Composition, film and method for producing the same, light emitting device, and electronic device

Abstract

The application discloses a composition, a film and a preparation method thereof, a light-emitting device and an electronic device, and relates to the technical field of light-emitting devices.The composition comprises a first metal oxide and a metal organic compound, the metal organic compound can passivate defect states of the first metal oxide, the number of defect states of the first metal oxide is reduced, and the performance stability of the first metal oxide is improved.The composition can be applied to the preparation of a light-emitting device, and is beneficial to improving the device efficiency, the device service life and the performance stability of the light-emitting device.

Description

Technical Field

[0001] This application relates to the field of organic materials technology, specifically to a composition, a thin film and its preparation method, a light-emitting device, and an electronic device. 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] In view of the shortcomings of the prior art, this application provides a composition, a thin film and a method for preparing the same, a light-emitting device and an electronic device.

[0005] In a first aspect, this application provides a composition comprising a first metal oxide and an organometallic compound, wherein the metal element in the first metal oxide comprises a first metal element, and the metal element in the organometallic compound comprises a second metal element, and the organometallic compound comprises a compound with the structure shown in the following general formula (I):

[0006] A m+ (R1-X - ) n (I);

[0007] In general formula (Ⅰ), A m+ R1-X is the m-valence ion of the second metallic element. - Selected from

[0008] R1 is selected from unsubstituted or R1-substituted. a Substituted C1–C30 aliphatic chain hydrocarbon groups, unsubstituted or with at least one R a Substituted C1–C30 aliphatic chain hydroxyl groups, unsubstituted or with at least one R a The substituted aliphatic cyclic hydrocarbon group having 3 to 30 substituted ring atoms, or the unsubstituted or substituted group having at least one R group. a The substituted aliphatic heterocyclic hydrocarbon group having 3 to 30 ring atoms, is unsubstituted or has been substituted with at least one R group.a The substituted aryl group has 6 to 30 ring atoms, is unsubstituted, or is substituted with at least one R. a The substituted heteroaryl group having 5 to 30 ring atoms, or a combination of the aforementioned groups;

[0009] R a Each time it appears, it is independently selected from -H, -D, C1-C20 aliphatic chain hydrocarbon groups, C1-C20 aliphatic chain hydroxyl 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, and heteroaryl groups with 5-20 ring atoms. Hydroxyl, halogen, aldehyde, mercapto, cyano, or combinations thereof;

[0010] m and n are each independently selected from integers from 1 to 6.

[0011] In a second aspect, this application provides a thin film, the material of which comprises the composition described in the first aspect, and / or the thin film is prepared using the composition described in the first aspect.

[0012] Thirdly, this application provides a method for preparing a thin film, the method comprising the steps of: depositing a composition as described in the first aspect, drying the deposited composition to form a film, and obtaining the thin film;

[0013] Alternatively, the method for preparing the thin film may include the following steps:

[0014] A deposition dispersion comprising a first metal oxide as described in the first aspect is performed, and the deposited dispersion is dried to form a film, thereby obtaining a first film layer; and

[0015] The first film layer is brought into contact with a first solution, the first solution comprising the organometallic compound as described in the first aspect, and then subjected to a first drying process to obtain the thin film.

[0016] Fourthly, this application provides a light-emitting device, comprising:

[0017] The anode and cathode are arranged opposite each other; and

[0018] Multiple functional layers are disposed between the anode and the cathode;

[0019] Wherein, at least one of the plurality of functional layers is made of a material comprising the composition described in the first aspect, and / or at least one of the plurality of functional layers comprises a thin film as described in the second aspect, and / or at least one of the plurality of functional layers is prepared using a thin film preparation method as described in the third aspect.

[0020] Fifthly, this application provides an electronic device, the electronic device including a display panel, the display panel including a plurality of pixel units arranged in an array, each pixel unit including a light-emitting device as described in the fourth aspect.

[0021] This application provides a composition, a thin film and a method for preparing the same, a light-emitting device, and an electronic device, which have the following technical effects:

[0022] The composition of this application includes metal oxides and organometallic compounds. The organometallic compounds can passivate the defect states of the metal oxides, reduce the number of defect states of the metal oxides, and thus improve the performance of the light-emitting device. Attached Figure Description

[0023] The technical solution and other beneficial effects of this application will become apparent from the following detailed description of specific embodiments in conjunction with the accompanying drawings.

[0024] Figure 1 This is a schematic diagram of the structure of a light-emitting device provided in an embodiment of this application. Detailed Implementation

[0025] 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.

[0026] 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.

[0027] 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.

[0028] In this application, unless otherwise stated, directional terms such as "upper" and "lower" generally refer to the upper and lower positions of the light-emitting 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 light-emitting device. The terms "first," "second," "third," etc., are used merely as indications and do not impose numerical requirements or establish a sequence.

[0029] 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.

[0030] 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.

[0031] 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.

[0032] 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, 2-ethylbutyl, 3,3-dimethylbutyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, 1-methylpentyl, 3-methylpentyl, 2-ethylpentyl, 4-methyl-2-pentyl, n-hexyl, 1-methylhexyl, 2-ethylhexyl, 2-butylhexyl, n-heptyl, 1-methylheptyl, 2,2-dimethylheptyl, 2-ethylheptyl, 2-butylheptyl, n-octyl, tert-octyl, 2-ethyloctyl, 2-butyloctyl, 2-hexyloctyl, 3,7-dimethyloctyl, n-nonyl, n-decyl, 2-ethyldecyl, 2-butyldecyl, 2-hexyl Decyl, 2-octyldecyl, n-undecyl, n-dodecyl, 2-ethyldodecyl, 2-butyldodecyl, 2-hexyldodecyl, 2-octyldodecyl, n-tridecyl, n-tetradecyl, n-pentadecanyl, n-hexadecyl, 2-ethylhexadecyl, 2-butylhexadecyl, 2-hexylhexadecyl, 2-octylhexadecyl, n-heptadecyl, n-octadecyl, n-octadecyl, n-heptadecyl, n-octadecyl, n-heptadecyl, n-eicosyl, 2-ethyleicosyl, 2-butyleicosyl, 2-hexyleicosyl, 2-octyleicosyl, n-monodecyl, n-eicosyl, n-eicosyl, n-eicosyl, n-eicosyl, n-eicosyl, n-eicosyl, n-eicosyl, or n-trianecanyl.

[0033] The term "aliphatic chain hydrocarbon group" refers to a group with the general formula *-O-aliphatic chain hydrocarbon group, where * indicates a bonding site and O represents an oxygen atom. 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-Decaalkoxy (-OC) 10 H 21 ), or n-dodecyloxy (-OC) 12 H 25 The number of carbon atoms in "C1 to C30 aliphatic chain hydroxyl 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.

[0034] 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. Suitable examples include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, or adamantyl.

[0035] 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.

[0036] 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.

[0037] 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.

[0038] 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.

[0039] 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.

[0040] 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.

[0041] 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.

[0042] This application provides a composition comprising a first metal oxide and an organometallic compound, wherein the metal element in the first metal oxide comprises a first metal element, the metal element in the organometallic compound comprises a second metal element, and the organometallic compound comprises a compound with the structure shown in general formula (I) below:

[0043] A m+ (R1-X - ) n (I);

[0044] In general formula (Ⅰ), A m+ R1-X is an m-valence ion of the second metallic element. - Selected from m and n are each independently selected from integers from 1 to 6.

[0045] Wherein, R1 is selected from unsubstituted or substituted by at least one R a Substituted C1–C30 aliphatic chain hydrocarbon groups, unsubstituted or with at least one R a Substituted C1–C30 aliphatic chain hydroxyl groups, unsubstituted or with at least one R a The substituted aliphatic cyclic hydrocarbon group having 3 to 30 substituted ring atoms, or the unsubstituted or substituted group having at least one R group. a The substituted aliphatic heterocyclic hydrocarbon group having 3 to 30 ring atoms, is unsubstituted or has been substituted with at least one R group. a The substituted aryl group has 6 to 30 ring atoms, is unsubstituted, or is substituted with at least one R. a The substituted heteroaryl group has a ring atom number of 5 to 30, or a combination of the aforementioned groups.

[0046] R a Each time it appears, it is independently selected from -H, -D, C1-C20 aliphatic chain hydrocarbon groups, C1-C20 aliphatic chain hydroxyl 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, and heteroaryl groups with 5-20 ring atoms. Hydroxyl, halogen, aldehyde, mercapto, cyano, or combinations thereof.

[0047] In the compositions of the embodiments of this application, the organometallic compound can passivate the defect states of the first metal oxide, reduce the number of defect states of the first metal oxide, and thereby improve the performance stability of the first metal oxide.

[0048] In some embodiments of this application, in the composition, at least a portion of the oxygen atoms in the organometallic compound fill at least a portion of the oxygen vacancies in the first metal oxide, thereby reducing the number of oxygen vacancy defect states in the first metal oxide; and / or, at least a portion of the A atoms in the organometallic compound fill at least a portion of the oxygen vacancy defects in the first metal oxide; m+ Filling at least a portion of the metal vacancies in the first metal oxide, thereby reducing the number of metal vacancy defect states in the first metal oxide.

[0049] To further improve the solution processing performance of the composition, in some embodiments of this application, R1 is selected from unsubstituted or substituted compounds. a Substituted C1–C20 aliphatic chain hydrocarbon groups, unsubstituted or with at least one R aSubstituted C1–C20 aliphatic chain hydroxyl groups, unsubstituted or substituted with at least one R a The substituted aliphatic cyclic hydrocarbon group having 3 to 20 substituted ring atoms, or the unsubstituted or substituted group having at least one R group. a The substituted aliphatic heterocyclic hydrocarbon group having 6 to 20 ring atoms, is unsubstituted or has been substituted with at least one R group. a The substituted aryl group has 6 to 20 ring atoms, is unsubstituted, or is substituted with at least one R. a The substituted heteroaryl group has 6 to 20 ring atoms, or a combination of these groups; R a Each occurrence is independently selected from C1–C20 aliphatic chain hydrocarbon groups, C1–C20 aliphatic chain alkyl groups, and Hydroxyl groups, or combinations of these groups.

[0050] To further improve the conductivity of the composition, in some embodiments of this application, R1-COO - It has a structure that can be represented by any of the following structural formulas:

[0051]

[0052] Where x1 and x2 are independently selected from positive integers from 0 to 10, for example, x1 and x2 are independently selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10; R b and R c Each group is independently selected from -H, -D, hydroxyl, and aliphatic chain hydrocarbon groups from C1 to C20.

[0053] In order to make A m+ It can easily fill the metal vacancies in the first metal oxide. In some embodiments of this application, the first metal element and the second metal element are the same.

[0054] In some embodiments of this application, the first metal element and the second metal element are independently selected from group IA metal elements, group IIA metal elements, group IIIA metal elements, group IVA metal elements, group VA metal elements or transition metal elements.

[0055] In some embodiments of this application, the first metal element and the second metal element are independently selected from Zn, Ti, Sn, Ba, Ta, Al, Zr, Mg, Ca, Ga, Li, Y, Ni, Mo, W, V, Cr, Cu or Hf.

[0056] The first metal oxide can be in the form of nanoparticles, nanosheets, or nanorods. In some embodiments of this application, the first metal oxide is in the form of nanoparticles, and the average particle size of the first metal oxide is 2 nm to 100 nm, for example, it can be 2 nm, 5 nm, 8 nm, 10 nm, 30 nm, 50 nm, 80 nm, 100 nm, or any two of the aforementioned values.

[0057] In some embodiments of this application, the first metal oxide is an N-type metal oxide or a P-type metal oxide.

[0058] In at least one embodiment of this application, the first metal oxide is an N-type metal oxide, including 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 quantity, and 0 < x ≤ 0.5.

[0059] In some embodiments of this application, the first metal oxide includes ZnO, Zn (1-x) Mg x O, Zn (1-x) Al x O, Zn (1-x) Li x O and Zn (1-x) Ti xOne or more of O, the organometallic compounds include one or more of zinc naphthenate (CAS No. 12001-85-3), zinc benzoate (CAS No. 553-72-0), zinc salicylate (CAS No. 16283-36-6), zinc pyridinecarboxylate (CAS No. 17949-65-4), zinc benzenesulfonate (CAS No. 127-82-2), zinc benzenesulfinate (CAS No. 12561-48-7), and zinc p-toluenesulfonate (CAS No. 123334-05-4). The organometallic compounds can effectively passivate the defect states of the first metal oxide, and based on the presence of aromatic ring structures in the organometallic compounds, further improve the electronic transport properties of the composition.

[0060] Preferably, the first metal oxide includes ZnO and Zn (1-x) Mg x One or more of O, and organometallic compounds including zinc naphthate. It should be noted that ZnO or Zn (1-x) Mg x O has strong adsorption and electrical sensitivity, ZnO or Zn (1-x) Mg x The surface of O contains adsorbed water (water molecules generated during synthesis and adsorbed water in the product). These water molecules will remain on ZnO or Zn (1-x) Mg x O forms adsorption coordination compounds on its surface, thereby altering ZnO or Zn (1-x) Mg x The electrical properties of O, therefore, ZnO or Zn (1-x) Mg x The amount of water adsorbed on the O surface is one of the key factors affecting its electrical stability. Furthermore, due to the synthesis process, nano-ZnO or nano-Zn... (1-x) Mg x The purity of O is low, and the product will be doped with some precursors. These precursors will be transformed into other impurities in the presence of water. These impurities will affect the purity of nano-ZnO or nano-Zn. (1-x) Mg x The storage stability and electrical properties of O are affected; therefore, changes in the surface adsorbed water content can influence ZnO or Zn. (1-x) Mg x The applicant discovered that when the organometallic compound includes zinc naphthate, zinc naphthate adsorbs onto ZnO or Zn. (1-x) Mg x A continuous thin film can form on the surface of O, reducing the solid-liquid interfacial energy and contact angle, which can promote the formation of ZnO or Zn (1-x) Mg x O allows for faster and more uniform surface drainage, thus enabling the removal of ZnO or Zn (1-x) Mgx Maintaining the surface adsorbed water content of O within a suitable range further enhances the performance of ZnO or ZnO. (1-x) Mg x O's performance stability.

[0061] In addition, zinc naphthate has a certain catalytic effect, which can extract oxygen atoms from organic groups, and based on the basicity of zinc naphthate, it is beneficial for the extraction of ZnO or ZnO. (1-x) Mg x After O-film formation, the byproducts in the membrane layer can be further purified into stable final products, which can further improve the performance stability of the membrane layer.

[0062] In some other embodiments of this application, the first metal oxide is a P-type metal oxide, which includes one or more of the following: nickel oxide, copper oxide, molybdenum oxide, chromium oxide, tungsten oxide, vanadium oxide, and hafnium oxide.

[0063] To further improve the hole transport performance of the composition, in some embodiments of this application, the first metal oxide is an oxide of nickel, and the organometallic compound includes one or more of nickel naphthenate (CAS No. 61788-71-4), nickel benzoate (CAS No. 553-71-9), and nickel cyclohexanebutyrate (CAS No. 3906-55-6).

[0064] To ensure the band gap of the composition is within a suitable range, thereby further improving the carrier transport performance of the composition, in some embodiments of this application, the mass ratio of the first metal oxide to the organometallic compound in the composition is 1:(0.001 to 0.05), for example, it can be 1:0.001, 1:0.003, 1:0.005, 1:0.008, 1:0.01, 1:0.02, 1:0.03, 1:0.04, 1:0.05, or any range between two of the aforementioned values. In at least one embodiment of this application, the mass ratio of the first metal oxide to the organometallic compound is 1:(0.02 to 0.05). Within the aforementioned range, while reducing the number of defect states of the first metal oxide, the conductivity of the composition is further improved, resulting in good performance stability and carrier transport performance.

[0065] In some embodiments of this application, the composition further includes a solvent, a first metal oxide and an organometallic compound dispersed in the solvent. The solvents include, but are not limited to, one or more of the following: alkanes, aromatic hydrocarbons, halogenated hydrocarbons, alcohols, ethers, ketones, esters, furans, pyridines, amides, and sulfones. Alkanes include, but are not limited to, one or more of the following: nonane, decane, dodecane, terpenes, butylcyclohexane, n-octane, n-hexane, n-heptane, n-nonane, n-decane, cyclohexane, and cyclopentane. Aromatic hydrocarbons include, but are not limited to, one or more of the following: diethylbenzene, trimethylbenzene, propylbenzene, isopropylbenzene, p-toluene, propylbenzene, and 1-methylnaphthalene or indene. Halogenated alkanes include, but are not limited to, one or more of the following: dichloromethane, chloroform, and carbon tetrachloride. Alcohols include, but are not limited to, one or more of the following: methanol, ethanol, propanol, butanol, ethylene glycol, and glycerol. Ethers include, but are not limited to, ethylene glycol monomethyl ether. Furans include, but are not limited to, tetrahydrofuran. Pyridines include, but are not limited to, pyridine. Amides include, but are not limited to, N,N-dimethylformamide. Sulfones include, but are not limited to, dimethyl sulfoxide.

[0066] In some embodiments of this application, the solvent includes one or more of ethanol, toluene, chlorobenzene, chloroform, carbon tetrachloride, dimethyl sulfoxide, N,N-dimethylformamide, tetrahydrofuran, N-methylpyrrolidone, acetone, tetrahydronaphthalene, trifluorotoluene, and chloronaphthalene.

[0067] To further improve the solution processing performance of the composition, in some embodiments of this application, the concentration of the first metal oxide in the composition is 5 mg / mL to 50 mg / mL, for example, it can be 5 mg / mL, 10 mg / mL, 20 mg / mL, 30 mg / mL, 40 mg / mL, 50 mg / mL or any two of the aforementioned values.

[0068] This application also provides a thin film, the material of which includes the composition described above (excluding solvent), and / or the thin film is prepared using the composition described above (including solvent). Compared to a first metal oxide thin film of the same size, the thin film of this application embodiment has fewer defect states and higher performance stability, and the surface flatness of the thin film of this application embodiment is better.

[0069] In some embodiments of this application, the oxygen vacancy content in the film is 1.1% to 2%, for example, it can be 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2% or any two of the aforementioned values.

[0070] In some embodiments of this application, the metal vacancy content in the thin film is 1.1% to 2%, for example, it can be 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2% or any two of the aforementioned values.

[0071] This application also provides a method for preparing a thin film, which can be used to prepare any of the thin films described above. The method for preparing the thin film (hereinafter referred to as the first method for preparing the thin film) includes the steps of: depositing a composition (including a solvent) as described above, drying the deposited composition to form a film, and obtaining the thin film. By modifying the first metal oxide with an organometallic compound, the surface of the first metal oxide in the thin film can generate fixed chemisorption sites for water molecules, and the organometallic compound can passivate the defect states of the first metal oxide, thereby improving the performance stability of the thin film.

[0072] Alternatively, the method for preparing the thin film (hereinafter referred to as the first method for preparing the thin film) includes the steps of: depositing a dispersion comprising a first metal oxide as described above to obtain a first film layer; and contacting the first film layer with a first solution comprising a metal-organic compound as described above, followed by a first drying treatment to obtain the thin film. By contacting the first film layer with the first solution, the metal-organic compound permeates into the first film layer. The metal ions in the metal-organic compound can attract oxygen atoms of the first metal oxide in the first film layer to fill metal vacancies, and a large number of carbonyl groups in the metal-organic compound can fill oxygen vacancies in a coordinated manner, thereby improving the performance stability of the thin film.

[0073] Specifically, the deposition method of the composition (including solvent) or 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.

[0074] The drying method of the composition (including solvent) or 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 may be, for example, 60°C to 200°C.

[0075] To further improve the performance stability of the thin film, in some embodiments of this application, after the deposited composition is dried to form a film and before the step of obtaining the thin film, the thin film preparation method further includes the steps of: drying the deposited composition to form a second film layer, contacting the second film layer with a second solution, the second solution including the organometallic compound as described above, and then performing a second drying treatment. The selection range of the solvent for the second solution refers to the description of solvents above; an example solvent for the second solution is ethanol. The contact method between the second film layer and the second solution includes, but is not limited to, one or more of spin coating, inkjet printing, blade coating, dip coating, immersion coating, spraying, roller coating, casting, slot coating, and strip coating. The concentration of the organometallic compound in the second solution is, for example, 0.1 mg / mL to 5 mg / mL, and the contact time between the second film layer and the second solution is, for example, 1 min to 10 min. The first solution and the second solution can be completely identical.

[0076] Furthermore, in some embodiments of this application, after the step of contacting the second film layer with the second solution and before the step of the second drying treatment, the method for preparing the film further includes the step of washing to remove the second solution from the second film layer.

[0077] In order to ensure that the water content in the obtained film is within a suitable range, after the second drying treatment step and before the step of obtaining the film, the film preparation method further includes the step of placing the film obtained after the second drying treatment in an inert gas atmosphere with a relative humidity of 55% to 60% for 10 min to 30 min. The inert gas includes, but is not limited to, one or more of nitrogen, argon, helium, neon, krypton and xenon.

[0078] In the second method for preparing the thin film, the selection range for the dispersion medium of the dispersion and the solvent of the first solution is the same as described above regarding solvents. Examples of the dispersion medium and the solvent of the first solution are ethanol. The contact method between the first film layer and the first solution includes, but is not limited to, one or more of spin coating, inkjet printing, blade coating, dip coating, immersion coating, spray coating, roller coating, casting, slot coating, and strip coating. The concentration of the organometallic compound in the first solution is, for example, 0.1 mg / mL to 5 mg / mL, and the contact time between the first film layer and the first solution is, for example, 1 min to 10 min.

[0079] In some embodiments of this application, after the first drying process and before the step of obtaining the film, the method for preparing the film further includes the step of washing to remove the first solution from the first film layer.

[0080] Furthermore, in order to ensure that the water content in the obtained film is within a suitable range, after the first drying treatment step and before the step of obtaining the film, the film preparation method further includes the step of placing the film layer obtained after the first drying treatment in an inert gas atmosphere with a relative humidity of 55% to 60% for 10 min to 30 min.

[0081] This application also provides an optoelectronic device, which includes, but is not limited to, light-emitting devices, photovoltaic cells, or photodetectors, such as... Figure 1 As shown, the light-emitting 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 any of the compositions described above (excluding solvents), and / or at least one of the multiple functional layers includes any of the thin films described above, and / or at least one of the multiple functional layers is prepared by any of the thin film preparation methods described above, which can improve the photoelectric performance, device lifetime and performance stability of the light-emitting device 10.

[0082] 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 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), magnesium-doped zinc oxide (MZO), TiO2, SnO2, ZnO, and In2O3.

[0083] 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.

[0084] In some embodiments of this application, see further reference. Figure 1 The multiple functional layers include an electronic functional layer 104, the material of which includes any of the compositions described above (excluding solvents), and / or the electronic functional layer 104 includes any of the thin films described above, and / or the electronic functional layer 104 is prepared using any of the thin film preparation methods described above, wherein the first metal oxide is an N-type metal oxide as described above; or, the material of the electronic functional layer 104 includes an N-type metal oxide as described above.

[0085] The electronic functional layer 104 can be a single-layer or multi-layer structure, and its thickness is, for example, 10 nm to 100 nm. When the electronic functional layer 104 is a multi-layer structure, it may include 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.

[0086] It should be noted that the electronic functional layer 104 is generally prepared using a solution method. As mentioned earlier, changes in the surface adsorbed water content will affect ZnO or Zn (1-x) Mg x The performance stability of O. In conventional light-emitting devices, when the material of the electronic functional layer is ZnO and / or Zn (1-x) Mg x At O, with the electronic functional layer containing ZnO and / or Zn(1-x) Mg x The desorption or escape of adsorbed water from the O surface gradually weakens or eliminates the positive aging effect of the light-emitting device, thus compromising its high efficiency and long lifespan. To improve the light-emitting performance of the device, it is necessary to ensure that ZnO and / or ZnO in the electronic functional layer... (1-x) Mg x The content of adsorbed water on the O surface is maintained within a suitable range. In some embodiments of this application, organometallic compounds (e.g., zinc naphthate) are used to control the adsorption of water on ZnO and / or ZnO. (1-x) Mg x Modification of O can enable ZnO and / or ZnO in electronic functional layer 104 to be modified. (1-x) Mg x O forms fixed chemisorption sites for water molecules, allowing ZnO and / or ZnO to adsorb onto them. (1-x) Mg x Maintaining the surface adsorbed water content of O within a suitable range enhances the stability of electron transport.

[0087] In some embodiments of this application, multiple functional layers include a hole functional layer 105. For the light-emitting device 10, which includes an electronic functional layer 104, please refer to [the relevant documentation]. Figure 1 A hole functional layer 105 is disposed between the electron functional layer 104 and the anode 101. The material of the hole functional layer 105 includes any of the compositions described above (excluding solvents), and / or the hole functional layer 105 includes any of the thin films described above, and / or the hole functional layer 105 is prepared using any of the thin film preparation methods described above, wherein the first metal oxide is a p-type metal oxide as described above; or, 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.

[0088] 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).

[0089] The first inorganic compound material includes, but is not limited to, one or more of graphene, C60, nickel oxide, molybdenum oxide, tungsten oxide, vanadium oxide, p-type gallium nitride, chromium oxide, copper oxide, copper sulfide, molybdenum sulfide, and tungsten sulfide.

[0090] The second inorganic compound material includes one or more doped first compounds. The host material of the doped first compound is selected from graphene, C60, nickel oxide (e.g., NiO), molybdenum oxide (e.g., MoO3), tungsten oxide (e.g., WO3), vanadium oxide (e.g., V2O5), p-type gallium nitride, chromium oxide (e.g., Cr2O3), copper oxide (e.g., CuO or Cu2O), copper sulfide (e.g., CuS), molybdenum sulfide (e.g., MoS2), or tungsten sulfide (e.g., WS2). The doping element of the doped first compound is selected from one or more of nickel, molybdenum, tungsten, vanadium, chromium, copper, 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 second compound.

[0091] The hole functional layer 105 can be a single-layer or multi-layer structure, and the thickness of the hole functional layer 105 is, for example, 10 nm to 100 nm. Further reference is made to some embodiments of this application. Figure 1 The hole functional layer 105 includes a hole injection layer 1051 and a hole transport layer 1052 stacked together. The hole injection layer 1051 is closer to the anode 101 than the hole transport layer 1052. The material of at least one of the hole injection layer 1051 and the hole transport layer 1052 includes any of the compositions described above (excluding solvents), and / or at least one of the hole injection layer 1051 and the hole transport layer 1052 includes any of the thin films described above, and / or at least one of the hole injection layer 1051 and the hole transport layer 1052 is prepared using any of the thin film preparation methods described above.

[0092] In some embodiments of this application, multiple functional layers include a light-emitting layer 103. For the light-emitting device 10, which includes an electronic functional layer 104 and a hole functional layer 105, please refer to [the relevant documentation]. Figure 1The light-emitting layer 103 is disposed between the hole functional layer 105 and the electron functional layer 104. 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.

[0093] 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.

[0094] 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.

[0095] 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.

[0096] 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 - .

[0097] 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 - .

[0098] 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+ Fe2+ 、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.

[0099] 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 light-emitting performance of the light-emitting 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 aromatic phosphate ligands and halogen ligands.

[0100] 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. 30Thiol 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.

[0101] In some embodiments of this application, see further reference. Figure 1 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 includes a hole injection layer 1051 and a hole transport layer 1052 stacked sequentially. The hole injection layer 1051 is closer to the anode 101 than the hole transport layer 1052. The electron functional layer 104 is an electron transport layer.

[0102] It is understood that the light-emitting device 10 may also include a substrate, which is disposed on the side of the anode 101 away from the multiple functional layers or 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.

[0103] This application also provides a method for fabricating a light-emitting device, which can be used to fabricate any of the light-emitting devices described above. The method for fabricating the light-emitting device includes the following steps:

[0104] S1. Provide a first electrode, and form multiple functional layers on one side of the first electrode;

[0105] S2. A second electrode is formed on the side of the multiple functional layers away from the first electrode.

[0106] In this process, at least one of the multiple functional layers is prepared using any of the thin film preparation methods described above.

[0107] 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, and the first metal oxide in the composition includes N-type metal oxides as described above.

[0108] In some embodiments of this application, multiple functional layers include a hole functional layer, an electron functional layer is prepared using any of the thin film preparation methods described above, and the first metal oxide in the composition includes a p-type metal oxide as described above.

[0109] 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.

[0110] 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.

[0111] It should be noted that the fabrication methods for each functional layer in the light-emitting device 10 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. After fabricating each functional layer of the light-emitting device, an encapsulation process is required. Encapsulation can be performed using common machine encapsulation or manual encapsulation. In the encapsulation environment, the oxygen and water content are both below 0.1 ppm to ensure the stability of the light-emitting device. Specifically, the encapsulation material used to form the encapsulation layer is selected from one or more of UV adhesive, metal film and glass adhesive. For example, the encapsulation material is acrylic resin or epoxy resin.

[0112] This application also provides an electronic device, which includes a display panel comprising a plurality of pixel units arranged in an array, each pixel unit including a light-emitting device as described in any of the preceding descriptions. The electronic device can be, for example, any electronic product with display functionality, 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.

[0113] 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.

[0114] The preparation method of nano-ZnO includes the following steps: 10 mmol of zinc acetate dihydrate is added to 20 mL of ethanol and completely dissolved to obtain a zinc acetate solution with a concentration of 0.5 mol / L. Then, at room temperature, a solution containing sodium hydroxide (sodium hydroxide concentration of 0.6 mol / L, solvent of ethanol) is added dropwise to the zinc acetate solution until OH... - With Zn 2+ The molar ratio was 1.1:1, the pH was adjusted to 12, and the mixture was stirred at room temperature for 1 hour to obtain the reaction product. Ethyl acetate was added to the reaction product to precipitate the product. After the precipitate stopped precipitating, the addition of ethyl acetate was stopped. The mixture was centrifuged at 7800 r / min for 3 min to collect the first precipitate. The first precipitate was then dispersed in n-octane and centrifuged at 7800 r / min for 3 min. The second precipitate collected was nano-ZnO.

[0115] Nano Zn 0.85 Mg 0.15The preparation method of O includes the following steps: 8.5 mmol of zinc acetate dihydrate and 1.5 mmol of magnesium acetate are added to 20 mL of ethanol and completely dissolved to obtain a metal precursor solution. A solution containing sodium hydroxide (0.6 mol / L concentration, ethanol solvent) is added dropwise to the metal 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 room temperature for 1 hour to obtain the reaction product. Ethyl acetate was added to the reaction product to precipitate the product. After the precipitation stopped, the addition of ethyl acetate was stopped, and the mixture was centrifuged at 7800 r / min for 3 min to collect the third precipitate. The third precipitate was then dispersed in n-octane and centrifuged at 7800 r / min for 3 min to collect the fourth precipitate, which is the nano-Zn. 0.85 Mg 0.15 O.

[0116] Material Example 1

[0117] This embodiment provides a thin film and its preparation method, the thin film comprising nano-ZnO and zinc naphthenate (CAS No. 12001-85-3).

[0118] The method for preparing the thin film includes the following steps:

[0119] S1.1. Nano ZnO is dispersed in ethanol to prepare a nano ZnO dispersion with a concentration of 30 mg / mL.

[0120] S1.2. Provide a substrate, and spin-coat a nano-ZnO dispersion onto one side of the substrate under a nitrogen atmosphere at room temperature and pressure. Then, place it under a nitrogen atmosphere at 100°C for constant temperature heat treatment for 10 minutes to obtain a first film layer with a thickness of 50nm.

[0121] S1.3. Immerse the first membrane layer in a zinc naphthenate solution (dispersion medium is ethanol, and the concentration of zinc naphthenate is 2.5 mg / mL) for 5 min, then remove the zinc naphthenate solution from the first membrane layer, dry it, and expose it to a nitrogen environment with a relative humidity (water) of 58% for 20 min to obtain the film.

[0122] Material Example 2

[0123] This embodiment provides a thin film and its preparation method. Compared with the preparation method of the thin film in Material Example 1, the difference in the preparation method of the thin film in this embodiment is that step S1.3 is replaced by "immersing the first film layer in a zinc naphthenate solution (dispersion medium is ethanol, and the concentration of zinc naphthenate is 2.5 mg / mL) for 5 min, then removing the zinc naphthenate solution on the first film layer, and drying to obtain the thin film".

[0124] Material Example 3

[0125] This embodiment provides a thin film and its preparation method. Compared with the preparation method of the thin film in Material Example 1, the difference in the preparation method of the thin film in this embodiment is that step S1.3 is replaced by "immersing the first film layer in a zinc benzoate solution (dispersion medium is ethanol, and the concentration of zinc benzoate is 2.5 mg / mL) for 5 min, then removing the zinc benzoate solution on the first film layer, drying it, and then exposing it to a nitrogen environment with a relative humidity (water) of 58% for 20 min to obtain the thin film".

[0126] Material Example 4

[0127] This embodiment provides a thin film and its preparation method. Compared with the preparation method of the thin film in Material Example 1, the difference in the preparation method of the thin film in this embodiment is that step S1.3 is replaced by "immersing the first film layer in a zinc salicylate solution (dispersion medium is ethanol, and the concentration of zinc salicylate is 2.5 mg / mL) for 5 min, then removing the zinc salicylate solution on the first film layer, drying it, and then exposing it to a nitrogen environment with a relative humidity (water) of 58% for 20 min to obtain the thin film".

[0128] Material Example 5

[0129] This embodiment provides a thin film and its preparation method. Compared with the preparation method of the thin film in Material Example 1, the difference in the preparation method of the thin film in this embodiment is that step S1.3 is replaced by "immersing the first film layer in a zinc pyridine carboxylate solution (dispersion medium is ethanol, and the concentration of zinc pyridine carboxylate is 2.5 mg / mL) for 5 min, then removing the zinc pyridine carboxylate solution on the first film layer, drying it, and then exposing it to a nitrogen environment with a relative humidity (water) of 58% for 20 min to obtain the thin film".

[0130] Material Example 6

[0131] This embodiment provides a thin film and its preparation method. Compared with the preparation method of the thin film in Material Example 1, the difference in the preparation method of the thin film in this embodiment is that step S1.3 is replaced by "immersing the first film layer in a zinc stearate solution (dispersion medium is ethanol, and the concentration of zinc stearate is 2.5 mg / mL) for 5 min, then removing the zinc stearate solution on the first film layer, drying it, and then exposing it to a nitrogen environment with a relative humidity (water) of 58% for 20 min to obtain the thin film".

[0132] Material Example 7

[0133] This embodiment provides a thin film and its preparation method. Compared with the preparation method of the thin film in Material Example 1, the difference in the preparation method of the thin film in this embodiment is that step S1.3 is replaced by "immersing the first film layer in a zinc benzenesulfonate solution (dispersion medium is ethanol, and the concentration of zinc benzenesulfonate is 2.5 mg / mL) for 5 min, then removing the zinc benzenesulfonate solution on the first film layer, drying it, and then exposing it to a nitrogen environment with a relative humidity (water) of 58% for 20 min to obtain the thin film".

[0134] Material Example 8

[0135] This embodiment provides a thin film and its preparation method, wherein the thin film comprises nano-ZnO and zinc naphthate.

[0136] The method for preparing the thin film includes the following steps:

[0137] S2.1. Nano ZnO is dispersed in ethanol to prepare a nano ZnO dispersion with a concentration of 30 mg / mL. Then, zinc naphthenate is dispersed in the nano ZnO dispersion at a mass ratio of 1:0.02 to nano ZnO to obtain the composition.

[0138] S2.2. Provide a substrate, spin-coat a composition on one side of the substrate under a nitrogen atmosphere at room temperature and pressure, and then place it under a nitrogen atmosphere at 100°C for 10 minutes to obtain a thin film with a thickness of 50nm.

[0139] Material Example 9

[0140] This embodiment provides a thin film and its preparation method. Compared with the preparation method of the thin film in Material Example 8, the difference in the preparation method of the thin film in this embodiment is that the step S2.1, "dispersing zinc naphthenate in the nano ZnO dispersion at a mass ratio of 1:0.02" is replaced with "dispersing zinc naphthenate in the nano ZnO dispersion at a mass ratio of 1:0.001".

[0141] Material Example 10

[0142] This embodiment provides a thin film and its preparation method. Compared with the preparation method of the thin film in Material Example 8, the difference in the preparation method of the thin film in this embodiment is that the step S2.1, "dispersing zinc naphthenate in the nano ZnO dispersion at a mass ratio of 1:0.02 of nano ZnO to zinc naphthenate", is replaced with "dispersing zinc naphthenate in the nano ZnO dispersion at a mass ratio of 1:0.05 of nano ZnO to zinc naphthenate".

[0143] Material Example 11

[0144] This embodiment provides a thin film and its preparation method, wherein the thin film comprises nano-ZnO and zinc naphthate.

[0145] The method for preparing the thin film includes the following steps:

[0146] S3.1, Same as step S2.1;

[0147] S3.2. Provide a substrate, spin-coat a composition on one side of the substrate under a nitrogen atmosphere at room temperature and pressure, and then place it under a nitrogen atmosphere at 100°C for constant temperature heat treatment for 10 minutes to obtain a second film layer with a thickness of 50nm.

[0148] S3.3 Immerse the second membrane layer in a zinc naphthenate solution (dispersion medium is ethanol, zinc naphthenate concentration is 2.5 mg / mL) for 5 min, then remove the zinc naphthenate solution from the first membrane layer, dry it, and expose it to a nitrogen environment with a relative humidity (water) of 58% for 20 min to obtain the film.

[0149] Material Example 12

[0150] This embodiment provides a thin film and its preparation method, the thin film comprising nano-Zn 0.85 Mg 0.15 O and zinc naphthate.

[0151] Compared to the thin film preparation method in Material Example 1, the difference in the thin film preparation method in this example is that "nano ZnO" in steps S1.1 and S1.2 is completely replaced with "nano Zn". 0.85 Mg 0.15 O".

[0152] Material Example 13

[0153] This embodiment provides a thin film and its preparation method, the thin film comprising nano-Zn 0.85 Mg 0.15 O and zinc naphthate.

[0154] Compared to the thin film preparation method in Material Example 11, the difference in the thin film preparation method in this example is that "nano ZnO" in step S3.1 is replaced with "nano Zn". 0.85 Mg 0.15 O".

[0155] Material Example 14

[0156] This embodiment provides a thin film and its preparation method, wherein the thin film comprises nano-nickel oxide and nickel naphthenate.

[0157] The method for preparing the thin film includes the following steps:

[0158] S4.1. Nano nickel oxide (CAS No. 1313-99-1) was dispersed in ethanol to prepare a nano nickel oxide dispersion with a concentration of 30 mg / mL.

[0159] S4.2. Provide a substrate, and spin-coat a nano-nickel oxide dispersion onto one side of the substrate under a nitrogen atmosphere at room temperature and pressure. Then, place it under a nitrogen atmosphere at 150°C for constant temperature heat treatment for 30 minutes to obtain a first film layer with a thickness of 50nm.

[0160] S4.3. Immerse the first membrane layer in a nickel naphthenate solution (dispersion medium is ethanol, and the concentration of nickel naphthenate is 2.5 mg / mL) for 5 min, then remove the nickel naphthenate solution from the first membrane layer, dry it, and expose it to a nitrogen environment with a relative humidity (water) of 58% for 20 min to obtain the membrane.

[0161] Material Example 15

[0162] This embodiment provides a thin film and its preparation method, wherein the thin film comprises nano-nickel oxide and nickel naphthenate.

[0163] The method for preparing the thin film includes the following steps:

[0164] S5.1. Disperse nano-nickel oxide in ethanol to prepare a nano-nickel oxide dispersion with a concentration of 30 mg / mL. Then, disperse nickel naphthenate in the nano-nickel oxide dispersion at a mass ratio of 1:0.02 to obtain the composition.

[0165] S5.2. Provide a substrate, spin-coat a composition on one side of the substrate under a nitrogen atmosphere at room temperature and pressure, and then place it under a nitrogen atmosphere at 150°C for 30 minutes to obtain a second film layer with a thickness of 50nm.

[0166] S5.3. Immerse the second membrane layer in a nickel naphthenate solution (dispersion medium is ethanol, and the concentration of nickel naphthenate is 2.5 mg / mL) for 5 min, then remove the nickel naphthenate solution from the second membrane layer, dry it, and expose it to a nitrogen environment with a relative humidity (water) of 58% for 20 min to obtain the membrane.

[0167] Material Comparison Example 1

[0168] This comparative example provides a thin film and its preparation method, wherein the material of the thin film includes nano-ZnO.

[0169] The preparation method of the thin film in this comparative example includes the following steps: providing a substrate, spin-coating a nano-ZnO dispersion onto one side of the substrate under a nitrogen atmosphere at room temperature and pressure (the preparation method is referred to Material Example 1), and then placing it under a nitrogen atmosphere at 100°C for constant temperature heat treatment for 10 min to obtain a thin film with a thickness of 50 nm.

[0170] Material Comparison Example 2

[0171] This comparative example provides a thin film and its preparation method, wherein the material of the thin film includes nano-Zn. 0.85 Mg 0.15 O.

[0172] The thin film preparation method in this comparative example includes the following steps: providing a substrate, and spin-coating nano-Zn onto one side of the substrate under a nitrogen atmosphere at room temperature and pressure. 0.85 Mg 0.15 The O dispersion (preparation method refers to Material Example 12) was then subjected to constant temperature heat treatment at 100°C under a nitrogen atmosphere for 10 min to obtain a film with a thickness of 50 nm.

[0173] Material Comparison Example 3

[0174] This comparative example provides a thin film and a method for preparing the same, wherein the material of the thin film includes nano-nickel oxide.

[0175] The preparation method of the thin film in this comparative example includes the following steps: providing a substrate, spin-coating a nano-nickel oxide dispersion onto one side of the substrate under a nitrogen atmosphere at room temperature and pressure (preparation method refers to Material Example 14), and then heat-treating it at a constant temperature of 150°C under a nitrogen atmosphere for 30 min to obtain a thin film with a thickness of 50 nm.

[0176] Device Example 1

[0177] This embodiment provides a light-emitting device and its fabrication method. The light-emitting device is a quantum dot light-emitting diode with a positive-position structure, such as... Figure 1 As shown, the light-emitting 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 sequentially, 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 light-emitting device 10 is 3.14 mm². 2 .

[0178] The materials and thicknesses of each layer in the light-emitting device 10 are as follows:

[0179] The anode 101 is made of ITO and has a thickness of 120 nm.

[0180] The cathode 102 is made of Ag and has a thickness of 60 nm.

[0181] The material of the light-emitting layer 103 includes CdSeS (core) / ZnS (shell) quantum dots, the light emission color is green, and the thickness of the light-emitting layer 103 is 70nm;

[0182] The electronic functional layer 104 is the thin film in Material Example 1;

[0183] The hole injection layer 1051 is made of PEDOT:PSS and has a thickness of 80 nm.

[0184] The hole transport layer 1052 is made of TFB material and has a thickness of 50 nm.

[0185] The fabrication method of the light-emitting device in this embodiment includes the following steps:

[0186] S10.1 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. After drying, perform ultraviolet-ozone surface treatment for 20 min to obtain a substrate containing an anode.

[0187] S10.2 Under normal temperature and pressure air environment, spin-coat PEDOT:PSS aqueous solution on one side of the anode, and then place it under nitrogen atmosphere at 150℃ for constant temperature heat treatment for 30 min to obtain hole injection layer.

[0188] S10.3 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.

[0189] S10.4 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.

[0190] S10.5, 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;

[0191] S10.6. 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 light-emitting device.

[0192] Device Examples 2-13

[0193] The structure of the light-emitting device in device embodiment n is basically the same as that in device embodiment 1. The main difference is that the electronic functional layer is different. In device embodiment n, the electronic functional layer is the thin film in material embodiment n, where n is an integer from 2 to 13. For example, in device embodiment 2, the electronic functional layer is the thin film in material embodiment n, and so on.

[0194] Compared to the fabrication method of the light-emitting device in Device Example 1, the difference in the fabrication method of the light-emitting device in Device Example n is that step S10.5 is replaced with "forming an electronic functional layer on the side of the light-emitting layer away from the hole transport layer by referring to the thin film fabrication method in Material Example n".

[0195] Device Example 14

[0196] This embodiment provides a light-emitting device. Compared with the light-emitting device in Device Embodiment 1, the difference of the light-emitting device in this embodiment is that the hole transport layer is the thin film in Material Embodiment 14, and the electronic functional layer is the thin film in Material Comparative Example 1.

[0197] Device Example 15

[0198] This embodiment provides a light-emitting device. Compared with the light-emitting device in Device Embodiment 1, the difference of the light-emitting device in this embodiment is that the hole transport layer is the thin film in Material Embodiment 15, and the electronic functional layer is the thin film in Material Comparative Example 1.

[0199] Device Example 16

[0200] This embodiment provides a light-emitting device. Compared with the light-emitting device in Device Embodiment 1, the difference of the light-emitting device in this embodiment is that the hole transport layer is the thin film in Material Embodiment 15.

[0201] Device Example 17

[0202] This embodiment provides a light-emitting device. Compared with the light-emitting device in device embodiment 1, the difference of the light-emitting device in this embodiment is that the hole transport layer is the thin film in material comparison example 3.

[0203] Device Comparison Example 1

[0204] This comparative example provides a light-emitting device. Compared with the light-emitting device in Device Example 1, the difference of the light-emitting device in this comparative example is that the electronic functional layer is the thin film in Material Comparative Example 1.

[0205] Device Comparison Example 2

[0206] This comparative example provides a light-emitting device. Compared with the light-emitting device in Device Example 1, the difference of the light-emitting device in this comparative example is that the electronic functional layer is the thin film in Material Comparative Example 1, and the hole transport layer is the thin film in Material Comparative Example 3.

[0207] Experimental Example 1

[0208] The performance of the films in Material Examples 1 to 15 and Material Comparative Examples 1 to 3 was tested. Specifically, the oxygen vacancy content (W2,%) and metal vacancy content (W3,%) of each film were detected by X-ray photoelectron spectroscopy (XPS).

[0209] The method for detecting oxygen vacancy content includes the following steps: In the thin film, XPS is used to detect the content of each form of oxygen in the thin film. The forms of oxygen in the thin film include lattice oxygen, oxygen vacancies and adsorbed oxygen. Then, the proportion of oxygen vacancies in all forms of oxygen is calculated by peak segmentation.

[0210] The method for detecting metal vacancy content includes the following steps: in the thin film, XPS is used to detect the content of each form of metal element in the thin film, and then the proportion of metal vacancies in all forms of oxygen is calculated by peak segmentation.

[0211] The test results are shown in Table 1 below:

[0212] Table 1

[0213]

[0214]

[0215] As shown in Table 1, compared with the film in Material Comparative Example 1, the films in Material Examples 1 to 11 have lower oxygen vacancy content and metal vacancy content; compared with the film in Material Comparative Example 2, the films in Material Examples 12 and 13 have lower oxygen vacancy content and metal vacancy content; compared with the film in Material Comparative Example 3, the films in Material Examples 14 and 15 have lower oxygen vacancy content and metal vacancy content. This indicates that organometallic compounds can passivate the defect states of the first metal oxide, reduce the number of defect states of the first metal oxide, and thus improve the performance stability of the first metal oxide.

[0216] Experiment Example 2

[0217] The performance of the light-emitting devices in Device Examples 1 to 17, Device Comparative Example 1 and Device Comparative Example 2 after 1 hour of encapsulation was tested. The performance tests were conducted in an environment with a temperature of 25°C and a relative humidity of 40%.

[0218] The photoelectric performance was tested using a Fostec FPD optical characteristic measurement system (comprising 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 test cassette, and a data acquisition system). The system acquired parameters such as the turn-on voltage, current, brightness, and emission spectrum of each light-emitting device. Key parameters such as external quantum efficiency and power efficiency were then calculated, and the maximum brightness (L) was obtained. max, cd / m 2 ).

[0219] The method for detecting current efficiency includes the following steps: setting the luminous area to 3.14 mm². 2 The luminance values ​​of the light-emitting device are intermittently collected within a voltage range of 0V to 8V, with a collection every 0.2V. The current efficiency of the light-emitting device under that collection condition is obtained by dividing the luminance value collected each time by the corresponding current density. The maximum current efficiency (CE) is then obtained. max ,cd / A).

[0220] The device lifetime testing method includes the following steps: Under constant current (2mA) driving, electroluminescence lifetime analysis is performed on each light-emitting device using lifetime testing equipment. The time (T95,h) required for each light-emitting device to decay from its maximum brightness to 95% is recorded. Then, the device lifetime (T95@1000nit,h) at a brightness of 1000nit is obtained through the extended exponential decay brightness decay fitting formula. The specific calculation formula is as follows:

[0221]

[0222] Among them, 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 It is 1000 nits, and A is the acceleration factor with a value of 1.7.

[0223] In addition, the current efficiency fluctuation rate (V,%) of each light-emitting device was tested. The testing method included the following steps: the light-emitting device was operated at 1000 nits for 1 hour, then turned off for 1 minute and restarted. The current efficiency of the light-emitting device before being turned off was C.E1, and the current efficiency of the light-emitting device after being restarted was C.E2. The current efficiency fluctuation rate (V,%) = |1-C.E2 / C.E1|×100%.

[0224] The performance test results of each light-emitting device are shown in Table 2 below:

[0225] Table 2

[0226]

[0227] As shown in Table 2, compared with the light-emitting devices in the device comparison examples, the light-emitting devices in Device Examples 1 to 17 have better light-emitting performance, device lifespan, and performance stability.

[0228] This demonstrates that using the composition of the embodiments of this application to prepare the electronic functional layer, and that the first metal oxide in the composition is an N-type metal oxide, can improve the performance stability of the electronic functional layer, thereby improving the electron transport stability of the light-emitting device. Further, the organometallic compound in the composition is zinc naphthate, and the first metal oxide is ZnO and Zn (1-x) Mg x One or more of the following can further improve the performance stability of light-emitting devices: zinc naphthate is adsorbed onto ZnO or Zn (1-x) Mg x A continuous thin film can form on the surface of O, reducing the solid-liquid interfacial energy and contact angle, which can promote the formation of ZnO or Zn (1-x) Mg x O allows for faster and more uniform surface drainage, thus enabling the removal of ZnO or Zn (1-x) Mg x Maintaining the surface adsorbed water content of O within a suitable range further enhances the performance of ZnO or ZnO. (1-x) Mg x O's performance stability.

[0229] The hole functional layer is prepared using the composition of the embodiments of this application, and the first metal oxide in the composition is a P-type metal oxide, which can improve the performance stability of the hole functional layer, thereby improving the hole transport stability of the light-emitting device, and further improving the light-emitting performance, device life, operational stability and reliability of the light-emitting device.

[0230] The foregoing has provided a detailed description of a composition, thin film, preparation method thereof, and light-emitting device provided in the embodiments of this application. Specific examples have been used to illustrate the principles and implementation methods of this application. The descriptions of the above embodiments are merely for the purpose of helping to understand the technical solutions and core ideas of this application. Those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features; and these modifications or substitutions do not cause the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of this application.

Claims

1. A composition, characterized in that, The composition comprises a first metal oxide and an organometallic compound, wherein the metal element in the first metal oxide comprises a first metal element, and the metal element in the organometallic compound comprises a second metal element, and the organometallic compound comprises a compound with the structure shown in general formula (I) below: A m+ (R1-X - ) n (Ⅰ); In general formula (Ⅰ), A m+ R1-X is the m-valence ion of the second metallic element. - Selected from R1 is selected from unsubstituted or R1-substituted. a Substituted C1–C30 aliphatic chain hydrocarbon groups, unsubstituted or with at least one R a Substituted C1–C30 aliphatic chain hydroxyl groups, unsubstituted or with at least one R a The substituted aliphatic cyclic hydrocarbon group having 3 to 30 substituted ring atoms, or the unsubstituted or substituted group having at least one R group. a The substituted aliphatic heterocyclic hydrocarbon group having 3 to 30 ring atoms, is unsubstituted or has been substituted with at least one R group. a The substituted aryl group has 6 to 30 ring atoms, is unsubstituted, or is substituted with at least one R. a The substituted heteroaryl group having 5 to 30 ring atoms, or a combination of the aforementioned groups; R a Each time it appears, it is independently selected from -H, -D, C1-C20 aliphatic chain hydrocarbon groups, C1-C20 aliphatic chain hydroxyl 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, and heteroaryl groups with 5-20 ring atoms. Hydroxyl, halogen, aldehyde, mercapto, cyano, or combinations thereof; m and n are each independently selected from integers from 1 to 6.

2. The composition according to claim 1, characterized in that, The first metallic element and the second metallic element are the same; and / or, In the composition, at least a portion of the oxygen atoms in the organometallic compound fill at least a portion of the oxygen vacancies in the first metal oxide, and / or at least a portion of the A atoms in the organometallic compound... m+ Filling at least a portion of the metal vacancies in the first metal oxide; and / or, The first metal oxide is in the form of nanoparticles, and the average particle size of the first metal oxide is 2 nm to 100 nm; and / or, The first metal oxide is an N-type metal oxide or a P-type metal oxide; and / or, The first metallic element and the second metallic element are each independently selected from Group IA, Group IIA, Group IIIA, Group IVA, Group VA, or transition metal elements; and / or, R1 is selected from unsubstituted or R1-dependent molecules. a Substituted C1–C20 aliphatic chain hydrocarbon groups, unsubstituted or with at least one R a Substituted C1–C20 aliphatic chain hydroxyl groups, unsubstituted or substituted with at least one R a The substituted aliphatic cyclic hydrocarbon group having 3 to 20 substituted ring atoms, or the unsubstituted or substituted group having at least one R group. a The substituted aliphatic heterocyclic hydrocarbon group having 6 to 20 ring atoms, is unsubstituted or has been substituted with at least one R group. a The substituted aryl group has 6 to 20 ring atoms, is unsubstituted, or is substituted with at least one R. a The substituted heteroaryl group has 6 to 20 ring atoms, or a combination of these groups; R a Each occurrence is independently selected from C1–C20 aliphatic chain hydrocarbon groups, C1–C20 aliphatic chain alkyl groups, and hydroxyl groups, or combinations of these groups; and / or, In the composition, the mass ratio of the first metal oxide to the organometallic compound is 1:(0.001 to 0.05).

3. The composition according to claim 2, characterized in that, The first metallic element and the second metallic element are each independently selected from Zn, Ti, Sn, Ba, Ta, Al, Zr, Mg, Ca, Ga, Li, Y, Ni, Mo, W, V, Cr, Cu, or Hf; and / or, The first metal oxide is an N-type metal oxide, including 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, wherein 0 < x ≤ 0.5; or, the first metal oxide is a p-type metal oxide, said p-type metal oxide including one or more of nickel oxide, copper oxide, molybdenum oxide, chromium oxide, tungsten oxide, vanadium oxide, and hafnium oxide; and / or, R1-COO - It has a structure that can be represented by any of the following structural formulas: Where x1 and x2 are independently selected from positive integers from 0 to 10; R b and R c Each group is independently selected from -H, -D, hydroxyl, and aliphatic chain hydrocarbon groups from C1 to C20.

4. The composition according to claim 3, characterized in that, The first metal oxide includes ZnO and Zn (1-x) Mg x O, Zn (1-x) Al x O, Zn (1-x) Li x O and Zn (1-x) Ti x One or more of O, wherein the organometallic compound includes one or more of zinc naphthate, zinc benzoate, zinc salicylate, zinc pyridinecarboxylate, zinc benzenesulfonate, zinc benzenesulfinate, and zinc p-toluenesulfonate; and / or, In the composition, the mass ratio of the first metal oxide to the organometallic compound is 1:(0.02 to 0.05).

5. The composition according to any one of claims 1 to 4, characterized in that, The composition further includes a solvent in which the first metal oxide and the organometallic compound are dispersed; optionally, the solvent includes one or more of alkanes, aromatic hydrocarbons, halogenated hydrocarbons, alcohols, ethers, ketones, esters, furans, pyridines, amides, and sulfones.

6. A thin film, characterized in that, The material of the film includes the composition as described in any one of claims 1 to 4, and / or the film is prepared using the composition as described in claim 5.

7. The thin film according to claim 6, characterized in that, The oxygen vacancy content in the film is 1.1% to 2%; and / or, The metal vacancy content in the thin film is 1.1% to 2%; and / or, The thickness of the film is 10 nm to 100 nm; optionally, the thickness of the film is 20 nm to 60 nm.

8. A method for preparing a thin film, characterized in that, The method for preparing the thin film includes the steps of: depositing the composition as described in claim 5, drying the deposited composition to form a film, and obtaining the thin film; Alternatively, the method for preparing the thin film may include the following steps: A deposition dispersion comprising a first metal oxide as described in any one of claims 1 to 4 is dried to form a film, thereby obtaining a first film layer. as well as The first film layer is brought into contact with a first solution, the first solution comprising the organometallic compound as described in any one of claims 1 to 4, and then subjected to a first drying process to obtain the film.

9. The method for preparing the thin film according to claim 8, characterized in that, After the deposited composition is dried to form a film and before the step of obtaining the thin film, the method for preparing the thin film further includes the steps of: drying the deposited composition to form a second film layer, contacting the second film layer with a second solution, the second solution comprising the organometallic compound as described in any one of claims 1 to 4, and then performing a second drying treatment; Optionally, after the step of contacting the second membrane layer with the second solution and before the step of the second drying treatment, the method for preparing the thin film further includes the step of: washing to remove the second solution from the second membrane layer; and / or, after the step of the second drying treatment and before the step of obtaining the thin film, the method for preparing the thin film further includes the step of: placing the membrane layer obtained after the second drying treatment in an inert gas atmosphere with a relative humidity of 55% to 60% for 10 min to 30 min; And / or, after the first drying treatment step and before the step of obtaining the film, the method for preparing the film further includes the step of: washing to remove the first solution from the first film layer; and / or, after the first drying treatment step and before the step of obtaining the film, the method for preparing the film further includes the step of: placing the film layer obtained after the first drying treatment in an inert gas atmosphere with a relative humidity of 55% to 60% for 10 min to 30 min.

10. A light-emitting 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 composition as described in any one of claims 1 to 4, and / or at least one of the plurality of functional layers comprises a thin film as described in claim 6 or 7, and / or at least one of the plurality of functional layers is prepared using a thin film preparation method as described in claim 8 or 9.

11. The light-emitting device according to claim 10, characterized in that, The plurality of functional layers include an electronic functional layer; the material of the electronic functional layer includes the composition as described in any one of claims 1 to 4, and / or the electronic functional layer includes a thin film as described in claim 6 or 7, and / or the electronic functional layer is prepared using the thin film preparation method as described in claim 8 or 9, wherein the first metal oxide is an N-type metal oxide; or, the material of the electronic functional layer includes an N-type metal oxide; and / or, The plurality of functional layers include a hole functional layer, the material of which includes the composition as described in any one of claims 1 to 4, and / or the hole functional layer includes the thin film as described in claim 6 or 7, and / or the hole functional layer is prepared by the method for preparing the thin film as described in claim 8 or 9, wherein the first metal oxide is a p-type metal oxide; or, the material of the hole functional layer includes one or more of an organic material, 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)-1,1' One or more of the following: -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, nickel oxide. The first inorganic compound material comprises one or more of the following: oxides of nickel, copper, molybdenum, chromium, tungsten, vanadium, hafnium, 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, oxides of nickel, copper, molybdenum, chromium, tungsten, vanadium, hafnium, copper sulfide, molybdenum sulfide, and tungsten sulfide; and / or, 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; 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, and DBP. Fluorescent materials, delayed fluorescence 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, 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.

12. The light-emitting device according to claim 11, characterized in that, The plurality of functional layers include the hole functional layer, the light-emitting layer and the electron functional layer stacked in sequence, wherein the hole functional layer is closer to the anode than the electron functional layer; The hole functional layer includes a hole injection layer and a hole transport layer stacked sequentially, wherein the hole injection layer is closer to the anode than the hole transport layer; The electronic functional layer is an electronic transport layer.

13. An electronic device, characterized in that, The electronic device includes a display panel, the display panel including a plurality of pixel units arranged in an array, each pixel unit including a light-emitting device as described in any one of claims 10 to 12.

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