reaction, the above method for preparing metal oxides has the following advantages: First, adding a base first can prevent excessive metal precursor and amine compound from reacting prematurely to form a precipitate, thus helping to control the reaction rate and product quality; Second, adding a base first helps to adjust the pH value of the solution, which can enhance the passivation effect of the amine compound, thereby more effectively reducing the defect states of the metal oxide; Third, adding a base before mixing the metal precursor and amine compound can create a more suitable environment for crystal growth, which helps to form higher quality crystals.

[0061] In step S1, the step of mixing the metal precursor and the alkali in the solution includes, for example, providing a first solution containing the metal precursor and a second solution containing the alkali, and then adding the first solution to the second solution, or adding the second solution to the first solution, wherein the addition method includes, but is not limited to, dripping or injection. It is understood that the step of mixing the metal precursor and the alkali in the solution may further include, for example, adding the metal precursor to the second solution containing the alkali and then dispersing it evenly; or, adding the alkali to the first solution containing the metal precursor and then dispersing it evenly.

[0062] In some embodiments of this application, the metal element of the metal precursor is selected from one or more of Group IA metals, Group IIA metals, Group IIIA metals, Group IVA metals, Group VA metals and transition metals. For example, the metal element of the metal precursor is selected from one or more of Zn, Ti, Sn, Ba, Ta, Al, Zr, Mg, Ca, Ga, Li, Y, In, Ni, Mo, W, V, Cr and Cu.

[0063] The metal precursor can be an inorganic salt or an organometallic compound. The anions constituting the inorganic salt include, but are not limited to, halide ions, sulfate ions, carbonate ions, nitrate ions, phosphate ions, monohydrogen phosphate ions, or dihydrogen phosphate ions. Taking Zn as an example, the selectable inorganic salts include, but are not limited to, one or more of zinc halides, zinc nitrates, zinc sulfates, zinc carbonates, and zinc phosphates. The organometallic compound can be, but is not limited to, one or more of organic salts and organic complexes. The anions constituting the organic salt include, but are not limited to, carboxylate ions with 2 to 20 carbon atoms. These carboxylate ions with 2 to 20 carbon atoms can be, for example, oxalate ions, acetate ions, citrate ions, lactate ions, stearate ions, tetradecanoate ions, or oleate ions. Taking Zn as an example, the organic salt includes, but is not limited to, one or more of zinc stearate, zinc acetate, zinc tetradecanoate, zinc oleate, zinc citrate, and zinc lactate. The organic complexes include, but are not limited to, zinc acetylacetonate. The concentration of the first metal element in the first metal precursor solution is, for example, 0.01 mmol / mL to 0.5 mmol / mL.

[0064] Bases include one or more of organic and inorganic bases. Inorganic bases include, but are not limited to, one or more of alkali metal oxides, alkali metal hydroxides, alkali metal bicarbonates, alkali metal carbonates, alkaline earth metal oxides, alkaline earth metal hydroxides, alkaline earth metal bicarbonates, barium hydroxide, and ammonia water. Inorganic bases are, for example, selected from one or more of lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium oxide, potassium oxide, calcium oxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, and calcium bicarbonate. Organic bases include, but are not limited to, one or more of alkanolamines, alkyl ammonium hydroxides, and urea. The alkyl group in alkyl ammonium hydroxide contains 1 to 20 carbon atoms. Alkyl ammonium hydroxides are, for example, selected from one or more of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide. Alkanolamines are, for example, selected from one or more of ethanolamine, diethanolamine, and triethanolamine.

[0065] In step S1, the solution may include a solvent with a polarity of 4 to 10, such as one or more of methanol, ethanol, ethylene glycol, acetonitrile, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, dichloromethane, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, 3-methoxybutanol, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, and diethylene glycol dimethyl ether.

[0066] In order to improve the purity of the obtained metal oxide, in some embodiments of this application, the metal precursor and the base are mixed in an inert gas atmosphere, including but not limited to nitrogen, helium, argon, krypton, xenon or neon.

[0067] In some embodiments of this application, the metal precursor and the alkali are mixed at a temperature of 25°C to 40°C, for example, 25°C, 30°C, 35°C, 40°C or any two of the aforementioned values.

[0068] In order to further improve the yield of metal oxides, in some embodiments of this application, in the step of mixing the metal precursor and the alkali in solution, the molar ratio of the metal precursor to the alkali is 1:(0.8 to 5), for example, it can be 1:0.8, 1:1, 1:2, 1:3, 1:4, 1:5 or any value between the two aforementioned ratios.

[0069] In some embodiments of this application, the pH of the first mixture is 12 to 14, for example, it can be 12, 13, 14 or any two of the aforementioned values.

[0070] To further improve the passivation effect of amine compounds on grain boundaries, in some embodiments of this application, the mixing time of the metal precursor and the alkali is 10 min to 30 min, for example, it can be 10 min, 15 min, 20 min, 25 min, 30 min or any two of the aforementioned values. The mixing time of the metal precursor and the alkali within the aforementioned range can ensure that the metal precursor and the alkali react sufficiently to form sufficiently uniform and numerous crystal nuclei, that is, to ensure sufficient nucleation, and can also avoid excessive growth of crystal nuclei to form larger grains, thereby further improving the problem of particle agglomeration.

[0071] To improve the solubility and / or dispersibility of amine compounds in the first mixture and to ensure good processing stability of the amine compounds in the first mixture, in some embodiments of this application, R1 and R2 are independently selected from hydrogen, D, or C1-C4 aliphatic chain hydrocarbon groups, and R3 is selected from unsubstituted or substituted groups. c Substituted C1–C10 aliphatic chain hydrocarbon groups, unsubstituted or with at least one R c Substituted C1-C10 aliphatic chain hydroxyl groups, substituted or substituted with at least one R cThe substituted aryl group having 6 to 14 ring atoms, or a combination of the aforementioned groups; and / or, R c Each occurrence is independently selected from deuterium and *-NR. a R b Halogen groups, C1-C10 aliphatic chain hydrocarbon groups, C1-C10 aliphatic chain hydroxyl groups, or combinations of the aforementioned groups; and / or, R a and R b Each time it appears, it is independently selected from hydrogen, deuterium, C1-C10 aliphatic chain hydrocarbon group, C1-C10 aliphatic chain hydroxyl group, or a combination of these groups.

[0072] To further improve the solubility and / or dispersibility of amine compounds in the first mixture, and to further enhance the passivation effect of amine compounds on grain boundaries, in some embodiments of this application, R3 has the structure shown in the following general formula (1-1):

[0073]

[0074] In general formula (1-1), R d Each time it appears, it is independently selected from a halogen group, an unsubstituted or substituted C1-C8 alkyl group, an unsubstituted or substituted C1-C8 alkoxy group, or a combination of these groups; m is a positive integer from 1 to 4;

[0075] R e Selected from single-bonded or C1-C4 alkylene groups;

[0076] # indicates the connection site between R3 and N.

[0077] To further improve the agglomeration of the colloidal dispersion and to further enhance the processing stability of the amine compound in the first mixture, in some embodiments of this application, R d Each time it appears, it is independently selected from a halogen group, a C2-C8 alkyl group substituted with at least one halogen group, a C2-C8 alkoxy group substituted with at least one halogen group, or a combination of these groups; R e Alkylenes selected from C1 to C4.

[0078] In some embodiments of this application, the amine compound is selected from benzylamine, diphenylamine, triphenylamine, chlorobenzylamine, bromobenzylamine, fluorobenzylamine, dichlorobenzylamine, difluorobenzylamine, dibromobenzylamine, 4-bromo-2-iodobenzylamine, 2-chloro-3-fluorobenzylamine, 3-bromo-5-chlorobenzylamine, 3-bromo-5-fluorobenzylamine, 3-chloro-2-fluorobenzylamine, 4-chloro-2-fluorobenzylamine, and p-chlorobenzylamine. One or more of the following: ethylamine, m-chlorophenethylamine, o-chlorophenethylamine, o-bromophenethylamine, p-bromophenethylamine, m-bromophenethylamine, p-fluorophenethylamine, m-fluorophenethylamine, o-fluorophenethylamine, dichlorophenethylamine, difluorophenethylamine, N-methyl-3-chlorophenethylamine, 2,5-dimethoxy-4-chlorophenethylamine, 2,5-dimethoxy-4-chlorophenpropylamine, m-bromophenpropylamine, p-chlorophenbutylamine, and 4-bromophenbutylamine.

[0079] In some embodiments of this application, in step S2, the molar ratio of the metal element to the amine compound in the metal precursor is 1:(0.05 to 0.5), for example, it can be 1:0.05, 1:0.1, 1:0.2, 1:0.3, 1:0.4, 1:0.5 or any two of the aforementioned values. Within the aforementioned range, the amine compound has good solubility and / or dispersibility in the first mixture, and the passivation layer formed by the amine compound on the surface of the obtained metal oxide has an appropriate thickness, which not only has a good passivation effect on the metal oxide, but also ensures that the obtained metal oxide has good conductivity.

[0080] To further improve the purity of the obtained metal oxide, in some embodiments of this application, after the step of mixing the first mixture and the amine compound and before the step of obtaining the metal oxide, the method for preparing the metal oxide further includes the step of: performing solid-liquid separation on the second mixture obtained by mixing the first mixture and the amine compound, wherein the solid-liquid separation is operably performed at least once. Solid-liquid separation includes, but is not limited to, one or more of sedimentation, filtration, and evaporation; sedimentation includes, but is not limited to, one or more of gravity sedimentation, centrifugal sedimentation, and electromagnetic sedimentation; filtration includes, but is not limited to, one or more of reverse osmosis, membrane filtration, nanofiltration, ultrafiltration, and microfiltration.

[0081] As an example, the solid-liquid separation includes the steps of: mixing the second mixture with a precipitant to precipitate a precipitate, then centrifuging and collecting the precipitate, wherein the precipitant includes one or more of ketones, esters, and alcohols, the ketones including but not limited to one or more of acetone and butanone, the esters including but not limited to one or more of ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate, and butyl acetate, and the alcohols including but not limited to one or more of methanol, ethanol, ethylene glycol, n-propanol, isopropanol, n-butanol, and isobutanol.

[0082] This application also provides a metal oxide, which can be prepared by the above-described method for preparing metal oxides. The surface of the metal oxide is attached with a ligand, and the ligand has the structure shown in the following general formula (II):

[0083]

[0084] In general formula (II), & represents the binding site between the ligand and the metal oxide; R1, R2 and R3 are described above.

[0085] The metal oxides of the present application embodiments have fewer defect states and exhibit good conductivity and performance stability.

[0086] In some embodiments of this application, the fluorescence intensity of the metal oxide is 0.01 × 10⁻⁶. 4 ~0.8×10 4 .

[0087] In some embodiments of this application, the average particle size of the metal oxide is 1 nm to 50 nm, for example, it can be 1 nm, 3 nm, 5 nm, 8 nm, 10 nm, 20 nm, 30 nm, 40 nm, 50 nm or any two of the aforementioned values.

[0088] In some embodiments of this application, the metal oxide is an N-type metal oxide, selected from ZnO, TiO2, SnO2, BaO, Ta2O3, Al2O3, ZrO2, and Zn. (1-x) Mg x O, Zn (1-x) Ca x O, Zn (1-x) Zr x O, Zn (1-x) Ga x O, Zn (1-x) Al x O, Zn (1-x) Li x O, Zn (1-x) Ti x O, Zn (1-x) Y x O、In (1-x) Sn x O or Ti (1-x) Li x O, where x is the molar quantity, 0 < x ≤ 0.5.

[0089] In some other embodiments of this application, the metal oxide is a p-type metal oxide, selected from oxides of nickel, copper, molybdenum, chromium, tungsten, vanadium, or hafnium.

[0090] This application also provides a thin film, which includes a metal oxide prepared by any of the metal oxide preparation methods described above, and / or the thin film includes any of the metal oxides described above, wherein the thin film has good surface flatness, conductivity and performance stability.

[0091] In some embodiments of this application, the thin film is a single-layer structure, that is, the material of the thin film is a metal oxide prepared by any of the metal oxide preparation methods described above, and / or the material of the thin film is a metal oxide as described above.

[0092] To reduce the amount of oxygen and / or moisture adsorbed by the film, thereby further improving the performance stability of the film, in some embodiments of this application, the film includes a first sublayer and a second sublayer stacked sequentially; the first sublayer includes a metal oxide prepared by any of the metal oxide preparation methods described above, and / or the first sublayer includes any of the metal oxides described above; the second sublayer includes a fluoropolymer, which has low surface energy (e.g., less than 30 mN / m) and good chemical stability, and can protect the first sublayer and reduce the amount of oxygen and / or moisture adsorbed.

[0093] In some embodiments of this application, the monomers of the fluoropolymer include one or more of perfluoroolefins, hydrofluoroolefins, chlorofluoroolefins, and hydrochlorofluoroolefins, such as one or more of trifluoroethylene, trichlorofluoroethylene, vinylidene fluoride, fluoroethylene, tetrafluoroethylene, and hexafluoropropylene.

[0094] To further reduce the adsorption of oxygen and / or moisture by the membrane and to further improve the performance stability of the membrane, in some embodiments of this application, the fluoropolymer is selected from one or more of polychlorotrifluoroethylene (CAS No. 9002-83-9), poly(ethylene-chlorotrifluoroethylene) (CAS No. 25101-45-5), poly(perfluoroethylene-propylene resin) (CAS No. 25067-11-2), polyvinylidene fluoride (CAS No. 24937-79-9), polyvinylidene fluoride (CAS No. 24981-14-4), polytetrafluoroethylene (CAS No. 9002-84-0), poly(vinylidene fluoride-co-hexafluoropropylene) (CAS No. 9011-17-0), and tetrafluoroethylene-hexafluoropropylene copolymer (CAS No. 25067-11-2).

[0095] In order to improve the conductivity of the thin film, in some embodiments of this application, the thickness of the first sublayer is 10nm to 100nm, for example, it can be 10nm, 25nm, 40nm, 50nm, 60nm, 80nm, 100nm or any two of the aforementioned values.

[0096] In some embodiments of this application, the thickness of the second sublayer is 1nm to 5nm, for example, 1nm, 2nm, 3nm, 4nm, 5nm or any two of the aforementioned values. The thickness of the second sublayer within the aforementioned range can ensure that the film has good conductivity and light transmittance, and can also improve the surface smoothness and performance stability of the film.

[0097] This application also provides a method for preparing a thin film, which can be used to prepare the thin film described above, including the steps of: depositing a first dispersion comprising a metal oxide, drying the deposited first dispersion to form a film layer, and obtaining a thin film; wherein the metal oxide is a metal oxide prepared by any of the metal oxide preparation methods described above, and / or the metal oxide is any of the metal oxides described above.

[0098] The deposition method of the first dispersion includes, but is not limited to, one or more of the following: spin coating deposition, inkjet printing deposition, blade coating deposition, dip-coating deposition, immersion deposition, spraying deposition, roller coating deposition, casting deposition, slot coating deposition, and strip coating deposition.

[0099] The drying method of the first dispersion includes, but is not limited to, one or more of natural air drying, heat treatment and vacuum drying, and the temperature of heat treatment can be, for example, 60°C to 200°C.

[0100] In some embodiments of this application, after the step of drying the deposited first dispersion to form a film layer and before the step of obtaining the film, the film preparation method further includes the step of spin-coating a second dispersion comprising a fluoropolymer onto one side of the film layer, and drying the deposited second dispersion to form a film. The deposition and drying methods of the second dispersion are described above in relation to the deposition and drying methods of the first dispersion, and the fluoropolymer is also described above.

[0101] The dispersion medium of the second dispersion is not specifically limited, as long as the fluoropolymer has good dispersibility therein, such as tetrahydrofuran.

[0102] In some embodiments of this application, the concentration of the fluoropolymer in the second dispersion is 5 mg / mL to 25 mg / mL, for example, it can be 5 mg / mL, 10 mg / mL, 15 mg / mL, 20 mg / mL, 25 mg / mL or any two of the aforementioned values.

[0103] This application also provides an optoelectronic device, which includes, but is not limited to, light-emitting devices, photovoltaic cells, or photodetectors, such as... Figure 2As shown, the optoelectronic device 10 includes: an anode 101 and a cathode 102 disposed opposite to each other, and a plurality of functional layers disposed between the anode 101 and the cathode 102. The material of at least one of the multiple functional layers includes a metal oxide prepared by any of the metal oxide preparation methods described above, or a metal oxide as described above, and / or at least one of the multiple functional layers includes a thin film as described above. This is beneficial to improving the surface flatness of the at least one functional layer and optimizing the interface defects between adjacent functional layers, thereby improving the optoelectronic performance, device life and performance stability of the optoelectronic device 10.

[0104] In some embodiments of this application, the materials of the anode 101 and the cathode 102 are independently selected from one or more of metals, carbon materials, and second metal oxides. The metals include, but are not limited to, one or more of Al, Ag, Cu, Mo, Au, Ba, Pt, Ca, Ir, Ni, and Mg. The carbon materials include, but are not limited to, one or more of graphite, carbon nanotubes, graphene, and carbon fibers. The second metal oxide may be doped or undoped. The doped second metal oxides include, but are not limited to, one or more of indium tin oxide (ITO), fluorine-doped tin oxide (FTO), antimony tin oxide (ATO), aluminum-doped zinc oxide (AZO), gallium-doped zinc oxide (GZO), indium-doped zinc oxide (IZO), and magnesium-doped zinc oxide (MZO). The undoped second metal oxides include, but are not limited to, one or more of TiO2, SnO2, ZnO, and In2O3.

[0105] The anode 101 or cathode 102 can also be a composite electrode with a sandwich-like structure. The upper and lower layers are independently selected from a second metal oxide or a metal sulfide, and the middle layer is a metal, such as one or more of AZO / Ag / AZO, AZO / Al / AZO, ITO / Ag / ITO, ITO / Al / ITO, ZnO / Ag / ZnO, ZnO / Al / ZnO, TiO2 / Ag / TiO2, TiO2 / Al / TiO2, ZnS / Ag / ZnS, ZnS / Al / ZnS, TiO2 / Ag / TiO2, and TiO2 / Al / TiO2. The thickness of the middle layer does not exceed 35 nm. The thickness of the anode 101 can be, for example, 20 nm to 300 nm, and the thickness of the cathode 102 can be, for example, 20 nm to 300 nm.

[0106] In some embodiments of this application, see further reference. Figure 2The multiple functional layers include an electronic functional layer 104. The material of the electronic functional layer 104 includes a metal oxide prepared by any of the metal oxide preparation methods described above, or a metal oxide prepared by any of the metal oxides described above, and / or the electronic functional layer 104 includes a thin film prepared by any of the metal oxides described above. Correspondingly, the metal oxide in the electronic functional layer 104 is an N-type metal oxide.

[0107] In other embodiments of this application, the material of the electronic functional layer 104 includes ZnO, TiO2, SnO2, BaO, Ta2O3, Al2O3, ZrO2, and Zn. (1-x) Mg x O, Zn (1-x) Ca x O, Zn (1-x) Zr x O, Zn (1-x) Ga x O, Zn (1-x) Al x O, Zn (1-x) Li x O, Zn (1-x) Ti x O, Zn (1-x) Y x O、In (1-x) Sn x O and Ti (1-x) Li x One or more of O, where x represents the molar amount, and 0 < x ≤ 0.5.

[0108] It should be noted that the electronic functional layer 104 can be a single-layer structure or a multi-layer structure, and the thickness of the electronic functional layer 104 is, for example, 10 nm to 100 nm. When the electronic functional layer 104 is a multi-layer structure, the electronic functional layer 104 includes, for example, one or more of an electron injection layer, an electron transport layer, and a hole blocking layer. For an electronic functional layer 104 including an electron injection layer, an electron transport layer, and a hole blocking layer, the electron transport layer is located between the electron injection layer and the hole blocking layer, and the electron injection layer is closer to the cathode 102 than the hole blocking layer. For an electronic functional layer 104 including an electron transport layer and a hole blocking layer, the electron transport layer is closer to the cathode 102 than the hole blocking layer. For an electronic functional layer 104 including an electron injection layer and an electron transport layer, the electron injection layer is closer to the cathode 102 than the electron transport layer. As an example, the electronic functional layer 104 is an electron transport layer, and the material of the electron transport layer includes a metal oxide prepared by any of the metal oxide preparation methods described above, or a metal oxide as described above, and / or the electron transport layer is a thin film as described above.

[0109] In some embodiments of this application, multiple functional layers include a hole functional layer 105. The material of the hole functional layer 105 includes a metal oxide prepared by any of the metal oxide preparation methods described above, or a metal oxide as described above, and / or the hole functional layer 105 includes a thin film as described above. Correspondingly, the metal oxide in the hole functional layer 105 is a P-type metal oxide.

[0110] In other embodiments of this application, the material of the hole functional layer 105 includes one or more of organic materials, a first inorganic compound material, and a second inorganic compound material.

[0111] The organic materials include poly(3,4-vinyldioxythiophene):poly(styrene sulfonic acid) (PEDOT:PSS, CAS No. 155090-83-8), copper phthalocyanine (CAS No. 147-14-8), titanium phthalocyanine (CAS No. 26201-32-1), 2,3,5,6-tetrafluoro-7,7',8,8'-tetracyanodimethyl-p-benzoquinone (CAS No. 29261-33-4), 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazabenzophenanthrene (CAS No. 105598-27-4), polyaniline (CAS No. 25233-30-1), and polypyrrole (CAS No. 30604-81-0). 3-Hexyl-substituted polythiophene (CAS No. 104934-50-1), poly(9-vinylcarbazole) (abbreviated as PVK, CAS No. 25067-59-8), 4,4'-bis(9-carbazole)biphenyl (abbreviated as CBP, CAS No. 58328-31-7), poly[bis(4-phenyl)(4-butylphenyl)amine] (abbreviated as Poly-TPD, CAS No. 472960-35-3), 4,4'-cyclohexylbis[N,N-bis(4-methylphenyl)aniline] (abbreviated as TAPC, CAS No. 58473-78-2), poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(4,4'-(N-(4-sec-butylphenyl)diphenylamine)] (abbreviated as... The following are listed as TFB (CAS No. 220797-16-0): poly[(N,N'-(4-n-butylphenyl)-N,N'-diphenyl-1,4-phenylenediamine)-ALT-(9,9-di-n-octylfluorenyl-2,7-diyl)] (CAS No. 223569-31-1), 4,4',4'-tris(N-3-methylphenyl-N-phenylamino)triphenylamine (CAS No. 124729-98-2), 4,4',4”-tris(carbazole-9-yl)triphenylamine (abbreviated as TCTA, CAS No. 139092-78-7), 4,4',4'-tris(2-naphthylphenylamino)triphenylamine (CAS No. 185690-41-9), N,N'-diphenyl-N, N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine (NPB, CAS No. 123847-85-8), N,N'-diphenyl-N,N'-di(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine (TPD, CAS No. 65181-78-4), N,N'-bis[4-(diphenylamino)phenyl]-N,N'-diphenylbenzidine (CAS No. 209980-53-0), N,N'-bis(3-methylphenyl)-N,N'-diphenyl-9,9-spirodifluorene-2,7-diamine (Spiro-TPD, CAS No. 1033035-83-4), N2,N7-di-1-naphthyl-N2One or more of the following: N7-diphenyl-9,9'-spirodi[9H-fluorene]-2,7-diamine (CAS No. 932739-76-9), poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTTA, CAS No. 1333317-99-9), and 2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirodifluorene (Spiro-omeTAD, CAS No. 207739-72-8).

[0112] The first inorganic compound material includes one or more of graphene, C60, nickel oxide, copper oxide, molybdenum oxide, chromium oxide, tungsten oxide, vanadium oxide, hafnium oxide, copper sulfide, molybdenum sulfide, and tungsten sulfide.

[0113] The second inorganic compound material includes one or more doped first compounds. The main material of the doped first compound includes one or more of graphene, C60, nickel oxide, copper oxide, molybdenum oxide, chromium oxide, tungsten oxide, vanadium oxide, hafnium oxide, copper sulfide, molybdenum sulfide, and tungsten sulfide. The doping element of the doped first compound is selected from one or more of nickel, molybdenum, tungsten, vanadium, chromium, copper, hafnium, and platinum group metals. The molar amount of the doping element accounts for no more than 50% of the total molar amount of the doped first compound.

[0114] It should be noted that the hole functional layer 105 can be a single-layer structure or a multi-layer structure, and the thickness of the hole functional layer 105 is, for example, 10nm to 100nm. When the hole functional layer 105 is a multi-layer structure, the hole functional layer 105 may include one or more of a hole injection layer, a hole transport layer, and an electron blocking layer. For a hole functional layer 105 including a hole injection layer, a hole transport layer, and an electron blocking layer, the hole transport layer is located between the hole injection layer and the electron blocking layer, and the hole injection layer is closer to the anode 101 than the electron blocking layer. For a hole functional layer 105 including a hole transport layer and an electron blocking layer, the hole transport layer is closer to the anode 101 than the electron blocking layer. For a hole functional layer 105 including a hole injection layer and a hole transport layer, the hole injection layer is closer to the anode 101 than the hole transport layer.

[0115] In some embodiments of this application, the optoelectronic device 10 is a light-emitting device, and the multiple functional layers include a light-emitting layer 103. For the optoelectronic device 10 including an electronic functional layer 104 and a hole functional layer 105, the light-emitting layer 103 is disposed between the electronic functional layer 104 and the hole functional layer 105.

[0116] The light-emitting material of the light-emitting layer 103 includes one or more of organic light-emitting materials and quantum dots, and the thickness of the light-emitting layer 103 is, for example, 10 nm to 100 nm.

[0117] Among them, organic light-emitting materials include, but are not limited to, one or more of the following: 4,4'-bis(N-carbazole)-1,1'-biphenyl:tri[2-(p-tolyl)pyridinium(III), 4,4',4”-tri(carbazole-9-yl)triphenylamine:tri[2-(p-tolyl)pyridinium, diaromatic anthracene derivatives, stilbene aromatic derivatives, pyrene derivatives, fluorene derivatives, TBPe fluorescent materials, TTPX fluorescent materials, TBRb fluorescent materials, DBP fluorescent materials, delayed fluorescent materials, TTA materials, thermally activated delayed materials, polymers containing BN covalent bonds, hybrid local charge transfer excited state materials, excitopolymer light-emitting materials, polyacetylene and its derivatives, poly(p-phenylene) and its derivatives, polythiophene and its derivatives, and polyfluorene and its derivatives.

[0118] Quantum dots include, but are not limited to, one or more of red, green, and blue quantum dots, and include, but are not limited to, single-component quantum dots, core-shell quantum dots, inorganic perovskite quantum dots, organic perovskite quantum dots, and organic-inorganic hybrid perovskite quantum dots, wherein the shell of the core-shell quantum dot has one or more layers. The average particle size of the quantum dots can be, for example, 2 nm to 20 nm, with examples being 2 nm, 5 nm, 6 nm, 7 nm, 8 nm, 9 nm, 10 nm, 15 nm, 20 nm, or any value between any two of the aforementioned values.

[0119] For single-component quantum dots and core-shell quantum dots, the material of the single-component quantum dot, the material of the core of the core-shell quantum dot, or the material of the shell of the core-shell quantum dot includes, but is not limited to, at least one of group II-VI compounds, group III-V compounds, group III-VI compounds, group IV-VI compounds, or group I-III-VI compounds. Among them, the II-VI group compounds include, but are not limited to, one or more of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, MgSe, MgS, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, MgZnSe, MgZnS, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, and HgZnSTe. III-VI group compounds include, but are not limited to, one or more of In2S3, In2Se3, InGaS3, and InGaSe3. III-V group compounds include, but are not limited to, one or more 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. Group IV-VI compounds include, but are not limited to, one or more of SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, SnPbSeTe, and SnPbSTe. Group I-III-VI compounds include, but are not limited to, one or more of AgInS, AgInS2, CuInS, CuInS2, AgGaS2, CuGaS2, CuGaO2, AgGaO2, AgAlO2, AgInGaS2, and CuInGaS2.

[0120] As an example, the core-shell structured quantum dots may include, but are not limited to, one or more of 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 in the core-shell structured quantum dots, " / " represents a shell. Taking CdSe / CdSeS / CdS as an example, CdSe is the quantum dot core, CdSeS is the first shell, and CdS is the second shell.

[0121] For inorganic perovskite quantum dots, the general structural formula is AMX3, where A is Cs. + M is a divalent metal cation, and M includes, but is not limited to, Pb. 2+ Sn 2+ Cu 2+ Ni 2+ Cd 2+ Cr 2+ Mn 2+ Co 2+ Fe 2+ 、Ge 2+ Yb 2+ Or Eu 2+ X is a halide anion, including but not limited to Cl. - ,Br - Or I - .

[0122] For organic perovskite quantum dots, the general structural formula is CMX3, where C is a formamidinyl group and M is a divalent metal cation, including but not limited to Pb. 2+ Sn 2+ Cu 2+ Ni 2+ Cd 2+ Cr 2+ Mn 2+ Co 2+ Fe 2+ 、Ge 2+ Yb 2+ Or Eu 2+ X is a halide anion, including but not limited to Cl. - ,Br - Or I - .

[0123] For organic-inorganic hybrid perovskite quantum dots, the general structural formula is BMX3, where B is selected from organic amine cations, including but not limited to CH3(CH2). n-2 NH 3+ (n≥2) or NH3(CH2) n NH3 2+ (n≥2), M is a divalent metal cation, and M includes, but is not limited to, Pb. 2+ Sn 2+ Cu 2+ Ni 2+ Cd 2+ Cr 2+ Mn 2+ Co 2+ Fe 2+ 、Ge 2+ Yb 2+ Or Eu 2+ X is a halide anion, including but not limited to Cl. - ,Br - Or I - When n=2, the inorganic metal halide octahedrons MX64- are connected by a common vertex, with the metal cation M located at the body center of the halogen octahedron and the organic amine cation B filling the gaps between the octahedrons, forming an infinitely extended three-dimensional structure. When n>2, the inorganic metal halide octahedrons MX64- connected by a common vertex extend in the two-dimensional direction to form a layered structure, with organic amine cation bilayers (protonated monoamines) or organic amine cation monolayers (protonated diamines) inserted between the layers. The organic and inorganic layers overlap to form a stable two-dimensional layered structure.

[0124] When the material of the light-emitting layer 103 includes quantum dots, in order to improve the solution processing performance of the quantum dots and further enhance the photoelectric performance of the optoelectronic device 10, in some embodiments of this application, ligands are also attached to the surface of the quantum dots. The ligands can be common ligands in the art, including but not limited to C1 to C2. 30 aliphatic carboxylic acid ligands, C6-C 30 Aromatic carboxylic acid ligands, C1-C 30 Aliphatic thiol ligands, C6-C 30 Thiol aromatic ligands, C1-C 30 fatty amine ligands, C6-C 30 Aromatic amine ligands, C1-C 30 Aliphatic phosphine ligands, C6~C 30 Aromatic phosphine ligands and C6-C 30 One or more of the aromatic phosphate ligands and halogen ligands.

[0125] Among them, C1~C 30 The aliphatic carboxylic acid ligands include, but are not limited to, one or more of the following: octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, octadecanoic acid, eicosanoic acid, teicosanoic acid, oleic acid, linoleic acid, arachidic acid, arachidonic acid, erucic acid, and docosahexaenoic acid; C6~C 30 Aromatic carboxylic acid ligands include, but are not limited to, one or more of benzoic acid, biphenylic acid, and 1-naphthoic acid. (C1-C2) 30 The aliphatic thiol ligands include, but are not limited to, one or more of hexamethylenetetramine, octanethiol, nonanethiol, decanethiol, undecylthiol, dodecathiol, hexadecylthiol, and octadecylthiol, C6–C6. 30 Thiol aromatic ligands include, but are not limited to, one or more of benzenethiol, triphenylmethanethiol, and p-terphenyl-4,4”-dithiol. C1~C 30 The aliphatic amine ligands include, but are not limited to, one or more of hexylamine, octylamine, dioctylamine, trioctylamine, nonylamine, decylamine, dodecylamine, trideamine, tetradeamine, pentadecylamine, hexadecylamine, heptadecanamine, octadecylamine, and oleylamine, C6-C6. 30 The aromatic amine ligands include, but are not limited to, one or more of aniline, indenepropylamine, 4-octylaniline, and benzidine. (C1-C2) 30 The aliphatic phosphine ligands include, but are not limited to, one or more of trimethylphosphine, triethylphosphine, tripropylphosphine, tributylphosphine, trihexylphosphine, trioctylphosphine, tridecylphosphine, tributylphosphine oxide, trihexylphosphine oxide, trioctylphosphine oxide, and tridecylphosphine oxide, C6–C6. 30 Aromatic phosphine ligands include, but are not limited to, one or more of bis(2-diphenylphosphineethyl)phenylphosphine and triphenylphosphine oxide, C6-C6. 30 The aromatic phosphate ligands include, but are not limited to, one or more of tetraethyl p-xylene diphosphate and ethyl diphenyl phosphate. Halogen ligands include, but are not limited to, -Cl, -F, -I, or -Br.

[0126] It should be noted that when the material of the electronic functional layer 104 includes a metal oxide prepared by any of the metal oxide preparation methods described above, or a metal oxide prepared by any of the metal oxides described above, and / or when the electronic functional layer 104 includes a thin film prepared by any of the thin films described above, the grain boundary defects and interface recombination at the interface between the light-emitting layer 103 and the electronic functional layer 104 can be reduced, and non-radiative recombination can be reduced, thereby improving the device efficiency and performance stability of the optoelectronic device 10. Furthermore, when the electronic functional layer 104 includes a thin film prepared by any of the thin films described above and includes a first sublayer and a second sublayer stacked sequentially, the adsorption of oxygen and / or moisture can be effectively reduced, effectively improving the corrosion phenomenon of the cathode 102 caused by the adsorption of water and oxygen by the metal oxide (e.g., ZnO), slowing down the forward aging process, thereby further improving the performance stability and device life of the optoelectronic device 10.

[0127] When the material of the hole functional layer 105 includes a metal oxide prepared by any of the metal oxide preparation methods described above, or a metal oxide prepared by any of the metal oxides described above, and / or the hole functional layer 105 includes a thin film prepared by any of the thin films described above, it can reduce grain boundary defects and interface recombination at the interface between the light-emitting layer 103 and the hole functional layer 105, reduce non-radiative recombination, and thus improve the device efficiency and performance stability of the optoelectronic device 10. Furthermore, when the hole functional layer 105 includes a thin film prepared by any of the thin films described above and includes a first sublayer and a second sublayer stacked sequentially, it can effectively reduce the adsorption of oxygen and / or moisture, effectively improve the corrosion phenomenon of the anode 101 caused by the adsorption of water and oxygen by the metal oxide, slow down the forward aging process, and thus further improve the performance stability and device lifespan of the optoelectronic device 10.

[0128] It is understood that the optoelectronic device 10 may also include a substrate, which is disposed on the side of the anode 101 away from the multiple functional layers or on the side of the cathode 102 away from the multiple functional layers. The substrate may be a rigid substrate or a flexible substrate. The material of the rigid substrate includes, but is not limited to, one or more of glass, ceramic and silicon wafer. The material of the flexible substrate includes, but is not limited to, one or more of polyimide, polycarbonate, polymethyl methacrylate, polyethylene terephthalate, polyethylene naphthalate and polyethersulfone.

[0129] This application also provides a method for fabricating an optoelectronic device, which can be used to fabricate any of the optoelectronic devices described above. The method for fabricating the optoelectronic device includes the following steps:

[0130] S100, Provide a first electrode, and form multiple functional layers on one side of the first electrode;

[0131] S200, A second electrode is formed on the side of the multiple functional layers away from the first electrode.

[0132] In this process, at least one of the multiple functional layers is prepared using any of the thin film preparation methods described above.

[0133] In some embodiments of this application, multiple functional layers include electronic functional layers, which are prepared using any of the thin film preparation methods described above, wherein the metal oxide includes N-type metal oxides as described above.

[0134] In some embodiments of this application, multiple functional layers include a hole functional layer, which is prepared using any of the thin film preparation methods described above, wherein the metal oxide includes the P-type metal oxide as described above.

[0135] In some embodiments of this application, when the first electrode is an anode and the second electrode is a cathode, the step of forming multiple functional layers includes: sequentially forming a hole functional layer, a light-emitting layer, and an electron functional layer on one side of the first electrode; and forming the second electrode on the side of the electron functional layer away from the light-emitting layer.

[0136] In some other embodiments of this application, when the first electrode is a cathode and the second electrode is an anode, the step of forming multiple functional layers includes: sequentially forming an electronic functional layer, a light-emitting layer and a hole functional layer on one side of the first electrode; and forming the second electrode on the side of the hole functional layer away from the light-emitting layer.

[0137] It is understood that the fabrication methods for various functional layers in optoelectronic devices include, but are not limited to, chemical and / or physical methods. Chemical methods include, but are not limited to, one or more of chemical vapor deposition, continuous ion layer adsorption and reaction, anodic oxidation, electrolytic deposition, and co-precipitation. Physical methods include, but are not limited to, physical deposition and solution methods. Physical deposition methods include, but are not limited to, one or more of thermal evaporation deposition, electron beam evaporation deposition, magnetron sputtering, multi-arc ion deposition, physical vapor deposition, atomic layer deposition, and pulsed laser deposition. Solution methods include, but are not limited to, one or more of spin coating, printing, inkjet printing, blade coating, dip coating, immersion coating, spray coating, roller coating, casting, slot coating, and strip coating.

[0138] This application also provides an electronic device, which includes any of the optoelectronic devices described in the embodiments of this application. The electronic device can be, for example, any electronic product with a display function, including but not limited to smartphones, tablet personal computers, mobile phones, video phones, e-book readers, laptop PCs, netbook computers, workstations, servers, personal digital assistants, portable multimedia players, MP3 players, mobile medical devices, cameras, game consoles, digital cameras, car navigation systems, electronic billboards, ATMs, smart bracelets, smartwatches, virtual reality (VR) devices, or wearable devices.

[0139] The technical solutions and effects of this application will be described in detail below through specific embodiments, comparative examples and experimental examples. The following embodiments are only some embodiments of this application and are not intended to limit this application.

[0140] Material Example 1

[0141] This embodiment provides a metal oxide and its preparation method, wherein the metal oxide is nano-ZnO with an average particle size of 5 nm.

[0142] The preparation method of nano ZnO in this embodiment includes the following steps:

[0143] S1.1. Add 10 mmol of zinc acetate dihydrate to 20 mL of ethanol. After complete dissolution, a zinc precursor solution with a concentration of 0.5 mol / L is obtained. Then, at room temperature, add an alkaline solution containing sodium hydroxide (sodium hydroxide concentration of 0.6 mol / L, solvent of ethanol) dropwise to the zinc precursor solution until OH... - With Zn 2+ The molar ratio was 1:0.9, the pH was adjusted to 12, and the mixture was stirred at 25°C for 10 min to obtain the first mixture;

[0144] S1.2 Add 2 mmol of 2,4-dichlorophenethylamine to the first mixture and continue stirring at 25°C for 3 h to obtain the second mixture;

[0145] S1.3 Add acetone to the second mixture until precipitation is complete, then centrifuge at 6000 r / min for 5 min, discard the supernatant and collect the precipitate, which is nano ZnO.

[0146] Material Example 2

[0147] This embodiment provides a metal oxide and its preparation method, wherein the metal oxide is nano-ZnO with an average particle size of 6 nm.

[0148] Compared with the preparation method of metal oxide in Material Example 1, the difference in the preparation method of metal oxide in this example is that "2 mmol of 2,4-dichlorophenylethylamine" in step S1.2 is replaced with "0.5 mmol of 2,4-dichlorophenylethylamine".

[0149] Material Example 3

[0150] This embodiment provides a metal oxide and its preparation method, wherein the metal oxide is nano-ZnO with an average particle size of 5 nm.

[0151] Compared with the preparation method of metal oxide in Material Example 1, the difference in the preparation method of metal oxide in this example is that "2 mmol of 2,4-dichlorophenylethylamine" in step S1.2 is replaced with "5 mmol of 2,4-dichlorophenylethylamine".

[0152] Material Example 4

[0153] This embodiment provides a metal oxide and its preparation method, wherein the metal oxide is nano-ZnO with an average particle size of 7 nm.

[0154] Compared to the preparation method of the metal oxide in Material Example 1, the difference in the preparation method of the metal oxide in this example is that "2 mmol of 2,4-dichlorophenethylamine" in step S1.2 is replaced with "2 mmol of p-bromophenethylamine".

[0155] Material Example 5

[0156] This embodiment provides a metal oxide and its preparation method, wherein the metal oxide is nano-ZnO with an average particle size of 5 nm.

[0157] Compared with the preparation method of metal oxide in Material Example 1, the difference in the preparation method of metal oxide in this example is that "2 mmol of 2,4-dichlorophenethylamine" in step S1.2 is replaced with "2 mmol of p-chlorophenethylamine".

[0158] Material Example 6

[0159] This embodiment provides a metal oxide and its preparation method, wherein the metal oxide is nano-ZnO with an average particle size of 4 nm.

[0160] Compared with the preparation method of metal oxide in Material Example 1, the difference in the preparation method of metal oxide in this example is that "2 mmol of 2,4-dichlorophenethylamine" in step S1.2 is replaced with "2 mmol of 4-chloro-2-fluorobenzylamine".

[0161] Material Example 7

[0162] This embodiment provides a metal oxide and its preparation method, wherein the metal oxide is nano-ZnO with an average particle size of 6 nm.

[0163] Compared with the preparation method of metal oxide in Material Example 1, the difference in the preparation method of metal oxide in this example is that "2 mmol of 2,4-dichlorophenethylamine" in step S1.2 is replaced with "2 mmol of p-chlorophenbutylamine".

[0164] Material Example 8

[0165] This embodiment provides a metal oxide and its preparation method, wherein the metal oxide is nano-ZnO with an average particle size of 5 nm.

[0166] Compared to the preparation method of the metal oxide in Material Example 1, the difference in the preparation method of the metal oxide in this example is that "2 mmol of 2,4-dichlorophenethylamine" in step S1.2 is replaced with "2 mmol of N-methyl-3-chlorophenethylamine".

[0167] Material Example 9

[0168] This embodiment provides a metal oxide and its preparation method, wherein the metal oxide is nano-ZnO with an average particle size of 6 nm.

[0169] Compared to the preparation method of the metal oxide in Material Example 1, the difference in the preparation method of the metal oxide in this example is that "2 mmol of 2,4-dichlorophenylethylamine" in step S1.2 is replaced with "2 mmol of 2,4-dichlorophenylmethylamine".

[0170] Material Example 10

[0171] This embodiment provides a metal oxide and its preparation method, wherein the metal oxide is nano-ZnO with an average particle size of 5 nm.

[0172] Compared with the preparation method of metal oxide in Material Example 1, the difference in the preparation method of metal oxide in this example is that "2 mmol of 2,4-dichlorophenylethylamine" in step S1.2 is replaced with "2 mmol of 3-chlorophenylmethylamine".

[0173] Material Example 11

[0174] This embodiment provides a metal oxide and its preparation method, wherein the metal oxide is nano-ZnO with an average particle size of 7 nm.

[0175] Compared with the preparation method of metal oxide in Material Example 1, the difference in the preparation method of metal oxide in this example is that "2 mmol of 2,4-dichlorophenylethylamine" in step S1.2 is replaced with "2 mmol of aniline".

[0176] Material Example 12

[0177] This embodiment provides a metal oxide and its preparation method, wherein the metal oxide is nano-zinc-magnesium oxide with an average particle size of 6 nm.

[0178] The preparation method of nano-zinc magnesium oxide in this embodiment includes the following steps:

[0179] S2.1. Add 9 mmol of zinc acetate dihydrate and 1 mmol of magnesium acetate to 20 mL of ethanol. After complete dissolution, a zinc precursor solution with a concentration of 0.5 mol / L is obtained. Then, at room temperature, add an alkaline solution containing sodium hydroxide (sodium hydroxide concentration of 0.6 mol / L, solvent of ethanol) dropwise to the zinc precursor solution until OH... - With Zn 2+ The molar ratio was 1:0.9, the pH was adjusted to 12, and the mixture was stirred at 25°C for 10 min to obtain the first mixture;

[0180] S2.2 Add 2 mmol of 2,4-dichlorophenethylamine to the first mixture and continue stirring at 25°C for 3 h to obtain the second mixture;

[0181] S2.3. Follow the steps in S1.3 to obtain nano-zinc magnesium oxide.

[0182] Material Example 13

[0183] This embodiment provides a metal oxide and its preparation method, wherein the metal oxide is nano-tin oxide with an average particle size of 13 nm.

[0184] The preparation method of nano-tin oxide in this embodiment includes the following steps:

[0185] S3.1. Add 10 mmol of tin dichloride to 20 mL of ethanol. After complete dissolution, a tin precursor solution with a concentration of 0.5 mol / L is obtained. Then, at room temperature, add an alkaline solution containing sodium hydroxide (0.6 mol / L sodium hydroxide, ethanol as solvent) dropwise to the tin precursor solution until OH... - With Sn 2+ The molar ratio was 1:0.9, the pH was adjusted to 12, and the mixture was stirred at 25°C for 60 min to obtain the first mixture;

[0186] S3.2 Add 2 mmol of 2,4-dichlorophenethylamine to the first mixture and continue stirring at 25°C for 3 hours to obtain the second mixture;

[0187] S3.3, Follow the steps in S1.3 to obtain nano-tin oxide.

[0188] Material Example 14

[0189] This embodiment provides a metal oxide and its preparation method, wherein the metal oxide is nano-nickel oxide with an average particle size of 15 nm.

[0190] The preparation method of nano-nickel oxide in this embodiment includes the following steps:

[0191] S4.1. Add 10 mmol of nickel nitrate to 20 mL of ethanol. After complete dissolution, obtain a nickel precursor solution with a concentration of 0.5 mol / L. Then, at room temperature, add an alkaline solution containing sodium hydroxide (sodium hydroxide concentration is 0.6 mol / L, solvent is ethanol) dropwise to the nickel precursor solution until OH- is reached. - with Ni 2+ The molar ratio was 1:0.9, the pH was adjusted to 12, and the mixture was stirred at 25°C for 2 hours to obtain the first mixture;

[0192] S4.2 Add 2 mmol of 2,4-dichlorophenethylamine to the first mixture and continue stirring at 25°C for 3 h to obtain the second mixture;

[0193] S4.3, Follow the steps in S1.3 to obtain nano-nickel oxide.

[0194] Material Example 15

[0195] This embodiment provides a metal oxide and its preparation method, wherein the metal oxide is nano-molybdenum oxide with an average particle size of 13 nm.

[0196] The preparation method of nano-molybdenum oxide in this embodiment includes the following steps:

[0197] S5.1. Take 10 mmol of molybdenum powder and add it to 20 mL of ethanol. After complete dissolution, obtain a molybdenum precursor solution with a concentration of 0.5 mol / L. Then, at room temperature, add an alkaline solution containing sodium hydroxide (sodium hydroxide concentration is 0.6 mol / L, solvent is ethanol) dropwise to the molybdenum precursor solution until OH... - with Mo 7+ The molar ratio was 1:1.1, and the reaction yielded the first mixture;

[0198] S5.2 Add 2 mmol of 2,4-dichlorophenethylamine to the first mixture and continue stirring at 25°C for 3 h to obtain the second mixture;

[0199] S5.3, Follow the steps in S1.3 to obtain nano-molybdenum oxide.

[0200] Material Comparison Example 1

[0201] This comparative example provides a nano-ZnO and its preparation method, wherein the average particle size of the nano-ZnO is 6 nm.

[0202] The preparation method of nano ZnO in this comparative example includes the following steps:

[0203] S6.1. Add 10 mmol of zinc acetate dihydrate to 20 mL of ethanol. After complete dissolution, a zinc precursor solution with a concentration of 0.5 mol / L is obtained. Then, at room temperature, add an alkaline solution containing sodium hydroxide (sodium hydroxide concentration of 0.6 mol / L, solvent of ethanol) dropwise to the zinc precursor solution until OH- is reached. - With Zn 2+ The molar ratio was 1:0.9, the pH was adjusted to 12, and the mixture was stirred at 25°C for 3.5 h to obtain the first mixture;

[0204] S6.2. Follow the steps in S1.3 to obtain nano-molybdenum oxide.

[0205] Material Comparison Example 2

[0206] This comparative example provides a nano-tin oxide, with an average particle size of 12 nm.

[0207] The preparation method of nano-tin oxide in this comparative example includes the following steps:

[0208] S7.1. Add 10 mmol of tin dichloride to 20 mL of ethanol. After complete dissolution, a tin precursor solution with a concentration of 0.5 mol / L is obtained. Then, at room temperature, add an alkaline solution containing sodium hydroxide (0.6 mol / L sodium hydroxide, ethanol as solvent) dropwise to the tin precursor solution until OH... - With Sn 2+The molar ratio was 1:0.9, the pH was adjusted to 12, and the mixture was stirred at 25°C for 60 min to obtain the first mixture;

[0209] S7.2, Follow the steps in S1.3 to obtain nano-tin oxide.

[0210] Material Comparison Example 3

[0211] This comparative example provides a nano-nickel oxide with an average particle size of 13 nm.

[0212] The preparation method of nano-nickel oxide in this embodiment includes the following steps:

[0213] S8.1. Add 10 mmol of nickel nitrate to 20 mL of ethanol. After complete dissolution, obtain a nickel precursor solution with a concentration of 0.5 mol / L. Then, at room temperature, add an alkaline solution containing sodium hydroxide (sodium hydroxide concentration is 0.6 mol / L, solvent is ethanol) dropwise to the nickel precursor solution until OH- is reached. - with Ni 2+ The molar ratio was 1:0.9, the pH was adjusted to 12, and the mixture was stirred at 25°C for 2 hours to obtain the first mixture;

[0214] S8.2. Follow the steps in S1.3 to obtain nano-nickel oxide.

[0215] Material Comparison Example 4

[0216] This comparative example provides a nano-molybdenum oxide with an average particle size of 14 nm.

[0217] The preparation method of nano-molybdenum oxide in this embodiment includes the following steps:

[0218] S9.1. Take 10 mmol of molybdenum powder and add it to 20 mL of ethanol. After complete dissolution, obtain a molybdenum precursor solution with a concentration of 0.5 mol / L. Then, at room temperature, add an alkaline solution containing sodium hydroxide (sodium hydroxide concentration is 0.6 mol / L, solvent is ethanol) dropwise to the molybdenum precursor solution until OH... - with Mo 7+ The molar ratio was 1:1.1, and the reaction yielded the first mixture;

[0219] S9.2, Follow the steps in S1.3 to obtain nano-nickel oxide.

[0220] Thin Film Example 1

[0221] This embodiment provides a thin film and its preparation method. The thin film includes a first sublayer and a second sublayer stacked sequentially. The material of the first sublayer includes nano-ZnO as described in this embodiment, and the thickness of the first sublayer is 30 nm. The material of the second sublayer includes polychlorotrifluoroethylene, and the thickness of the second sublayer is 3 nm.

[0222] The method for preparing the thin film includes the following steps:

[0223] S10.1 Provide a substrate, and spin-coat a first dispersion containing nano-ZnO on one side of the substrate under a nitrogen atmosphere at room temperature and pressure. The nano-ZnO in the first dispersion is the nano-ZnO obtained in step S1.3. The concentration of nano-ZnO in the first dispersion is 30 mg / mL. The dispersion medium of the first dispersion is ethanol. Then, place it under a nitrogen atmosphere at 100°C for constant temperature heat treatment for 10 min to obtain a first sublayer with a thickness of 30 nm.

[0224] S10.2 Under a nitrogen atmosphere at room temperature and pressure, a second dispersion containing polychlorotrifluoroethylene (CAS No. 9002-83-9) (the concentration of polychlorotrifluoroethylene is 10 mg / mL, and the dispersion medium is tetrahydrofuran) is spin-coated on the side of the first sublayer away from the substrate. Then, it is placed under a nitrogen atmosphere at 100°C for 10 min to obtain a second sublayer with a thickness of 3 nm.

[0225] Thin Film Examples 2-15

[0226] Compared to Thin Film Example 1, Thin Film Example n differs only in that the material of the first sublayer includes the metal oxide from Thin Film Example n, where n is a positive integer from 2 to 15. In Thin Film Examples 2 to 15, the thickness of the first sublayer is 30 nm.

[0227] The preparation methods of the thin films in Thin Film Examples 2 to 15 are the same as those in Thin Film Example 1.

[0228] Thin Film Example 16

[0229] This embodiment provides a thin film and its preparation method. Compared with the thin film in Material Example 1, the only difference of the thin film in this embodiment is that the "polychlorotrifluoroethylene" in the second sublayer is replaced with "poly(ethylene-chlorotrifluoroethylene) (CAS No. 25101-45-5)".

[0230] Compared to the thin film preparation method in Example 1, the difference in the thin film preparation method in this example is only that step S10.2 is replaced with "spin-coating a second dispersion containing poly(ethylene-trifluorochloroethylene) (the concentration of poly(ethylene-trifluorochloroethylene) is 10 mg / mL, and the dispersion medium is tetrahydrofuran) on the side of the first sublayer away from the substrate under normal temperature and pressure nitrogen atmosphere, and then heat-treating it at a constant temperature of 100°C under nitrogen atmosphere for 10 min to obtain a second sublayer with a thickness of 3 nm".

[0231] Thin Film Example 17

[0232] This embodiment provides a thin film and its preparation method. Compared with the thin film in Material Example 1, the only difference in this embodiment is that the "polychlorotrifluoroethylene" in the second sublayer is replaced with "polyperfluoroethylene-propylene resin (CAS No. 25067-11-2)".

[0233] Compared to the thin film preparation method in Example 1, the difference in the thin film preparation method in this example is only that step S10.2 is replaced with "in a nitrogen atmosphere at room temperature and pressure, a second dispersion including perfluoroethylene-propylene resin (the concentration of perfluoroethylene-propylene resin is 10 mg / mL, and the dispersion medium is tetrahydrofuran) is spin-coated on the side of the first sublayer away from the substrate, and then placed in a nitrogen atmosphere at 100°C for constant temperature heat treatment for 10 min to obtain a second sublayer with a thickness of 3 nm".

[0234] Thin Film Example 18

[0235] This embodiment provides a thin film and its preparation method. Compared with the thin film in Material Example 1, the only difference in this embodiment is that the "polychlorotrifluoroethylene" in the second sublayer is replaced with "polyvinylidene fluoride (CAS No. 24937-79-9)".

[0236] Compared with the thin film preparation method in Thin Film Example 1, the difference in the thin film preparation method in this example is only that step S10.2 is replaced with "in a nitrogen atmosphere at room temperature and pressure, a second dispersion containing polyvinylidene fluoride (the concentration of polyvinylidene fluoride is 10 mg / mL, and the dispersion medium is tetrahydrofuran) is spin-coated on the side of the first sublayer away from the substrate, and then placed in a nitrogen atmosphere at 100°C for constant temperature heat treatment for 10 min to obtain a second sublayer with a thickness of 3 nm".

[0237] Thin Film Example 19

[0238] This embodiment provides a thin film and its preparation method. Compared with the thin film in Material Example 1, the only difference of the thin film in this embodiment is that the second sublayer is omitted.

[0239] Compared to the thin film preparation method in Thin Film Example 1, the only difference in the thin film preparation method in this example is that step S10.1 is omitted, and the first sublayer is the thin film.

[0240] Thin Film Example 20

[0241] This embodiment provides a thin film and its preparation method. Compared with the thin film in Material Example 1, the only difference of the thin film in this embodiment is that the thickness of the second sublayer is replaced with "5nm".

[0242] The thin film preparation method in this embodiment is the same as that in Thin Film Example 1.

[0243] Thin Film Example 21

[0244] This embodiment provides a thin film and its preparation method. The material of the thin film includes nano-tin oxide as described in Material Example 13.

[0245] The method for preparing the thin film includes the following steps: providing a substrate, and spin-coating a first dispersion containing nano-tin oxide on one side of the substrate under a nitrogen atmosphere at room temperature and pressure. The nano-tin oxide in the first dispersion is the nano-tin oxide from Material Example 13, the concentration of nano-tin oxide in the first dispersion is 30 mg / mL, and the dispersion medium of the first dispersion is ethanol. Then, the film is subjected to constant temperature heat treatment at 100°C under a nitrogen atmosphere for 10 min to obtain a thin film with a thickness of 30 nm.

[0246] Thin Film Example 22

[0247] This embodiment provides a thin film and its preparation method. The material of the thin film includes the nano-nickel oxide from Material Example 14.

[0248] The method for preparing the thin film includes the following steps: providing a substrate, and spin-coating a first dispersion containing nano-nickel oxide on one side of the substrate under a nitrogen atmosphere at room temperature and pressure. The nano-nickel oxide in the first dispersion is the nano-nickel oxide from Material Example 13, the concentration of nano-nickel oxide in the first dispersion is 30 mg / mL, and the dispersion medium of the first dispersion is ethanol. Then, the film is subjected to constant temperature heat treatment at 100°C under a nitrogen atmosphere for 10 min to obtain a thin film with a thickness of 30 nm.

[0249] Thin Film Example 23

[0250] This embodiment provides a thin film and its preparation method. The material of the thin film includes the nano molybdenum oxide from Material Example 15.

[0251] The method for preparing the thin film includes the following steps: providing a substrate, and spin-coating a first dispersion containing nano-molybdenum oxide on one side of the substrate under a nitrogen atmosphere at room temperature and pressure. The nano-molybdenum oxide in the first dispersion is the nano-molybdenum oxide from Material Example 13, the concentration of nano-molybdenum oxide in the first dispersion is 30 mg / mL, the dispersion medium of the first dispersion is ethanol, and then heat-treating it at a constant temperature of 100°C under a nitrogen atmosphere for 10 min to obtain a thin film with a thickness of 30 nm.

[0252] Thin film comparative examples 1-4

[0253] Compared to Thin Film Example 1, the only difference in Thin Film Comparative Example m is that the second sublayer is omitted, the first sublayer is the thin film, and the material of the thin film in Thin Film Comparative Example m includes the metal oxide in Material Comparative Example m, where m is a positive integer from 1 to 4. For example, the material of the thin film in Thin Film Comparative Example 1 includes nano-ZnO in Material Comparative Example 1, and so on.

[0254] Device Example 1

[0255] This embodiment provides an optoelectronic device and its fabrication method. The optoelectronic device is a quantum dot light-emitting diode with a positive-position structure, such as... Figure 1 As shown, the optoelectronic device 10 includes an anode 101, multiple functional layers, and a cathode 102 stacked sequentially. From bottom to top, the multiple functional layers include a hole functional layer 105, a light-emitting layer 103, and an electron functional layer 104 stacked sequentially. The hole functional layer 105 is closer to the anode 101 than the electron functional layer 104. The hole functional layer 105 consists of a hole injection layer 1051 and a hole transport layer 1052 stacked together, with the hole injection layer 1051 closer to the anode 101 than the hole transport layer 1052. The electron functional layer 104 is a single-layer structure. The light-emitting area of ​​the optoelectronic device 10 is 3.14 mm². 2 .

[0256] The materials and thicknesses of each layer in optoelectronic device 10 are as follows:

[0257] The anode 101 is made of ITO and has a thickness of 100 nm.

[0258] The cathode 102 is made of Ag and has a thickness of 80 nm.

[0259] The material of the light-emitting layer 103 includes CdSe (core) / ZnS (shell) quantum dots, the light emission color is green, and the thickness of the light-emitting layer 103 is 70nm;

[0260] The electronic functional layer 104 is the thin film in thin film embodiment 1;

[0261] The hole injection layer 1051 is made of PEDOT:PSS and has a thickness of 30nm.

[0262] The hole transport layer 1052 is made of TFB material and has a thickness of 33 nm.

[0263] The method for fabricating the optoelectronic device in this embodiment includes the following steps:

[0264] S11.1 Provide a substrate, sputter ITO on one side of the substrate to obtain an ITO layer, wipe the surface of the ITO layer with a small amount of soapy water using a cotton swab to remove visible impurities, and then sequentially ultrasonically clean the substrate containing ITO with deionized water for 15 min, acetone for 15 min, ethanol for 15 min, and isopropanol for 15 min, and after drying, perform ultraviolet-ozone surface treatment for 20 min to obtain a substrate containing an anode.

[0265] S11.2 Under normal temperature and pressure air environment, spin-coat a PEDOT:PSS aqueous solution on one side of the anode, and then place it under a nitrogen atmosphere at 150℃ for constant temperature heat treatment for 30 min to obtain the hole injection layer.

[0266] S11.3 Under normal temperature and pressure nitrogen atmosphere, spin-coat a solution containing TFB (solvent is chlorobenzene, TFB concentration is 8mg / mL) on the side of the hole injection layer away from the anode, and then place it under nitrogen atmosphere at 150℃ for constant temperature heat treatment for 30min to obtain hole transport layer.

[0267] S11.4 Under normal temperature and pressure nitrogen atmosphere, spin-coat a solution containing quantum dots (quantum dot concentration of 30 mg / mL, dispersion medium of n-octane) on the side of the hole transport layer away from the hole injection layer, and then place it under nitrogen atmosphere at 100℃ for constant temperature heat treatment for 10 min to obtain the light-emitting layer.

[0268] S11.5, Referring to the thin film preparation method in Example 1, an electronic functional layer is formed on the side of the light-emitting layer away from the hole transport layer;

[0269] S11.6. Place the laminated structure that has completed step S10.5 under a vacuum of no more than 3 × 10⁻⁶. -4 In the vapor deposition chamber of Pa, Ag is thermally vaporized on the side of the electronic functional layer away from the light-emitting layer through a mask to obtain the cathode, and then encapsulated with epoxy resin to obtain the optoelectronic device.

[0270] Device Examples 2 to 13

[0271] Device embodiment X is basically the same as device embodiment 1, except that in device embodiment X, the electronic functional layer is the thin film in thin film embodiment X, and X is a positive integer from 2 to 13.

[0272] For example, in device embodiment 2, the electronic functional layer is the thin film in thin film embodiment 2, and the preparation method of the electronic functional layer is the same as that of the thin film in thin film embodiment 2, and so on.

[0273] Device Example 14

[0274] This embodiment provides an optoelectronic device. Compared with device embodiment 1, the difference of the optoelectronic device in this embodiment is that the electronic functional layer is the thin film in thin film embodiment 16.

[0275] The preparation method of the electronic functional layer is the same as that of the thin film in Thin Film Example 16.

[0276] Device Example 15

[0277] This embodiment provides an optoelectronic device. Compared with device embodiment 1, the difference of the optoelectronic device in this embodiment is that the electronic functional layer is the thin film in thin film embodiment 17.

[0278] The preparation method of the electronic functional layer is the same as that of the thin film in Thin Film Example 17.

[0279] Device Example 16

[0280] This embodiment provides an optoelectronic device. Compared with device embodiment 1, the difference of the optoelectronic device in this embodiment is that the electronic functional layer is the thin film in thin film embodiment 18.

[0281] The preparation method of the electronic functional layer is the same as that of the thin film in Thin Film Example 18.

[0282] Device Example 17

[0283] This embodiment provides an optoelectronic device. Compared with device embodiment 1, the difference of the optoelectronic device in this embodiment is that the electronic functional layer is the thin film in thin film embodiment 19.

[0284] The preparation method of the electronic functional layer is the same as that of the thin film in Thin Film Example 19.

[0285] Device Example 18

[0286] This embodiment provides an optoelectronic device. Compared with device embodiment 1, the difference of the optoelectronic device in this embodiment is that the electronic functional layer is the thin film in thin film embodiment 20.

[0287] The preparation method of the electronic functional layer is the same as that of the thin film in Thin Film Example 20.

[0288] Device Example 19

[0289] This embodiment provides an optoelectronic device. Compared with device embodiment 1, the difference of the optoelectronic device in this embodiment is that the electronic functional layer is the thin film in thin film embodiment 21.

[0290] The preparation method of the electronic functional layer is the same as that of the thin film in Thin Film Example 21.

[0291] Device Example 20

[0292] This embodiment provides an optoelectronic device. Compared with device embodiment 1, the difference of the optoelectronic device in this embodiment is that the electronic functional layer is the thin film in thin film comparative example 1, and the hole transport layer is the thin film in thin film embodiment 14.

[0293] Device Example 21

[0294] This embodiment provides an optoelectronic device. Compared with device embodiment 1, the difference of the optoelectronic device in this embodiment is that the electronic functional layer is the thin film in thin film comparative example 1, and the hole transport layer is the thin film in thin film embodiment 15.

[0295] Device Example 22

[0296] This embodiment provides an optoelectronic device. Compared with device embodiment 1, the difference of the optoelectronic device in this embodiment is that the electronic functional layer is the thin film in thin film comparative example 1, and the hole transport layer is the thin film in thin film embodiment 22.

[0297] Device Example 23

[0298] This embodiment provides an optoelectronic device. Compared with device embodiment 1, the difference of the optoelectronic device in this embodiment is that the electronic functional layer is the thin film in thin film comparative example 1, and the hole transport layer is the thin film in thin film embodiment 23.

[0299] Device Example 24

[0300] This embodiment provides an optoelectronic device. Compared with device embodiment 1, the difference of the optoelectronic device in this embodiment is that the hole transport layer is the thin film in thin film embodiment 14.

[0301] Device Comparison Example 1

[0302] This comparative example provides an optoelectronic device. Compared with device embodiment 1, the difference in this comparative example is that the electronic functional layer is the thin film in thin film comparative example 1.

[0303] Device Comparison Example 2

[0304] This comparative example provides an optoelectronic device. Compared with device embodiment 1, the difference in this comparative example is that the electronic functional layer is the thin film in thin film comparative example 2.

[0305] Device Comparison Example 3

[0306] This comparative example provides an optoelectronic device. Compared with device embodiment 1, the difference of the optoelectronic device in this comparative example is that the electronic functional layer is the thin film in thin film comparative example 1, and the hole transport layer is the thin film in material comparative example 3.

[0307] Device Comparison Example 4

[0308] This comparative example provides an optoelectronic device. Compared with device embodiment 1, the difference in this comparative example is that the electronic functional layer is the thin film in thin film comparative example 1, and the hole transport layer is the thin film in material comparative example 4.

[0309] Experimental Example 1

[0310] Fluorescence intensity was measured for the metal oxides in Material Examples 1 to 15 and Material Comparative Examples 1 to 4. The detection method included the following steps: dispersing each metal oxide in ethanol to prepare a test sample with a concentration of 1 mg / mL; using a steady-state fluorescence spectrometer (model FS5) from Edinburgh Instruments to detect each test sample; and using an accessory SC-05 to measure the fluorescence intensity to obtain the fluorescence intensity PL of each metal oxide.

[0311] The test results are shown in Table 1 below:

[0312] Table 1

[0313]

[0314]

[0315] As shown in Table 1, compared to the metal oxide in Comparative Example 1, the metal oxides in Examples 1 to 12 exhibited lower fluorescence intensity, indicating that they possessed fewer defect states. Similarly, compared to tin oxide in Comparative Example 2, the tin oxide in Example 13 exhibited lower fluorescence intensity, indicating that it possessed fewer defect states. Likewise, compared to nickel oxide in Comparative Example 3, the nickel oxide in Example 14 exhibited lower fluorescence intensity, indicating that it possessed fewer defect states. Finally, compared to molybdenum oxide in Comparative Example 4, the nickel oxide in Example 15 possessed fewer defect states.

[0316] This demonstrates that the metal oxides prepared using the metal oxide preparation method described in the embodiments of this application have a smaller number of defect states and exhibit good performance stability.

[0317] Experiment Example 2

[0318] The performance of the optoelectronic devices in Device Examples 1 to 24 and Device Comparative Examples 1 to 4 after 1 day of packaging was tested. The performance tests were conducted in an environment with a temperature of 25°C and a relative humidity of 50%.

[0319] The testing instruments include the Fostar FPD optical characteristic measurement equipment and the external quantum efficiency optical testing instrument. The Fostar FPD optical characteristic measurement equipment is an efficiency testing system constructed from components such as a Marine Optics USB2000, a LabVIEW-controlled QE-PRO spectrometer, a Keithley 2400, a high-precision digital source meter Keithley 6485, a 50μm inner diameter optical fiber, device test probes and fixtures, various connecting cables and data cards, an efficiency testing cassette, and a data acquisition system. This system acquires the turn-on voltage (Ub) of each optoelectronic device. T Parameters such as current, brightness, and emission spectrum are obtained, and then key parameters such as external quantum efficiency and power efficiency are calculated to obtain the maximum external quantum efficiency (EQE) of each optoelectronic device. max ,%)

[0320] The formula for calculating external quantum efficiency is as follows:

[0321]

[0322] 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.

[0323] The device lifetime testing method includes the following steps: Under constant current (2mA) driving, a 128-channel QLED lifetime testing system is used to perform electroluminescence lifetime analysis on each optoelectronic device, record the time (T95,h) required for each optoelectronic device to decay from maximum brightness to 95%, and calculate the time (T95@1000nit,h) required for each optoelectronic device to decay from 100% brightness to 95% brightness at 1000nit using the decay fitting formula.

[0324] The formula for calculating device lifetime is as follows:

[0325]

[0326] In the above 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, which is usually between 1.6 and 2. In this experimental example, the value of A for the optoelectronic device is 1.7.

[0327] In addition, the optoelectronic devices that have completed the above performance tests were placed in an environment with room temperature, light protection and relative humidity of 80% for 10 days. Then, the maximum external quantum efficiency (EQEmax@10 days, %) and device lifetime (T95@1000nit@10 days, h) of each optoelectronic device were detected using the aforementioned method.

[0328] The performance test results of each optoelectronic device are shown in Table 2 below:

[0329] Table 2

[0330]

[0331]

[0332] As shown in Table 2, compared with the optoelectronic devices in Comparative Examples 1 to 4, the optoelectronic devices in Device Examples 1 to 24 have better overall performance. Specifically, the optoelectronic devices in Device Examples 1 to 24 have higher device efficiency, longer device life, and better performance stability.

[0333] This indicates that the materials of the electronic functional layer and / or hole functional layer include the metal oxide prepared by the metal oxide preparation method in the embodiments of this application, or the metal oxide in the embodiments of this application; or, the electronic functional layer and / or hole functional layer includes the thin film in the embodiments of this application, which can improve the surface flatness of the film layer and optimize the interface defects between adjacent functional layers, thereby improving the optoelectronic performance, device life and performance stability of the optoelectronic device.

[0334] In Comparative Examples 1 to 4, the electronic functional layer and / or hole functional layer of the optoelectronic devices are made of metal oxides prepared by conventional methods. This results in a large number of defect states, leading to poor performance stability of the film layer and thus poor overall performance of the optoelectronic devices. In addition, metal oxides prepared by conventional methods will adsorb water and oxygen, resulting in electrode corrosion and accelerating the forward aging process, which further degrades the performance stability of the optoelectronic devices.

[0335] This document uses specific examples to illustrate the principles and implementation methods of this application. The descriptions of the above embodiments are only for the purpose of helping to understand the methods 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 method for preparing a metal oxide, characterized in that, Including the following steps: The metal precursor and the alkali were mixed in solution to obtain a first mixture; as well as The first mixture is mixed with an amine compound to obtain the metal oxide; The amine compounds have the structure shown in general formula (Ⅰ): In general formula (Ⅰ), R1, R2, and R3 are independently selected from hydrogen, deuterium, and *-NR, respectively. a R b Unreplaced or replaced by at least one R c Substituted C1–C30 aliphatic chain hydrocarbon groups, unsubstituted or with at least one R c Substituted C1–C30 aliphatic chain hydroxyl groups, unsubstituted or with at least one R c Substituted C3–C30 aliphatic cyclic hydrocarbon groups, unsubstituted or with at least one R c Substituted C3–C30 aliphatic heterocyclic hydrocarbon groups, unsubstituted or with at least one R c The substituted aryl group has 6 to 30 cyclic atoms, is unsubstituted, or is substituted with at least one R. c The substituted aryloxy group has 6 to 30 cyclic atoms, and is either unsubstituted or substituted with at least one R. c The substituted heteroaryl group has 5 to 30 cyclic atoms, is unsubstituted, or is substituted with at least one R c The substituted ring atoms are 5 to 30 heteroaryloxy groups, or combinations of these groups; R1 to R3 are not simultaneously selected from hydrogen, deuterium, *-NH2 or *-ND2; R c Each occurrence is independently selected from deuterium and *-NR. a R b Halogen groups, hydroxyl groups, carboxyl groups, nitro groups, sulfonic acid groups, aldehyde groups, mercapto groups, cyano groups, C1-C20 aliphatic chain hydrocarbon groups, C1-C20 aliphatic chain alkyloxy groups, aliphatic cyclic hydrocarbon groups with 3-20 ring atoms, aliphatic heterocyclic hydrocarbon groups with 3-20 ring atoms, aryl groups with 6-20 ring atoms, aryloxy groups with 6-20 ring atoms, heteroaryl groups with 5-20 ring atoms, heteroaryloxy groups with 5-20 ring atoms, or combinations of these groups; Among them, R a and R b Each time it appears, it is independently selected from hydrogen, deuterium, C1-C20 aliphatic chain hydrocarbon group, C1-C20 aliphatic chain hydrocarbon oxygen group, aliphatic cyclic hydrocarbon group with 3-20 ring atoms, aliphatic heterocyclic hydrocarbon group with 3-20 ring atoms, aryl group with 6-20 ring atoms, aryloxy group with 6-20 ring atoms, heteroaryl group with 5-20 ring atoms, heteroaryloxy group with 5-20 ring atoms, or a combination of these groups; * indicates a connection point.

2. The method for preparing the metal oxide according to claim 1, characterized in that, R1 and R2 are each independently selected from hydrogen, D, or C1-C4 aliphatic chain hydrocarbon groups, and R3 is selected from unsubstituted or substituted hydrocarbons. c Substituted C1–C10 aliphatic chain hydrocarbon groups, unsubstituted or with at least one R c Substituted C1-C10 aliphatic chain hydroxyl groups, substituted or substituted with at least one R c The substituted aryl group having a ring atom number of 6 to 14, or a combination of the aforementioned groups; And / or, R c Each occurrence is independently selected from deuterium and *-NR. a R b Halogen groups, C1-C10 aliphatic chain hydrocarbon groups, C1-C10 aliphatic chain hydroxyl groups, or combinations of the aforementioned groups; And / or, R a and R b Each time it appears, it is independently selected from hydrogen, deuterium, C1-C10 aliphatic chain hydrocarbon group, C1-C10 aliphatic chain hydroxyl group, or a combination of these groups; And / or, the metal element of the metal precursor is selected from one or more of Group IA metals, Group IIA metals, Group IIIA metals, Group IVA metals, Group VA metals and transition metals; optionally, the metal element of the metal precursor is selected from one or more of Zn, Ti, Sn, Ba, Ta, Al, Zr, Mg, Ca, Ga, Li, Y, In, Ni, Mo, W, V, Cr and Cu; And / or, the base includes one or more of organic bases and inorganic bases, wherein the inorganic base is selected from one or more of alkali metal oxides, alkali metal hydroxides, alkali metal bicarbonates, alkali metal carbonates, alkaline earth metal oxides, alkaline earth metal hydroxides, alkaline earth metal bicarbonates, and ammonia water; the organic base is selected from one or more of alkanolamine compounds, alkyl ammonium hydroxides, and urea, wherein the alkyl group in the alkyl ammonium hydroxide contains 1 to 20 carbon atoms; And / or, in the step of mixing the metal precursor and the base in solution, the molar ratio of the metal precursor to the base is 1:(0.8-5), and / or the metal precursor and the base are mixed at a temperature of 25°C to 40°C, and / or the mixing time of the metal precursor and the base is 10 min to 30 min, and / or the solution includes one or more of methanol, ethanol, ethylene glycol, acetonitrile, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, dichloromethane, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, 3-methoxybutanol, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, and diethylene glycol dimethyl ether, and / or the pH of the first mixture is 12 to 14; And / or, the molar ratio of the metal element to the amine compound in the metal precursor is 1:(0.05~0.5); And / or, after the step of mixing the first mixture and the amine compound and before the step of obtaining the metal oxide, the method for preparing the metal oxide further includes the step of: performing solid-liquid separation on a second mixture obtained by mixing the first mixture and the amine compound, the solid-liquid separation being operably performed at least once; optionally, the solid-liquid separation includes the step of: mixing the second mixture and a precipitant to precipitate a precipitate, then centrifuging and collecting the precipitate, wherein the precipitant includes one or more of ketone compounds, ester compounds, and alcohol compounds.

3. The method for preparing the metal oxide according to claim 2, characterized in that, R3 has the structure shown in the general formula (1-1): In general formula (1-1), R d Each time it appears, it is independently selected from a halogen group, an unsubstituted or substituted C1-C8 alkyl group, an unsubstituted or substituted C1-C8 alkoxy group, or a combination of these groups; m is a positive integer from 1 to 4; R e Selected from single-bonded or C1-C4 alkylene groups; # indicates the connection site between R3 and N; And / or, the amine compound is selected from benzylamine, diphenylamine, triphenylamine, chlorobenzylamine, bromobenzylamine, fluorobenzylamine, dichlorobenzylamine, difluorobenzylamine, dibromobenzylamine, 4-bromo-2-iodobenzylamine, 2-chloro-3-fluorobenzylamine, 3-bromo-5-chlorobenzylamine, 3-bromo-5-fluorobenzylamine, 3-chloro-2-fluorobenzylamine, 4-chloro-2-fluorobenzylamine, p-chlorophenethylamine, One or more of the following: m-chlorophenethylamine, o-chlorophenethylamine, o-bromophenethylamine, p-bromophenethylamine, m-bromophenethylamine, p-fluorophenethylamine, m-fluorophenethylamine, o-fluorophenethylamine, dichlorophenethylamine, difluorophenethylamine, N-methyl-3-chlorophenethylamine, 2,5-dimethoxy-4-chlorophenethylamine, 2,5-dimethoxy-4-chlorophenacetin, m-bromophenacetin, p-chlorophenbutamine, and 4-bromophenbutamine.

4. A metal oxide, characterized in that, The surface of the metal oxide is attached with ligands, which have the structure shown in general formula (II): In general formula (II), & represents the connection site between the ligand and the metal oxide; R1 is selected from the R1 as described in any one of claims 1 to 3, R2 is selected from the R2 as described in any one of claims 1 to 3, and R3 is selected from the R3 as described in any one of claims 1 to 3.

5. The metal oxide according to claim 4, characterized in that, The metal oxide is prepared using the preparation method of the metal oxide as described in any one of claims 1 to 3; And / or, the fluorescence intensity of the metal oxide is 0.01 × 10⁻⁶. 4 ~0.8×10 4 ; And / or, the average particle size of the metal oxide is 1 nm to 50 nm; And / or, the metal oxide is an N-type metal oxide, selected from ZnO, TiO2, SnO2, BaO, Ta2O3, Al2O3, ZrO2, Zn (1-x) Mg x O, Zn (1-x) Ca x O, Zn (1-x) Zr x O, Zn (1-x) Ga x O, Zn (1-x) Al x O, Zn (1-x) Li x O, Zn (1-x) Ti x O, Zn (1-x) Y x O、In (1-x) Sn x O or Ti (1-x) Li x O, where 0 < x ≤ 0.5; or, the metal oxide is a p-type metal oxide selected from oxides of nickel, copper, molybdenum, chromium, tungsten, vanadium, or hafnium.

6. A thin film, characterized in that, The thin film includes a metal oxide prepared by the method of preparing the metal oxide as described in any one of claims 1 to 3, and / or the thin film includes a metal oxide as described in claim 4 or 5.

7. The thin film according to claim 6, characterized in that, The film has a single-layer structure; Alternatively, the film comprises a first sublayer and a second sublayer stacked sequentially; the first sublayer comprises a metal oxide prepared by the method for preparing a metal oxide as described in any one of claims 1 to 3, and / or the first sublayer comprises a metal oxide as described in claim 4 or 5; the second sublayer comprises a fluoropolymer.

8. The thin film according to claim 7, characterized in that, The monomers of the fluoropolymer include one or more of perfluoroolefins, hydrofluoroolefins, chlorofluoroolefins, and hydrochlorofluoroolefins; optionally, the monomers of the fluoropolymer include one or more of trifluoroethylene, trifluorochloroethylene, vinylidene fluoride, vinyl fluoride, tetrafluoroethylene, and hexafluoropropylene. And / or, the fluoropolymer is selected from one or more of polychlorotrifluoroethylene, poly(ethylene-chlorotrifluoroethylene), poly(perfluoroethylene-propylene resin), polyvinylidene fluoride, polyvinylidene fluoride, polytetrafluoroethylene, poly(vinylidene fluoride-co-hexafluoropropylene), and tetrafluoroethylene-hexafluoropropylene copolymer; And / or, the thickness of the first sublayer is 10nm to 100nm; And / or, the thickness of the second sublayer is 1 nm to 5 nm.

9. An optoelectronic device, characterized in that, include: The anode and cathode are positioned opposite each other; as well as Multiple functional layers are disposed between the anode and the cathode; Wherein, at least one of the plurality of functional layers is made of a metal oxide prepared by the method of preparing a metal oxide as described in any one of claims 1 to 3, or a metal oxide as described in claim 4 or 5, and / or at least one of the plurality of functional layers is made of a thin film as described in any one of claims 6 to 8.

10. The optoelectronic device according to claim 9, characterized in that, The plurality of functional layers include an electronic functional layer; the material of the electronic functional layer includes a metal oxide prepared by the method for preparing the metal oxide as described in any one of claims 1 to 3, or a metal oxide as described in claim 4 or 5, and / or the electronic functional layer includes a thin film as described in any one of claims 6 to 8, wherein the metal oxide in the electronic functional layer is an N-type metal oxide; or, the material of the electronic functional layer includes ZnO, TiO2, SnO2, BaO, Ta2O3, Al2O3, ZrO2, Zn (1-x) Mg x O, Zn (1-x) Ca x O, Zn (1-x) Zr x O, Zn (1-x) Ga x O, Zn (1-x) Al x O, Zn (1-x) Li x O, Zn (1-x) Ti x O, Zn (1-x) Y x O、In (1-x) Sn x O and Ti (1-x) Li x One or more of O, where 0 < x ≤ 0.5; And / or, the plurality of functional layers include a hole functional layer; the material of the hole functional layer includes a metal oxide prepared by the method of preparing the metal oxide as described in any one of claims 1 to 3, or a metal oxide as described in claim 4 or 5, and / or the hole functional layer includes a thin film as described in any one of claims 6 to 8, wherein the metal oxide in the hole functional layer is a p-type metal oxide; or, the material of the hole functional layer includes one or more of organic materials, a first inorganic compound material, and a second inorganic compound material;The organic materials include poly(3,4-vinyldioxythiophene): poly(styrene sulfonic acid), copper phthalocyanine, titanium phthalocyanine, 2,3,5,6-tetrafluoro-7,7',8,8'-tetracyanodimethyl-p-benzoquinone, 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazabenzophenanthrene, polyaniline, polypyrrole, 3-hexyl-substituted polythiophene, poly(9-vinylcarbazole), 4,4'-bis(9-carbazole)biphenyl, poly[bis(4-phenyl)(4-butylphenyl)amine], 4,4'-cyclohexylbis[N,N-bis(4-methylphenyl)aniline], poly[(9,9-dioctylfluorenyl-2,7-diyl)- Co-(4,4'-(N-(4-sec-butylphenyl)diphenylamine)], poly[(N,N'-(4-n-butylphenyl)-N,N'-diphenyl-1,4-phenylenediamine)-ALT-(9,9-di-n-octylfluorenyl-2,7-diyl)], 4,4',4'-tris(N-3-methylphenyl-N-phenylamino)triphenylamine, 4,4',4”-tris(carbazole-9-yl)triphenylamine, 4,4',4’-tris(2-naphthylphenylamino)triphenylamine, N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine, N,N'-diphenyl-N,N'-di(3-methylphenyl)-1 One or more of 1'-biphenyl-4,4'-diamine, N,N'-bis[4-(diphenylamino)phenyl]-N,N'-diphenylbenzidine, N,N'-bis(3-methylphenyl)-N,N'-diphenyl-9,9-spirodifluorene-2,7-diamine, N2,N7-di-1-naphthyl-N2,N7-diphenyl-9,9'-spirodi[9H-fluorene]-2,7-diamine, poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine], and 2,2',7,7'-tetratetra[N,N-di(4-methoxyphenyl)amino]-9,9'-spirodifluorene, and / or the first inorganic compound material includes graphene, C60, The second inorganic compound material comprises one or more of the following: nickel oxide, copper oxide, molybdenum oxide, chromium oxide, tungsten oxide, vanadium oxide, hafnium oxide, copper sulfide, molybdenum sulfide, and tungsten sulfide; and / or the second inorganic compound material comprises one or more doped first compounds, wherein the host material of the doped first compound comprises one or more of the following: graphene, C60, nickel oxide, copper oxide, molybdenum oxide, chromium oxide, tungsten oxide, vanadium oxide, hafnium oxide, copper sulfide, molybdenum sulfide, and tungsten sulfide; and the doping element of the doped first compound is selected from one or more of the following: nickel, molybdenum, tungsten, vanadium, chromium, copper, hafnium, and platinum group metals. And / or, the plurality of functional layers include a light-emitting layer, the material of which includes one or more of organic light-emitting materials and quantum dots; the organic light-emitting material is selected from 4,4'-bis(N-carbazole)-1,1'-biphenyl:tris[2-(p-tolyl)pyridinium(III), 4,4',4”-tris(carbazole-9-yl)triphenylamine:tris[2-(p-tolyl)pyridinium, diaromatic anthracene derivatives, stilbene aromatic derivatives, pyrene derivatives, fluorene derivatives, TBPe fluorescent materials, TTPX fluorescent materials, TBRb fluorescent materials, D One or more of the following: BP fluorescent materials, delayed fluorescent materials, TTA materials, thermally activated delayed materials, polymers containing BN covalent bonds, hybrid localized charge transfer excited-state materials, excitocomplex luminescent materials, polyacetylene and its derivatives, poly(p-phenylene) and its derivatives, polythiophene and its derivatives, and polyfluorene and its derivatives; and / or, the quantum dots are selected from one or more of single-component quantum dots, core-shell structured quantum dots, inorganic perovskite quantum dots, organic perovskite quantum dots, and organic-inorganic hybrid perovskite quantum dots, wherein the core-shell structured quantum dots include one or more shells;The materials of the single-component quantum dots, the core of the core-shell quantum dots, and the shell of the core-shell quantum dots are each independently selected from at least one of group II-VI compounds, group III-VI compounds, group III-V compounds, group IV-VI compounds, or group I-III-VI compounds, wherein the group II-VI compounds are selected from CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, and CdZnTe. CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, and HgZnSTe, and / or the III-V compound is selected from GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, and AlPA. One or more of the following: s, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, and InAlPSb, and / or the III-VI compound is selected from one or more of In2S3, In2Se3, InGaS3, and InGaSe3, and / or the IV-VI compound is selected from SnS, SnSe, SnTe. The inorganic perovskite quantum dots are selected from one or more of the following: PbS, PbSe, PbTe, SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, SnPbSeTe, and SnPbSTe; and / or the group I-III-VI compounds are selected from one or more of the following: AgInS, AgInS2, CuInS, CuInS2, AgGaS2, CuGaS2, CuGaO2, AgGaO2, AgAlO2, AgInGaS2, and CuInGaS2; and / or the general structural formula of the inorganic perovskite quantum dots is AMX3, where A is Cs. + M is a divalent metal cation, and M is selected from Pb. 2+ Sn 2+ Cu 2+ Ni 2+ Cd 2+ Cr 2+ Mn 2 + Co 2+ Fe 2+ 、Ge 2+ Yb 2+ and Eu 2+ One or more of the following, where X is a halide anion; and / or, the general structural formula of the organic perovskite quantum dot is CMX3, where C is formamidinyl; and / or, the general structural formula of the organic-inorganic hybrid perovskite quantum dot is BMX3, where B is an organic amine cation.

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