Metal oxide nanoparticles, preparation method thereof, photoelectric device and display device

Abstract

The invention discloses a metal oxide nanoparticle and a preparation method thereof, a photoelectric device and a display device, and the preparation method comprises the following steps: providing a plurality of raw material components which comprise a metal salt, an organic amine, an alkali and a first solvent; mixing the plurality of raw material components, and carrying out a first reaction to obtain metal oxide nanoparticles; wherein the organic amine is an organic compound containing amino. According to the invention, the uniformity of the metal oxide is greatly improved, the size of the metal oxide is controllably improved, and the surface defects of the metal oxide are reduced.

Description

Technical Field

[0001] The present application relates to the field of displays, and in particular, to a metal oxide nanoparticle, a preparation method thereof, an optoelectronic device, and a display device. Background Art

[0002] Metal oxide nanoparticles refer to nanomaterials composed of one or more metal ions and oxygen ions. Metal oxide nanoparticles usually have a high surface area, good surface activity, and exhibit special properties in terms of magnetic, optical, and electronic properties, etc., thus making metal oxide nanoparticles have broad application prospects in the fields of photocatalysis, sensors, biomedicine, electronic devices, catalysts, etc.

[0003] Nowadays, the mainstream preparation methods of metal oxide nanoparticles are solution methods or sol-gel methods. However, metal oxides prepared by solution methods or sol-gel methods often have the problem of many surface defects. Summary of the Invention

[0004] In view of this, the present application provides a metal oxide nanoparticle, a preparation method thereof, an optoelectronic device, and a display device.

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

[0006] In a first aspect, the present application provides a preparation method of a metal oxide nanoparticle, including the following steps:

[0007] Provide a metal salt, an organic amine, a base, and a first solvent;

[0008] Mix the metal salt, the organic amine, the base, and the first solvent, and carry out a first reaction to obtain metal oxide nanoparticles.

[0009] Optionally, in some embodiments of the present application, the step of mixing the metal salt, the organic amine, and the base includes:

[0010] Mix the organic amine and the metal salt, and then add the base; or,

[0011] Mix the base, the organic amine, and the metal salt.

[0012] Optionally, in some embodiments of the present application, the ratio of the molar amount of the metal ion in the metal salt to the molar amount of the organic amine is 1:(10 - 30); and / or,

[0013] The temperature of the first reaction is 25 - 60°C; and / or,

[0014] The time of the first reaction is 0.5 - 6h; and / or,

[0015] The organic amine includes one or more of the compounds with the structural formula NR1R2R3, where R1, R2, and R3 are each independently selected from one or more combinations of hydrogen, deuterium, amino group, halogen, hydroxyl group, carboxyl group, nitro group, sulfonic acid group, aldehyde group, mercapto group, cyano group, unsubstituted or substituted C1-C20 hydrocarbon groups, unsubstituted or substituted C1-C20 hydrocarbon oxy groups, unsubstituted or substituted alicyclic hydrocarbon groups with 3 to 60 ring atoms, unsubstituted or substituted heterocyclic hydrocarbon groups with 3 to 60 ring atoms, unsubstituted or substituted aryl groups with 6 to 60 ring atoms, unsubstituted or substituted heteroaryl groups with 5 to 60 ring atoms, unsubstituted or substituted aryloxy groups with 6 to 60 ring atoms, and unsubstituted or substituted heteroaryloxy groups with 5 to 60 ring atoms; where the heteroatoms in the heterocyclic hydrocarbon group, the heteroaryl group, or the heteroaryloxy group are one or more of N, S, O, P, Si, and the number of heteroatoms is 1 to 20; each time the substituent appears, it is independently selected from one or more combinations of amino group, halogen, hydroxyl group, carboxyl group, nitro group, sulfonic acid group, aldehyde group, mercapto group, and cyano group.

[0016] Optionally, in some embodiments of the present application, the total number of carbon atoms contained in R1, R2, and R3 is 3 to 8; and / or,

[0017] Two of R1, R2, and R3 are selected from hydrogen; and / or,

[0018] R1, R2, and R3 are each independently selected from any one of hydrogen and unsubstituted hydrocarbon groups.

[0019] Optionally, in some embodiments of the present application, the organic amine includes one or more of n-propylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, and n-octylamine.

[0020] Optionally, in some embodiments of the present application, the metal salt includes at least one of zinc salt, titanium salt, tin salt, zirconium salt, aluminum salt, copper salt, molybdenum salt, nickel salt, gallium salt, cobalt salt, manganese salt, and iron salt; and / or,

[0021] The base includes one or more of metal hydroxides and alkylammonium hydroxides. The metal hydroxides include one or more of sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, and barium hydroxide. The alkylammonium hydroxides include one or more of tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrapropylammonium hydroxide; and / or,

[0022] The first solvent includes one or more of dimethyl sulfoxide, N,N-dimethylformamide, and alcohol solvents.

[0023] Optionally, in some embodiments of the present application, the ratio of the molar amount of metal ions in the metal salt to the molar amount of hydroxide ions in the base is 1:(1.5 - 3.0).

[0024] Optionally, in some embodiments of the present application, the preparation method further includes:

[0025] providing a second solvent and a ligand compound;

[0026] dispersing the metal oxide nanoparticles in the second solvent to obtain a mixed solution;

[0027] mixing the mixed solution and the ligand compound to carry out a second reaction to obtain metal oxide nanoparticles with halogen atoms connected to the surface.

[0028] Optionally, in some embodiments of the present application, the ligand compound includes metal halides; and / or,

[0029] the temperature of the second reaction is 25 - 40 °C; and / or,

[0030] the time of the second reaction is 10 - 120 min; and / or,

[0031] the second solvent includes one or more of dimethyl sulfoxide, N,N-dimethylformamide, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, 3-methoxybutanol, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, and alcohol solvents.

[0032] Optionally, in some embodiments of the present application, the metal halides include one or more of zinc chloride, lithium chloride, aluminum chloride, zinc bromide, lithium bromide, aluminum bromide, zinc iodide, lithium iodide, aluminum iodide, zinc fluoride, lithium fluoride, and aluminum fluoride; and / or,

[0033] the ratio of the molar amount of metal atoms in the metal oxide nanoparticles to the molar amount of halogen atoms in the metal halides is 1:(0.05 - 0.5); and / or,

[0034] the temperature of the second reaction is 25 - 40 °C; and / or,

[0035] the time of the second reaction is 10 - 120 min.

[0036] In a second aspect, the present application also provides a metal oxide nanoparticle, including the metal oxide nanoparticle prepared by the preparation method described above.

[0037] Optionally, in some embodiments of the present application, the metal oxide nanoparticles include at least one of zinc oxide, titanium oxide, tin oxide, zirconium oxide, aluminum oxide, copper oxide, molybdenum oxide, nickel oxide, gallium oxide, cobalt oxide, manganese oxide, and iron oxide; and / or,

[0038] Halogen atoms are connected to the surface of the metal oxide nanoparticles.

[0039] In a third aspect, the present application also provides an optoelectronic device, including an anode, an optical functional layer, an electron functional layer, and a cathode. The material of the electron functional layer includes the metal oxide nanoparticles prepared by the preparation method described above, or includes the metal oxide nanoparticles described above.

[0040] Optionally, in some embodiments of the present application, the material of the optical functional layer includes an organic light-emitting material or a quantum dot light-emitting material. The organic light-emitting material is selected from one or more of 4,4'-bis(N-carbazolyl)-1,1'-biphenyl: tris[2-(p-tolyl)pyridineiridium(III)], 4,4',4''-tris(carbazol-9-yl)triphenylamine: tris[2-(p-tolyl)pyridineiridium, poly[(9,9-dioctylfluorene-2,7-diyl)-alternating-(2,1,3-benzothiadiazole-4,7-diyl)], diarylanthracene derivatives, stilbene aromatic derivatives, pyrene derivatives, fluorene derivatives, TBPe fluorescent material, TTPX fluorescent material, TBRb fluorescent material, DBP fluorescent material, delayed fluorescence material, TTA material, thermally activated delayed material, a polymer containing B-N covalent bonding, a hybrid local charge transfer excited state material, and exciplex luminescent material. The quantum dot light-emitting material is selected from at least one of single-structure quantum dots, core-shell structure quantum dots, and perovskite semiconductor materials. The materials of the single-structure quantum dots, the core materials of the core-shell structure quantum dots, and the shell materials of the core-shell structure quantum dots are each selected from at least one of II-VI group compounds, IV-VI group compounds, III-V group compounds, and I-III-VI group compounds. The II-VI group compounds are selected from at least one of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, and HgZnSTe. The IV-VI group compounds are selected from at least one of SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, SnPbSeTe, and SnPbSTe.The III-V compound is selected from the group consisting of GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, GaNP, GaNAs, GaNSb, GaPAs, GaPSb, and AlN P, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInN P, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs and InAlPSb; the I-III-VI group compound is selected from at least one of CuInS2, CuInSe2 and AgInS2; the perovskite semiconductor material is selected from doped or undoped inorganic perovskite semiconductors, or organic-inorganic hybrid perovskite semiconductors; the inorganic perovskite semiconductor has a general structural formula of AMX3, wherein A is Cs; + ion, M is a divalent metal cation selected from Pb 2+ Sn 2+ , Cu 2+ 、Ni 2+ 、Cd 2+ Cr 2+ , Mn 2+ 、Co 2+ , Fe 2+ ,Ge 2+ , Yb 2+ 、Eu 2+ At least one of, X is a halogen anion selected from Cl - Br - ,I - At least one of the following; the general structural formula of the organic-inorganic hybrid perovskite semiconductor is BMX3, wherein B is an organic amine cation selected from CH3(CH2) n-2 NH 3+ or [NH3(CH2) n NH3] 2+ , where n≥2, M is a divalent metal cation selected from Pb 2+ Sn 2+ , Cu 2+ 、Ni 2+ 、Cd 2+ Cr 2+ , Mn 2+ 、Co 2+ , Fe 2+ ,Ge 2+ , Yb 2+ 、Eu2+ at least one of, X is a halogen anion, selected from Cl - , Br - , I - at least one of; and / or,

[0041] The anode and the cathode are each independently selected from doped metal oxide particle electrodes, composite electrodes of metal and metal oxide, graphene electrodes, carbon nanotube electrodes, metal electrodes or alloy electrodes. The material of the doped metal oxide particle electrode is selected from one or more of indium-doped tin oxide, fluorine-doped tin oxide, antimony-doped tin oxide, aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, magnesium-doped zinc oxide and aluminum-doped magnesium oxide. The composite electrode of metal and metal oxide is selected from AZO / Ag / AZO, AZO / Al / AZO, ITO / Ag / ITO, ITO / Al / ITO, ZnO / Ag / ZnO, ZnO / Al / ZnO, TiO2 / Ag / TiO2, TiO2 / Al / TiO2, ZnS / Ag / ZnS, ZnS / Al / ZnS. The material of the metal electrode is selected from one or more of Ag, Al, Cu, Mo, Au, Pt, Si, Ca, Mg and Ba.

[0042] In a fourth aspect, the present application further provides a display device, and the display device includes the optoelectronic device described above.

[0043] In the preparation method provided by the present application, the nucleation frequency is regulated by an organic amine, thereby regulating the nucleation sites and growth rate of the metal oxide, reducing the formation of surface defects of the metal oxide, and lowering the surface defects of the metal oxide. Description of the Drawings

[0044] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the following will briefly introduce the drawings required for the description of the embodiments. Obviously, the following drawings are only some embodiments of the present application. For those skilled in the art, without creative efforts, other drawings can be obtained based on these drawings.

[0045] Figure 1 is a schematic flow chart of a method for preparing a metal oxide proposed in an embodiment of the present application;

[0046] Figure 2 is a schematic flow chart of a method for preparing a metal oxide proposed in another embodiment of the present application;

[0047] Figure 3 is a schematic structural diagram of an optoelectronic device proposed in an embodiment of the present application;

[0048] Figure 4It is a schematic structural diagram of an optoelectronic device proposed in another embodiment of the present application;

[0049] Reference numerals:

[0050] 100 - optoelectronic device; 10 - anode; 20 - optical functional layer; 21 - light-emitting layer; 30 - electronic functional layer; 40 - hole transport layer; 50 - hole injection layer; 60 - cathode. Detailed implementation manners

[0051] Next, the technical solutions in the embodiments of the present application will be clearly and completely described in conjunction with the accompanying drawings in the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative efforts belong to the scope of protection of the present application. In addition, it should be understood that the specific implementation manners described herein are only used to illustrate and explain the present application, and are not used to limit the present application.

[0052] In the present application, unless otherwise stated, the orientation words such as "upper" and "lower" specifically refer to the drawing direction in the drawings. In addition, in the description of the specification of the present application, the term "including" means "including but not limited to".

[0053] The various embodiments of the present application may exist in the form of a range; it should be understood that the description in the form of a range is only for convenience and brevity, and should not be construed as a rigid limitation on the scope of the present application; therefore, it should be considered that the described range description has specifically disclosed all possible sub-ranges and single values within that range. For example, it should be considered that the range description from 1 to 6 has specifically disclosed sub-ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., and single numbers within that range, such as 1, 2, 3, 4, 5, and 6, regardless of the range. Additionally, whenever a numerical range is indicated herein, it means including any cited number (fraction or integer) within the indicated range.

[0054] In the present application, "and / or" describes the association relationship of associated objects, indicating that three relationships may exist. For example, A and / or B may represent: A exists alone, A and B exist simultaneously, and B exists alone. Wherein A and B may be singular or plural.

[0055] In this application, "at least one" means one or more, and "a plurality" means two or more. "At least one kind", "at least one of the following items", or similar expressions refer to any combination of these items, including any combination of single items or plural items. For example, "at least one of a, b, or c", or "at least one of a, b, and c" can both represent: a, b, c, a - b (i.e., a and b), a - c, b - c, or a - b - c, where a, b, and c can be single or multiple respectively.

[0056] Glossary of Terms

[0057] In this application, "substituted" means that a hydrogen atom in the substituent is replaced by a substituent.

[0058] In this application, when the same substituent appears multiple times, it can be independently selected from different groups. For example, if the general formula contains multiple R1s, then R1s can be independently selected from different groups. For example 6 Rs on the benzene ring 1 can be the same as or different from each other.

[0059] In this application, "a combination of multiple kinds" means a situation where at least one hydrogen in a group is replaced by other groups (it can be replaced by one other group or multiple other groups). For example, a combination of a hydroxyl group, a halogen, and an amino group can mean that at least two hydrogens in the amino group are respectively replaced by a hydroxyl group and a halogen.

[0060] In the present application, "aliphatic hydrocarbon group" may represent a straight-chain alkyl group or a branched-chain alkyl group. The number of carbon atoms in the aliphatic hydrocarbon group may be 1-50, 1-30, 1-20, 1-10 or 1-6. Non-limiting examples of the aliphatic hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 2-ethylbutyl, 3,3-dimethylbutyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, 1-methylpentyl, 3-methylpentyl, 2-ethylpentyl, 4-methyl-2-pentyl, n-hexyl, 1-methylhexyl, 2-ethylhexyl, 2-butylhexyl, cyclohexyl, 4-methylcyclohexyl, 4-tert-butylcyclohexyl, n-heptyl, 1-methylheptyl, 2,2-dimethylheptyl, 2-ethylheptyl, 2-butylheptyl, n-octyl, tert-octyl, 2-ethyloctyl, 2-butyl octyl, 2-hexyloctyl, 3,7-dimethyloctyl, cyclooctyl, n-nonyl, n-decyl, adamantyl, 2-ethyl decyl, 2-butyl decyl, 2-hexyl decyl, 2-octyl decyl, n-undecyl, n-dodecyl, 2-ethyldodecyl, 2-butyl dodecyl, 2-hexyl dodecyl, 2-octyl dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, 2-ethylhexadecyl, 2-butyl hexadecyl, 2-hexyl hexadecyl, 2-octyl hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, 2-ethyl eicosyl, 2-butyl eicosyl, 2-hexyl eicosyl, 2-octyl eicosyl, n-heneicosyl, n-docosyl, n-tricosyl, n-tetracosyl, n-pentacosyl, n-hexacosyl, n-heptacosyl, n-octacosyl, n-nonacosyl, n-triacontyl, etc. "alicyclic hydrocarbon group" may represent a group formed by removing one hydrogen from a cyclic alkane. "heterocyclic hydrocarbon group" may represent a group formed by removing one hydrogen from a cyclic compound containing at least one heteroatom.

[0061] In the present application, "number of ring atoms" refers to the number of atoms that form a ring in a structural compound formed by bonding atoms in a ring (e.g., a monocyclic compound or a polycyclic compound). It can be understood that the ring atoms are not limited to carbon atoms. When a heterocycle is contained in a cyclic compound, heteroatoms are also atoms that form the heterocycle and belong to the ring atoms. When the ring is substituted by a substituent, the atoms contained in the substituent are not included in the ring-forming atoms. The same applies to the "number of ring atoms" described below under the condition of no special description. For example, the number of ring atoms in a benzene ring is 6, the number of ring atoms in a naphthalene ring is 10, and the number of ring atoms in a thiophenyl group is 5.

[0062] In the present application, "aryl, aryl group or aromatic group" refers to a hydrocarbon group containing at least one aromatic ring, such as a monocyclic compound, a fused-ring compound or a polycyclic non-fused compound, etc. "Heteroaryl or heteroaryl group" refers to an aromatic hydrocarbon group containing at least one heteroatom, such as a monocyclic compound containing at least one heteroatom, a fused-ring compound containing at least one heteroatom or a polycyclic non-fused compound containing at least one heteroatom, etc. The heteroatom is preferably selected from Si, N, P, O, S and / or Ge, and particularly preferably selected from Si, N, P, O and / or S. Among them, the fused-ring compound or the fused compound has the same meaning and can be interchanged, specifically referring to a compound that can have two or more rings, where two ring atoms are shared by two adjacent rings, that is, a fused ring. For the purposes of the present application, the aromatic group or heteroaryl group includes not only the system of the aromatic ring, but also the non-aromatic ring system. Therefore, systems such as pyridine, thiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, pyrazine, pyridazine, pyrimidine, triazine, carbene, etc. are also considered aromatic groups or heteroaromatic groups for the purposes of this invention. For the purposes of the present application, the fused-ring aromatic or fused heteroaromatic ring system includes not only the system of the aromatic group or heteroaryl group, but also, in which multiple aromatic groups or heteroaromatic groups can also be interrupted by short non-aromatic units (<10% of non-H atoms, preferably less than 5% of non-H atoms, such as C, N or O atoms). Therefore, systems such as 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ether, etc. are also considered fused-ring aromatic ring systems for the purposes of this invention.

[0063] In a preferred embodiment, the aromatic group is selected from: benzene, naphthalene, anthracene, fluoranthene, phenanthrene, benzo[a]phenanthrene, dibenzo[a,h]anthracene, tetracene, pyrene, benzo[a]pyrene, acenaphthene, fluorene, and their derivatives; the heteroaryl group is selected from triazine, pyridine, pyrimidine, imidazole, furan, thiophene, benzofuran, benzothiophene, indole, carbazole, pyrroloimidazole, pyrrolopyrrole, thiophenopyrrole, thiophenothiophene, furanopyrrole, furanofuran, thiophenofuran, benzisoxazole, benzisothiazole, benzimidazole, quinoline, isoquinoline, phthalazine, quinoxaline, phenanthridine, perimidine, quinazoline, quinazolinone, dibenzothiophene, dibenzofuran, carbazole and their derivatives.

[0064] In the present application, amino represents -NR 1 R 2 wherein, R 1 and R 2 each independently represents H or an alkyl group, that is, the amino group can refer to -NH2, or -NH(alkyl), or -N(alkyl)(alkyl).

[0065] In this application, "halogen or halogen group" 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 aldehyde group represents -CHO; alkyloxy group represents -O-alkyl; alkoxy group represents -OR; aryloxy group represents -OAr; heteroaryloxy group represents -OAr'; formyl group represents alkoxycarbonyl group represents alkylcarbonyl group represents wherein, R represents a straight-chain alkyl group or a branched-chain alkyl group; Ar represents an aromatic group; Ar' represents a heteroaromatic group.

[0066] In a first aspect, an embodiment of this application provides a method for preparing metal oxide nanoparticles. Please refer to Figure 1 The preparation method includes the following steps:

[0067] S10, providing a metal salt, an organic amine, a base, and a first solvent;

[0068] S20, mixing the metal salt, the organic amine, the base, and the first solvent, and performing a first reaction to obtain metal oxide nanoparticles;

[0069] wherein, the organic amine is an organic compound containing an amino group, for example, it can be an alkylamine compound, an alkanolamine compound, an amide compound, a cycloalkylamine compound, an aromatic amine compound, etc.

[0070] Crystal formation mainly includes nucleation and growth. In this application, the nucleation frequency is regulated by an organic amine, so that more precursors (metal ions, hydroxide ions, etc.) tend to continue growing on the already formed nuclei rather than constructing new nuclei, thereby effectively regulating the nucleation sites and growth rate of metal oxides, promoting grain growth, and reducing the formation of surface defects during crystal growth, thereby controllably increasing the size of metal oxides to a certain extent and reducing the surface defects of metal oxides; in addition, the uniformity of metal oxides is also greatly improved, which helps to improve the film-forming effect of nanoparticles and the optoelectronic properties of thin films. The metal oxide nanoparticles prepared in this application have uniform sizes and good charge transport properties.

[0071] When the metal oxide nanoparticles are used to fabricate the electronic functional layer 30, the formation of electron capture centers and exciton recombination centers can be avoided, thereby effectively improving the transport efficiency of the electronic functional layer 30, reducing the attenuation of the device, and further improving the optoelectronic properties and service life of the optoelectronic device 100.

[0072] In some embodiments, in the step of mixing the multiple raw material components: first mix the organic amine with the metal salt, and then add the base and continue mixing. Specifically, the organic amine, the first solvent and the metal salt can be first mixed, and then the base is added for mixing; or the first solvent can be divided into two parts, one part is mixed with the organic amine and the metal salt to form a first mixed solution, and the remaining part is mixed with the base to form a second mixed solution, and then the second mixed solution is mixed with the first mixed solution. The metal salt is first mixed with the organic amine, and then the base is added for reaction. In a solution environment, the organic amine can coordinate with metal ions and compete with the base precursor, thereby playing a role in regulating the nucleation sites and the growth rate.

[0073] In other embodiments, in the step of mixing the multiple raw material components: the base and the organic amine are mixed with the metal salt simultaneously; specifically, the metal salt can be first dispersed in the first solvent, and then the base and the organic amine are added simultaneously; or the metal salt, the organic amine, the base and the first solvent can be directly mixed synchronously; or the first solvent can be divided into two parts, one part is mixed with the metal salt to form a third mixed solution, and the remaining part is mixed with the organic amine and the base to form a fourth mixed solution, and then the fourth mixed solution is mixed with the third mixed solution. The metal salt, the organic amine and the base are in synchronous contact, and the organic amine can play a competitive role, thereby effectively regulating the nucleation sites and the growth rate.

[0074] In some embodiments, the organic amine includes one or more of the compounds having the structural formula NR1R2R3. Wherein, R1, R2, and R3 are each independently selected from one or more combinations of hydrogen, deuterium, amino group, halogen, hydroxyl group, carboxyl group, nitro group, sulfonic acid group, aldehyde group, mercapto group, cyano group, unsubstituted or substituted C1-C20 hydrocarbon groups, unsubstituted or substituted C1-C20 hydrocarbon oxy groups, unsubstituted or substituted alicyclic hydrocarbon groups with 3 to 60 ring atoms, unsubstituted or substituted heterocyclic hydrocarbon groups with 3 to 60 ring atoms, unsubstituted or substituted aryl groups with 6 to 60 ring atoms, unsubstituted or substituted heteroaryl groups with 5 to 60 ring atoms, unsubstituted or substituted aryloxy groups with 6 to 60 ring atoms, unsubstituted or substituted heteroaryloxy groups with 5 to 60 ring atoms; wherein, the heteroatoms in the heterocyclic hydrocarbon group, the heteroaryl group or the heteroaryloxy group are one or more of N, S, O, P, Si, and the number of heteroatoms is 1 to 20; each time the substituent appears, it is independently selected from amino group, halogen, hydroxyl group, carboxyl group, nitro group, sulfonic acid group, aldehyde group, mercapto group, cyano group.

[0075] In some embodiments, the organic amine is an alkylamine, that is, at least one of R1, R2, and R3 is selected from alkyl groups. In other embodiments, the total number of carbon atoms contained in R1, R2, and R3 is 1 to 18; for example, one of R1, R2, and R3 can be selected from H, and the remaining two are each independently selected from substituted or unsubstituted C1-C18 alkyl groups, or two of R1, R2, and R3 can be selected from H, and the remaining one is selected from substituted or unsubstituted C1-C18 alkyl groups. Among them, the alkyl group can be a straight-chain alkyl group or a branched-chain alkyl group, and the number of its carbon atoms is 1 to 18, for example, it can be 1 to 4, 1 to 8, 1 to 10, 1 to 12, 1 to 15, 2 to 5, 2 to 8, 2 to 10, 2 to 12, 3 to 7, 3 to 8, 3 to 10, 3 to 12, 4 to 10, and so on; further, regardless of how many of R1, R2, and R3 are selected from alkyl groups, the structural formula of the organic amine satisfies that the total number of carbon atoms contained in R1, R2, and R3 is 1 to 18, for example, it can be 1 to 4, 1 to 8, 1 to 10, 1 to 12, 1 to 15, 2 to 5, 2 to 8, 2 to 10, 2 to 12, 3 to 7, 3 to 8, 3 to 10, 3 to 12, 4 to 10, and so on.

[0076] In some embodiments, R1, R2, and R3 are each independently selected from any one of hydrogen and unsubstituted straight-chain alkyl groups. Straight-chain alkylamines are more conducive to subsequent ligand exchange and help improve the exchange efficiency.

[0077] In some embodiments, the total number of carbon atoms contained in R1, R2, and R3 is 3 to 8; for example, it can be 3, 4, 5, 6, 7, or 8. Controlling the number of carbon atoms within the range of 3 to 8 not only helps to control the reaction to proceed stably and smoothly, but also is more conducive to subsequent ligand exchange.

[0078] In some embodiments, two of R1, R2, and R3 are selected from hydrogen; the alkylamine is a primary amine.

[0079] In some embodiments, the organic amine includes one or more of n-propylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, and n-octylamine.

[0080] In some embodiments, the metal salt includes at least one of zinc salt, titanium salt, tin salt, zirconium salt, aluminum salt, copper salt, molybdenum salt, nickel salt, gallium salt, cobalt salt, manganese salt, and iron salt. It can be understood that taking the metal salt MX n as a raw material, the metal oxide MO composed of metal M and oxygen element can be correspondingly prepared n. Specifically, when the metal salt is taken from zinc salt, titanium salt, tin salt, zirconium salt, aluminum salt, copper salt, molybdenum salt, nickel salt, gallium salt, cobalt salt, manganese salt or iron salt respectively, zinc oxide, titanium oxide, tin oxide, zirconium oxide, aluminum oxide, copper oxide, molybdenum oxide, nickel oxide, gallium oxide, cobalt oxide, manganese oxide, iron oxide can be prepared respectively. Among them, n can be any positive number that satisfies the charge balance in the compound. For example, when M is a divalent metal cation and X is a monovalent anion, n can be 2; when M is a monovalent metal cation and X is a divalent anion, n can be 0.5.

[0081] In some embodiments, the anion X in the metal salt can be nitrate, halide ion, acetate, sulfate, etc. Exemplarily, the metal salt can be at least one of zinc nitrate, zinc chloride, zinc acetate, titanium nitrate, titanium chloride, titanium acetate, tin nitrate, tin chloride, tin acetate, zirconium nitrate, zirconium chloride, zirconium acetate, aluminum nitrate, aluminum chloride, aluminum acetate, copper nitrate, copper chloride, copper acetate, molybdenum nitrate, molybdenum chloride, molybdenum acetate, nickel nitrate, nickel chloride, nickel acetate, gallium nitrate, gallium chloride, gallium acetate, cobalt nitrate, cobalt chloride, cobalt acetate, manganese nitrate, manganese chloride, manganese acetate, iron nitrate, iron chloride, iron acetate.

[0082] In some embodiments, the base includes one or more of metal hydroxides and alkyl ammonium hydroxides. The metal hydroxides include one or more of sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, barium hydroxide. The alkyl ammonium hydroxides include one or more of tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropyl ammonium hydroxide.

[0083] In some embodiments, the first solvent includes one or more of dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF) and alcohol solvents. The alcohol solvents can be one or more of methanol, ethanol, isopropanol, n-propanol, n-butanol, pentanol, ethylene glycol; in some embodiments, the alcohol solvents are linear monohydric alcohols, such as one or more of methanol, ethanol, n-propanol, n-butanol, n-pentanol.

[0084] In some embodiments, the molar ratio of the metal ions in the metal salt to the molar amount of the organic amine is 1:(10 - 30); for example, it can be 1:10, 1:12, 1:15, 1:17, 1:20, 1:23, 1:25, 1:28, 1:30 and the values between any two of the above. Controlling the addition amounts of the metal salt and the organic amine within the above range can ensure that the organic amine fully plays the roles of coordination and competitive reaction, and promotes the formation of metal oxide nanoparticles with few surface defects, large size and uniformity.

[0085] In some embodiments, the temperature of the first reaction is 25 to 60 °C; for example, it can be 25 °C, 30 °C, 35 °C, 40 °C, 45 °C, 50 °C, 55 °C, 60 °C, and values between any two of the above. Controlling the temperature within this range can promote the reaction.

[0086] In some embodiments, the time of the first reaction is 0.5 to 6 h; for example, it can be 0.5 h, 1 h, 1.5 h, 2 h, 2.5 h, 3 h, 3.5 h, 4 h, 4.5 h, 5 h, 5.5 h, 6 h, and values between any two of the above.

[0087] The base is metal hydroxide and / or alkyl ammonium hydroxide, which contains hydroxide. In some embodiments, the ratio of the molar amount of metal ions in the metal salt to the molar amount of hydroxide in the base is 1:(1.5 to 3.0); for example, it can be 1:1.5, 1:1.8, 1:2, 1:2.2, 1:2.5, 1:2.7, 1:3, and values between any two of the above. Controlling the addition amounts of the metal salt and the base within the above range can ensure a sufficient reaction and promote the formation of metal oxides.

[0088] In some embodiments, the volume ratio of the first solvent to the organic amine is 1:(1 to 5); for example, it can be 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, and values between any two of the above.

[0089] Please refer to Figure 2 , in some embodiments, the preparation method further includes the following steps:

[0090] S30, providing a second solvent and a ligand compound;

[0091] S40, dispersing the metal oxide nanoparticles in the second solvent to obtain a mixed solution;

[0092] S50, mixing the mixed solution and the ligand compound to carry out a second reaction to obtain metal oxide nanoparticles with halogen atoms connected to the surface.

[0093] By adding a ligand compound to carry out an in-situ ligand exchange reaction, the oxygen vacancies on the surface of the nanoparticles can be further passivated, the surface defects can be reduced, and the exciton recombination efficiency can be improved; at the same time, the dispersibility of the nanoparticles can be improved.

[0094] The ligand compound includes, but is not limited to, one or more of organic acids, organic amines, thiol compounds, and halogen ligand compounds; for example, it can be one or more of oleic acid, oleylamine, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, n-octanethiol, and metal chlorides.

[0095] In some embodiments, the ligand compound includes metal halides, and the metal halides include one or more of zinc chloride, lithium chloride, aluminum chloride, zinc bromide, lithium bromide, aluminum bromide, zinc iodide, lithium iodide, aluminum iodide, zinc fluoride, lithium fluoride, and aluminum fluoride. When the ligand compound is selected from metal halides, it can not only further passivate the oxygen vacancies on the surface of the nanoparticles, reduce surface defects, and improve the dispersibility of the nanoparticles, but also promote electron transport, making the nanoparticles have higher conductivity.

[0096] In some embodiments, the second solvent includes one or more of dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, 3-methoxybutanol, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, and alcohol solvents.

[0097] In some embodiments, the ratio of the molar amount of metal atoms in the metal oxide nanoparticles to the molar amount of halogen atoms in the metal halides is 1:(0.05 - 0.5); for example, it can be 1:0.05, 1:0.08, 1:0.1, 1:0.15, 1:0.2, 1:0.25, 1:0.3, 1:0.35, 1:0.4, 1:0.45, and values between any two of the above. Controlling the addition amounts of the metal salt and halogen atoms within the above range can ensure the full progress of the ligand exchange reaction and promote the full passivation of the metal oxide nanoparticles.

[0098] In some embodiments, the temperature of the second reaction is 25 - 40°C; for example, it can be 25°C, 28°C, 30°C, 33°C, 35°C, 37°C, 40°C, and values between any two of the above. In this way, the ligand exchange reaction can be promoted.

[0099] In some embodiments, the time of the second reaction is 10 - 120 min; for example, it can be 10 min, 20 min, 30 min, 40 min, 50 min, 60 min, 70 min, 80 min, 90 min, 100 min, 110 min, 120 min, and values between any two of the above. In this way, the reaction can be promoted to proceed fully, ensuring the full passivation of the metal oxide nanoparticles.

[0100] In a second aspect, the present application also provides a metal oxide nanoparticle, including the metal oxide nanoparticle prepared by the preparation method described above.

[0101] The metal oxide nanoparticles prepared by the preparation method of the above embodiments are large and uniform in size, have fewer surface defects, and have good charge transport performance.

[0102] In some embodiments, the metal oxide nanoparticles include at least one of zinc oxide, titanium oxide, tin oxide, zirconium oxide, aluminum oxide, copper oxide, molybdenum oxide, nickel oxide, gallium oxide, cobalt oxide, manganese oxide, and iron oxide. In some embodiments, when the metal oxide nanoparticles are zinc oxide nanoparticles, the average particle size of the metal oxide nanoparticles is 6 to 7 nm.

[0103] In some embodiments, halogen atoms are connected to the surface of the metal oxide nanoparticles. By connecting halogen atoms to the surface of the metal oxide nanoparticles, it helps to improve the charge transport performance of the nanoparticles, reduce surface defects, and improve dispersibility.

[0104] In a third aspect, the present application also proposes an optoelectronic device 100. Please refer to Figure 3 , the optoelectronic device 100 includes an anode 10, an optical functional layer 20, an electronic functional layer 30, and a cathode 60. The material of the electronic functional layer 30 includes the metal oxide nanoparticles prepared by the preparation method described above, or includes the metal oxide nanoparticles described above.

[0105] The metal oxide nanoparticles prepared by the preparation method of the above embodiments are large and uniform in size, have fewer surface defects, and have good charge transport performance; when the metal oxide nanoparticles are used to fabricate the electronic functional layer 30, the formation of electron trapping centers and exciton recombination centers can be avoided, thereby effectively improving the transport efficiency of the electronic functional layer 30, reducing the attenuation of the device, and further improving the optoelectronic performance and service life of the optoelectronic device 100.

[0106] In some embodiments, the optoelectronic device 100 is a light-emitting device, such as an organic light-emitting diode or a quantum dot light-emitting diode, etc. The optical functional layer 20 includes a light-emitting layer 21. The light-emitting layer 21 can be an organic light-emitting layer or a quantum dot light-emitting layer. When the light-emitting layer 21 is an organic light-emitting layer, the optoelectronic device 100 can be an organic light-emitting device; when the light-emitting layer 21 is a quantum dot light-emitting layer, the optoelectronic device 100 can be a quantum dot light-emitting device.

[0107] The material of the organic light-emitting layer is a material known in the art for the organic light-emitting layer of optoelectronic device 100. For example, it can be selected from, but not limited to, the materials of the light-emitting layer 21 including one or more of an organic light-emitting material and a quantum dot light-emitting material. The organic light-emitting material is selected from one or more of 4,4'-bis(N-carbazolyl)-1,1'-biphenyl: tris[2-(p-tolyl)pyridineiridium(III)], 4,4',4''-tris(carbazol-9-yl)triphenylamine: tris[2-(p-tolyl)pyridineiridium, poly[(9,9-dioctylfluorene-2,7-diyl)-alternating-(2,1,3-benzothiadiazole-4,7-diyl)], diarylanthracene derivatives, stilbene aromatic derivatives, pyrene derivatives, fluorene derivatives, TBPe fluorescent material, TTPX fluorescent material, TBRb fluorescent material, DBP fluorescent material, delayed fluorescence material, TTA material, thermally activated delayed material, a polymer containing a B-N covalent bond, a hybrid locally charge-transfer excited state material, and an exciplex luminescent material.

[0108] The material of the quantum dot light-emitting layer is a quantum dot material known in the art for use in optoelectronic device 100. For example, it can be selected from, but not limited to, at least one of single-structure quantum dots, core-shell structure quantum dots, and perovskite semiconductor materials; the materials of the single-structure quantum dots, the core materials of the core-shell structure quantum dots, and the shell materials of the core-shell structure quantum dots are respectively selected from at least one of II-VI group compounds, IV-VI group compounds, III-V group compounds, and I-III-VI group compounds; the II-VI group compounds are selected from at least one of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, and HgZnSTe; the IV-VI group compounds are selected from at least one of SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, SnPbSeTe, and SnPbSTe; the III-V group compounds are selected from at least one of GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, and InAlPSb; the I-III-VI group compounds are selected from at least one of CuInS2, CuInSe2, and AgInS2.

[0109] As an example, the quantum dots of the core-shell structure can be selected from but not limited to at least one of CdZnSe / CdZnSe / ZnSe / CdZnS / ZnS, CdZnSe / CdZnSe / CdZnS / ZnS CdSe / CdSeS / CdS, InP / ZnSeS / ZnS, CdZnSe / ZnSe / ZnS, CdSeS / ZnSeS / ZnS, CdSe / ZnS, CdSe / ZnSe / ZnS, ZnSe / ZnS, ZnSeTe / ZnS, CdSe / CdZnSeS / ZnS, and InP / ZnSe / ZnS.

[0110] It should be noted that for the materials of the aforementioned single-structure quantum dots, or the core materials of the core-shell structure quantum dots, or the shell materials of the core-shell structure quantum dots, the chemical formulas provided only indicate the elemental composition and do not indicate the content of each element. For example, CdZnSe only represents the composition of three elements, Cd, Zn, and Se. If the content of each element is to be represented, it corresponds to Cd x Zn 1-x Se, where 0 < x < 1.

[0111] The perovskite semiconductor material is selected from doped or undoped inorganic perovskite semiconductors, or organic-inorganic hybrid perovskite semiconductors; the general structural formula of the inorganic perovskite semiconductor is AMX3, where A is a Cs + ion, M is a divalent metal cation selected from at least one of Pb 2+ , Sn 2+ , Cu 2+ , Ni 2+ , Cd 2+ , Cr 2+ , Mn 2+ , Co 2+ , Fe 2+ , Ge 2+ , Yb 2+ , Eu 2+ , and X is a halogen anion selected from at least one of Cl - , Br - , I - ; the general structural formula of the organic-inorganic hybrid perovskite semiconductor is BMX3, where B is an organic amine cation selected from CH3(CH2) n-2 NH 3+ or [NH3(CH2) n NH3] 2+ , where n ≥ 2, M is a divalent metal cation selected from Pb 2+ , Sn 2+ , Cu 2+ , Ni 2+ , Cd2+ , Cr 2+ , Mn 2+ , Co 2+ , Fe 2+ , Ge 2+ , Yb 2+ , Eu 2+ at least one of, X is a halogen anion, selected from Cl - , Br - , I - at least one of.

[0112] The anode 10 can be an anode 10 known in the art for use in the optoelectronic device 100. For example, it can be selected from, but not limited to, a doped metal oxide particle electrode, a composite electrode of a metal and a metal oxide, a graphene electrode, a carbon nanotube electrode, a metal electrode, or an alloy electrode. The material of the doped metal oxide particle electrode is selected from one or more of indium-doped tin oxide, fluorine-doped tin oxide, antimony-doped tin oxide, aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, magnesium-doped zinc oxide, and aluminum-doped magnesium oxide. The composite electrode of a metal and a metal oxide is selected from AZO / Ag / AZO, AZO / Al / AZO, ITO / Ag / ITO, ITO / Al / ITO, ZnO / Ag / ZnO, ZnO / Al / ZnO, TiO2 / Ag / TiO2, TiO2 / Al / TiO2, ZnS / Ag / ZnS, ZnS / Al / ZnS. The material of the metal electrode is selected from one or more of Ag, Al, Cu, Mo, Au, Pt, Si, Ca, Mg, and Ba. Among them, " / " represents a laminated structure. For example, the composite electrode AZO / Ag / AZO represents an electrode with a three-layer laminated composite structure composed of an AZO layer, an Ag layer, and an AZO layer.

[0113] The cathode 60 can be a cathode 60 known in the art for optoelectronic devices 100. For example, it can be selected from, but not limited to, doped metal oxide particle electrodes, composite electrodes of metals and metal oxides, graphene electrodes, carbon nanotube electrodes, metal electrodes or alloy electrodes. The material of the doped metal oxide particle electrode is selected from one or more of indium-doped tin oxide, fluorine-doped tin oxide, antimony-doped tin oxide, aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, magnesium-doped zinc oxide, and aluminum-doped magnesium oxide. The composite electrode of metal and metal oxide is selected from AZO / Ag / AZO, AZO / Al / AZO, ITO / Ag / ITO, ITO / Al / ITO, ZnO / Ag / ZnO, ZnO / Al / ZnO, TiO2 / Ag / TiO2, TiO2 / Al / TiO2, ZnS / Ag / ZnS, ZnS / Al / ZnS. The material of the metal electrode is selected from one or more of Ag, Al, Cu, Mo, Au, Pt, Si, Ca, Mg, and Ba.

[0114] Please refer to Figure 4, in some embodiments, the optoelectronic device 100 further includes a hole functional layer disposed between the light-emitting layer 21 and the anode 10, and the hole functional layer includes one or both of a hole transport layer 40 and a hole injection layer 50. It should be noted that when the hole functional layer includes both the hole transport layer 40 and the hole injection layer 50, the hole transport layer 40 is located between the hole injection layer 50 and the light-emitting layer 21. The material of the hole functional layer can be a material commonly used in the art and having hole injection or transport performance. For example, in some embodiments, the material of the hole transport layer 40 is selected from 4,4'-N,N'-dicarbazolyl-biphenyl (CBP), N,N'-diphenyl-N,N'-bis(1-naphthyl)-1,1'-biphenyl-4,4”-diamine, N,N'-diphenyl-N,N'-bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine, N,N'-bis(3-methylphenyl)-N,N'-bis(phenyl)-spiro(spiro-TPD), N,N'-bis(4-(N,N'-diphenyl-amino)phenyl)-N,N'-diphenylbenzidine, 4,4',4'-tris(N-carbazolyl)-triphenylamine, 4,4',4'-tris(N-3-methylphenyl-N-phenylamino)triphenylamine, poly[(9,9'-dioctylfluorene-2,7-diyl)-co-(4,4'-(N-(4-sec-butylphenyl)diphenylamine))], poly(4-butylphenyl-diphenylamine) (poly-TPD), polyaniline, polypyrrole, poly(p-phenylene vinylene), poly(phenylene vinylene), poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene vinylene] and poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylene vinylene], copper phthalocyanine, aromatic tertiary amines, polynuclear aromatic tertiary amines, 4,4'-bis(p-carbazolyl)-1,1'-biphenyl compounds, N,N,N',N'-tetraarylbenzidine, PEDOT:PSS and its derivatives, poly(N-vinylcarbazole) (PVK) and its derivatives, polymethacrylate and its derivatives, poly(9,9-octylfluorene) and its derivatives, poly(spirofluorene) and its derivatives, N,N'-bis(naphthalen-1-yl)-N,N'-diphenylbenzidine, spiro-NPB, doped graphene, undoped graphene, C60, doped or undoped NiO, doped or undoped MoO3, doped or undoped WO3, doped or undoped V2O5, doped or undoped p-type gallium nitride, doped or undoped CrO3, doped or undoped CuO, at least one of them.The material of the hole injection layer 50 may include but is not limited to one or more of poly(ethylenedioxythiophene):polystyrenesulfonate (PEDOT:PSS), poly(9,9-dioctylfluorene-co-N-(4-butylphenyl)-diphenylamine) (TFB), polyarylamine, poly(N-vinylcarbazole), polyaniline, polypyrrole, N,N,N',N'-tetrakis(4-methoxyphenyl)-benzidine (TPD), 4-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (α-NPD), 4,4',4''-tris[phenyl(m-tolyl)amino]triphenylamine (m-MTDATA), 4,4',4''-tris(N-carbazolyl)-triphenylamine (TCTA), 1,1-bis[(di-4-tolylamino)phenyl]cyclohexane (TAPC), 4,4',4''-tris(diphenylamino)triphenylamine (TDATA) doped with tetrafluoro-tetracyano-quinodimethane (F4-TCNQ), p-doped phthalocyanine (e.g., zinc phthalocyanine (ZnPc) doped with F4-TCNQ), α-NPD doped with F4-TCNQ, hexaazatriphenylenehexanitrile (HAT-CN).

[0115] It can be understood that the materials of the respective layers of the optoelectronic device 100 can be adjusted according to the light emission requirements of the optoelectronic device 100.

[0116] It can be understood that the optoelectronic device 100 can be a normal device or an inverted device.

[0117] Based on the above embodiments of the optoelectronic device 100, an embodiment of the present application further provides a method for manufacturing an optoelectronic device 100, including the following steps:

[0118] The manufacturing method includes the following steps: preparing a plurality of film layers in sequence according to a preset film layer order to obtain the optoelectronic device 100; wherein, the plurality of film layers include an anode 10, a cathode 60, and at least one functional layer disposed between the anode 10 and the cathode 60, and the at least one functional layer includes an electron functional layer 30, or includes at least one of a light-emitting layer 21 (optical functional layer 20), a hole transport layer 40, a hole injection layer 50, and an electron functional layer 30. Among them, the preset film layer order refers to the order in which the optoelectronic device 100 is stacked layer by layer from bottom to top.

[0119] In the optoelectronic device 100 provided by the present application, for the functional layer, the anode 10, and the cathode 60, conventional preparation methods can also be used for preparation. Specifically, the conventional preparation methods can be chemical methods or physical methods. Among them, the chemical methods include chemical vapor deposition, successive ionic layer adsorption and reaction, anodic oxidation, electrolytic deposition, and coprecipitation. The physical methods include physical coating methods and solution methods. Among them, the physical coating methods include: thermal evaporation coating, electron beam evaporation coating, magnetron sputtering, multi-arc ion plating, physical vapor deposition, atomic layer deposition, pulsed laser deposition, etc.; the solution method can be spin coating, printing, inkjet printing, doctor blading, printing, dip coating, immersion, spraying, roll coating, casting, slot die coating, and bar coating, etc.

[0120] In some embodiments, after the optoelectronic device 100 is prepared, it further includes a step of encapsulating the optoelectronic device 100. The encapsulation process can use common machine encapsulation or manual encapsulation. Preferably, in the environment of the encapsulation process, both the oxygen content and the water content are lower than 0.1 ppm to ensure the stability of the optoelectronic device 100.

[0121] In addition, the present application also relates to a display device, and the display device includes the optoelectronic device 100 described above. The display device can be any electronic product with a display function, and the electronic products include but are not limited to smartphones, tablet computers, laptop computers, digital cameras, digital video cameras, smart wearable devices, intelligent weighing electronic scales, in-vehicle displays, televisions, or e-book readers. Among them, the smart wearable devices can be, for example, smart bracelets, smart watches, virtual reality (VR) helmets, etc.

[0122] Hereinafter, the technical solutions and technical effects of the present application will be described in detail through specific examples and comparative examples. The following examples are only partial examples of the present application and do not specifically limit the present application.

[0123] Material Example 1

[0124] 1) Add metal salt to DMF to form a first solution with a metal ion concentration of 0.5 mol / L; disperse the base in a mixed solution of ethanol and organic amine to form a second solution with a hydroxide concentration of 0.6 mol / L. Among them, the metal salt is zinc chloride, the base is sodium hydroxide, the organic amine is n-butylamine, and the first solvent is DMF and ethanol.

[0125] 2) Drop the second solution into the first solution at room temperature and continue to stir at 35 °C for 2 h to obtain a clear and transparent solution. Among them, Zn 2+ 、OH -The molar ratio with the organic amine is 1:2:25. Acetone is added to the clear and transparent solution, stirred evenly and allowed to stand for precipitation, collected after centrifugation, and metal oxide nanoparticles (ZnO nanoparticles) are obtained.

[0126] 3) Disperse the ZnO nanoparticles in ethanol to prepare a metal oxide dispersion with a concentration of 30 mg / ml.

[0127] Material Example 2

[0128] This material example is basically the same as Material Example 1, except that in this material example, step 3) is changed to:

[0129] 3) Disperse the ZnO nanoparticles in ethanol. After making a mixed solution, add the ligand compound zinc chloride, stir and react at 30 °C for 120 min, then add acetone, stir evenly and allow to stand for precipitation, collect after centrifugation, and obtain metal oxide nanoparticles with chloride ions connected to the surface; Disperse the nanoparticles in ethanol to prepare a metal oxide dispersion with a concentration of 30 mg / ml.

[0130] In addition, other parameters and steps remain unchanged.

[0131] Material Example 3

[0132] This material example is basically the same as Material Example 2, except that in this material example, the organic amine is first mixed with the zinc salt and then with the base. Correspondingly, step 1) is changed to:

[0133] 1) Add the metal salt and the organic amine to DMF to form a first solution with a metal ion concentration of 0.5 mol / L; Disperse the base in ethanol to form a second solution with a hydroxide concentration of 0.6 mol / L.

[0134] In addition, other parameters and steps remain unchanged.

[0135] Material Example 4

[0136] This material example is basically the same as Material Example 2, except that in this material example, the organic amine is changed to n-hexylamine. In addition, other parameters and steps remain unchanged.

[0137] Material Example 5

[0138] This material example is basically the same as Material Example 2, except that in this material example, the organic amine is changed to n-octylamine. In addition, other parameters and steps remain unchanged.

[0139] Material Example 6

[0140] This material example is basically the same as Material Example 2, except that in this material example, the organic amine is changed to octadecylamine. Other parameters and steps remain unchanged.

[0141] Material Example 7

[0142] This material example is basically the same as Material Example 2, except that in this material example, the molar ratio of Zn 2+ , OH - and the organic amine is 1:2:10. Other parameters and steps remain unchanged.

[0143] Material Example 8

[0144] This material example is basically the same as Material Example 2, except that in this material example, the molar ratio of Zn 2+ , OH - and the organic amine is 1:2:30. Other parameters and steps remain unchanged.

[0145] Material Example 9

[0146] This material example is basically the same as Material Example 2, except that in this material example, the molar ratio of Zn 2+ , OH - and the organic amine is 1:2:8. Other parameters and steps remain unchanged.

[0147] Material Example 10

[0148] This material example is basically the same as Material Example 2, except that in step 3) of this material example, the ligand compound zinc chloride is changed to oleic acid. Other parameters and steps remain unchanged.

[0149] Material Example 11

[0150] This material example is basically the same as Material Example 1, except that in this material example, the metal salt is titanium chloride. Other parameters and steps remain unchanged.

[0151] Material Comparative Example 1

[0152] This material comparative example is basically the same as Material Example 1, except that in this material comparative example, no organic amine is added, that is, the second solution is changed to: dispersing the base in ethanol to form a second solution with a hydroxide concentration of 0.6 mol / L. Other parameters and steps remain unchanged.

[0153] Material Comparative Example 2

[0154] This comparative example of the material is basically the same as Example 1 of the material, except that in this comparative example of the material, the organic amine is added after the metal salt and the base are mixed. Correspondingly, Steps 1 and 2 are changed to:

[0155] 1) Add the metal salt to DMF to form a first solution with a metal ion concentration of 0.5 mol / L; disperse the base in ethanol to form a second solution with a hydroxide concentration of 0.6 mol / L; wherein, the metal salt is zinc chloride, the base is sodium hydroxide, the organic amine is n-butylamine, and the first solvent is DMF and ethanol.

[0156] 2) Dropwise add the second solution to the first solution at room temperature, then add the organic amine, and continue to stir at 35 °C for 2 h to obtain a clear and transparent solution, wherein the molar ratio of Zn 2+ , OH - and the organic amine is 1:2:25. Add acetone to the clear and transparent solution, stir evenly and let it stand for precipitation, collect after centrifugation to obtain metal oxide nanoparticles (ZnO nanoparticles). Except for this, other parameters and steps remain unchanged.

[0157] Comparative Example 3 of the material

[0158] This comparative example of the material is basically the same as Example 11 of the material, except that in this comparative example of the material, no organic amine is added, that is, the second solution is changed to: disperse the base in ethanol to form a second solution with a hydroxide concentration of 0.6 mol / L. Except for this, other parameters and steps remain unchanged.

[0159] Device Example 1

[0160] (1) Clean the ITO anode substrate, and then treat it under UV conditions for 15 min;

[0161] (2) Spin-coat 50 nm thick PEDOT:PSS on the treated ITO substrate and bake it at 150 °C in an air atmosphere for 20 min to obtain a hole injection layer;

[0162] (3) Spin-coat a chlorobenzene solution of TFB on the hole transport layer, and then bake it at 180 °C in a nitrogen environment for 60 min to obtain a hole transport layer with a thickness of 40 nm;

[0163] (4) Spin-coat CdSeS quantum dots on the hole transport layer and bake it at 100 °C for 30 min to obtain a light-emitting layer.

[0164] (5) Spin-coat the metal oxide dispersion prepared in Example 1 of the material on the light-emitting layer and bake it at 80 °C for 30 min to obtain an electron transport layer with a thickness of 30 nm;

[0165] (6) A 70-nm-thick Al is vacuum-evaporated on the electron transport layer to obtain the cathode, and then the optoelectronic device is encapsulated.

[0166] Device Examples 2 to 11

[0167] The scheme of Device Example n is basically the same as that of Device Example 1, except that in Device Example n, step (5) is changed to spin-coating the metal oxide dispersion prepared in Material Example n on the light-emitting layer, where n is any integer from 2 to 11. Except for this, other parameters and steps remain unchanged.

[0168] Device Comparative Examples 1 to 3

[0169] The scheme of Device Comparative Example m is basically the same as that of Device Example 1, except that in Device Comparative Example m, step (5) is changed to spin-coating the metal oxide dispersion prepared in Material Comparative Example m on the light-emitting layer, where m is any integer from 1 to 3. Except for this, other parameters and steps remain unchanged.

[0170] Experimental Example

[0171] (I) Examine the performance of the metal oxide nanoparticles prepared in the above Material Examples 1-11 and Material Comparative Examples 1-3. The test methods are as follows:

[0172] Average particle size: detected by TEM;

[0173] Hydrodynamic particle size: characterized by a dynamic light scattering particle size analyzer to detect the particle size uniformity in the solution, which is used to characterize the size uniformity. Specifically, the detection results show that only when the particle size peak is a single peak or has fewer peaks, the uniformity is better, and the results show that when there are more particle size peaks or there are multiple discrete particle size values of larger sizes, the uniformity is worse;

[0174] Defect peak intensity: Use fluorescence emission spectroscopy to scan the metal oxide dispersions prepared in each example or comparative example, and record the intensity of the defect emission peak (appearing in the range of 490-520 nm), which can be used to characterize the amount of surface defects. The higher the defect peak intensity, the more surface defects;

[0175] Conductivity: detected by a conductivity tester.

[0176] The results are recorded in Table 1.

[0177] Table 1

[0178]

[0179]

[0180] As can be seen from the above table:

[0181] Comparing Material Examples 1 to 10 with Material Comparative Example 1 and Material Example 11 with Material Comparative Example 3, it can be seen that each material example has a larger size, lower defect peak intensity, and higher conductivity. At the same time, its hydrated particle size shows a single peak, indicating that the metal oxide nanoparticles prepared by the preparation method of the present application have the characteristics of large size, good uniformity, few surface defects, and good conductivity;

[0182] Furthermore, comparing Material Example 1 with Material Examples 2 to 10, Material Example 1 shows two particle size peaks in its hydrated particle size, while Material Examples 2 to 10 show a single peak, indicating that Material Example 2 has better size uniformity. By further performing ligand exchange on the metal oxide nanoparticles in the present application, it helps to further improve its size uniformity;

[0183] In addition, compared with Material Comparative Example 1, Material Comparative Example 2 does not show obvious changes in terms of size uniformity and conductivity except for having a lower defect peak intensity. This may be because the reaction activity between the base and the metal salt is relatively high, and the organic amine is added after the base and the metal salt are mixed. At this time, the base and the metal salt have already reacted, and the organic amine tends to modify the surface of the formed metal oxide and exists as a ligand. Therefore, although it reduces the surface defects to a certain extent, it does not significantly contribute to the size, size uniformity, and conductivity of the nanoparticles.

[0184] (2) Take the devices prepared in the above Device Examples 1 - 11 and Device Comparative Examples 1 - 3 for driving voltage, current efficiency, and T95@1000nit tests. The detection method refers to the conventional methods in the art, and the results are recorded in Table 2. Among them:

[0185] The lifetime T95@1000nit represents the time required for the device to reduce the brightness to a certain proportion of the maximum brightness under constant current or voltage drive. The time when the brightness drops to 95% of the maximum brightness is defined as T95, and this lifetime is the measured lifetime. To shorten the test cycle, the device lifetime test is usually carried out by accelerating the device aging at high brightness and fitting the high-brightness lifetime through an extended exponential decay brightness decay fitting formula. For example, the lifetime at 1000nit is denoted as T95@1000nit. The specific calculation formula is as follows:

[0186]

[0187] Among them, T95 L is the lifetime at low brightness, T95 H is the measured lifetime at high brightness, L H is the device accelerated to the maximum brightness, L LIt is 1000 nits, and A is the acceleration factor. In this experiment, the value of A is obtained as 1.7 by measuring the lifetimes of several groups of light-emitting devices at the rated brightness.

[0188] The detection method of the driving voltage @J10 is as follows: By measuring the trend of the device current changing with the voltage through the voltammetry method, the voltage at a current density of 10 mA / cm 2 is obtained.

[0189] Table 2

[0190]

[0191]

[0192] It can be seen from the above table that:

[0193] Compared with Comparative Examples 1 and 2 of the device, Examples 1 to 10 of the device have lower driving voltages, higher current efficiencies and longer service lives. At the same time, Example 11 of the device also has a lower driving voltage, higher current efficiency and longer service life than Comparative Example 3 of the device, indicating that the use of the metal oxide nanoparticles proposed in this application helps to improve the electrical performance of the device, reduce its driving voltage, and extend the service life of the device.

[0194] The above has introduced in detail the metal oxide nanoparticles, their preparation methods, optoelectronic devices and display devices provided in the embodiments of the present application. Specific examples are used in this article to elaborate on the principles and implementation manners of the present application. The descriptions of the above embodiments are only used to help understand the method and its core idea of the present application; at the same time, for those skilled in the art, based on the idea of the present application, there will be changes in the specific implementation manners and application scopes. In summary, the content of this specification should not be construed as a limitation to the present application.

Claims

1. A method for preparing metal oxide nanoparticles, characterized in that, Comprising the following steps: Providing a metal salt, an organic amine, a base, and a first solvent; Mixing the metal salt, the organic amine, the base, and the first solvent, and performing a first reaction to obtain metal oxide nanoparticles.

2. The preparation method according to claim 1, characterized in that, The step of mixing the metal salt, the organic amine, and the base includes: Mixing the organic amine with the metal salt, and then adding the base; or Mixing the base, the organic amine, and the metal salt.

3. The preparation method according to claim 1, characterized in that, The ratio of the molar amount of metal ions in the metal salt to the molar amount of the organic amine is 1:(10 - 30); and / or The temperature of the first reaction is 25 - 60 °C; and / or The time of the first reaction is 0.5 - 6 h; and / or The organic amine includes one or more of the compounds with the structural formula NR1R2R3, wherein R1, R2, and R3 are each independently selected from one or more combinations of hydrogen, deuterium, amino, halogen, hydroxyl, carboxyl, nitro, sulfonic acid group, aldehyde group, mercapto group, cyano group, unsubstituted or substituted C1 - C20 alkylene groups, unsubstituted or substituted C1 - C20 alkoxy groups, unsubstituted or substituted alicyclic hydrocarbon groups with 3 to 60 ring atoms, unsubstituted or substituted heterocyclic hydrocarbon groups with 3 to 60 ring atoms, unsubstituted or substituted aryl groups with 6 to 60 ring atoms, unsubstituted or substituted heteroaryl groups with 5 to 60 ring atoms, unsubstituted or substituted aryloxy groups with 6 to 60 ring atoms, and unsubstituted or substituted heteroaryloxy groups with 5 to 60 ring atoms; wherein, the heteroatoms in the heterocyclic hydrocarbon group, the heteroaryl group, or the heteroaryloxy group are one or more of N, S, O, P, and Si, and the number of heteroatoms is 1 - 20; each time the substituent appears, it is independently selected from one or more combinations of amino, halogen, hydroxyl, carboxyl, nitro, sulfonic acid group, aldehyde group, mercapto group, and cyano group.

4. The preparation method according to claim 3, characterized in that, The total number of carbon atoms contained in R1, R2, and R3 is 3 - 8; and / or Two of R1, R2, and R3 are selected from hydrogen; and / or R1, R2, and R3 are each independently selected from one of hydrogen and unsubstituted alkylene groups.

5. The preparation method according to claim 4, characterized in that, The organic amine includes one or more of n - propylamine, n - butylamine, n - pentylamine, n - hexylamine, n - heptylamine, and n - octylamine.

6. The preparation method according to any one of claims 2 to 5, characterized in that, The metal salt includes at least one of zinc salt, titanium salt, tin salt, zirconium salt, aluminum salt, copper salt, molybdenum salt, nickel salt, gallium salt, cobalt salt, manganese salt, and iron salt; and / or The base includes one or more of metal hydroxides and alkyl ammonium hydroxides. The metal hydroxides include one or more of sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, and barium hydroxide. The alkyl ammonium hydroxides include one or more of tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, and tetrapropyl ammonium hydroxide; and / or The first solvent includes one or more of dimethyl sulfoxide, N,N - dimethylformamide, and alcohol solvents.

7. The preparation method according to claim 6, characterized in that, The ratio of the molar amount of metal ions in the metal salt to the molar amount of hydroxide ions in the base is 1:(1.5 - 3.0).

8. The preparation method according to claim 1, characterized in that, The preparation method further includes: A second solvent and a ligand compound are provided; The metal oxide nanoparticles are dispersed in the second solvent to obtain a mixed solution; The mixed solution and the ligand compound are mixed to carry out a second reaction to obtain metal oxide nanoparticles with halogen atoms connected to the surface.

9. The preparation method according to claim 8, characterized in that, The ligand compound includes metal halides; and / or, The second solvent includes one or more of dimethyl sulfoxide, N,N-dimethylformamide, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, 3-methoxybutanol, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, and alcohol solvents.

10. The preparation method according to claim 9, characterized in that, The metal halides include one or more of zinc chloride, lithium chloride, aluminum chloride, zinc bromide, lithium bromide, aluminum bromide, zinc iodide, lithium iodide, aluminum iodide, zinc fluoride, lithium fluoride, and aluminum fluoride; and / or, The ratio of the molar amount of metal atoms in the metal oxide nanoparticles to the molar amount of halogen atoms in the metal halides is 1:(0.05 - 0.5); and / or, The temperature of the second reaction is 25 - 40 °C; and / or, The time of the second reaction is 10 - 120 min.

11. A metal oxide nanoparticle, characterized in that, It includes metal oxide nanoparticles prepared by the preparation method according to any one of claims 1 to 10.

12. The metal oxide nanoparticles according to claim 11, wherein, The metal oxide nanoparticles include at least one of zinc oxide, titanium oxide, tin oxide, zirconium oxide, aluminum oxide, copper oxide, molybdenum oxide, nickel oxide, gallium oxide, cobalt oxide, manganese oxide, and iron oxide; and / or, Halogen atoms are connected to the surface of the metal oxide nanoparticles.

13. An optoelectronic device, wherein, It includes an anode, a light functional layer, an electron functional layer, and a cathode. The material of the electron functional layer includes metal oxide nanoparticles prepared by the preparation method according to any one of claims 1 to 10, or includes the metal oxide nanoparticles according to claim 11 or 12.

14. The optoelectronic device according to claim 13, wherein, The materials of the optical functional layer include organic light-emitting materials or quantum dot light-emitting materials. The organic light-emitting materials are selected from one or more of 4,4'-bis(N-carbazolyl)-1,1'-biphenyl: tris[2-(p-tolyl)pyridineiridium(III)], 4,4',4”-tris(carbazol-9-yl)triphenylamine: tris[2-(p-tolyl)pyridineiridium, poly[(9,9-dioctylfluorene-2,7-diyl)-alt-(2,1,3-benzothiadiazole-4,7-diyl)], diarylanthracene derivatives, stilbene aromatic derivatives, pyrene derivatives, fluorene derivatives, TBPe fluorescent materials, TTPX fluorescent materials, TBRb fluorescent materials, DBP fluorescent materials, delayed fluorescence materials, TTA materials, thermally activated delayed materials, polymers containing B-N covalent bonds, hybrid local charge transfer excited state materials, exciplex luminescent materials. The quantum dot light-emitting materials are selected from at least one of single-structure quantum dots, core-shell structure quantum dots and perovskite semiconductor materials; the materials of the single-structure quantum dots, the core materials of the core-shell structure quantum dots and the shell materials of the core-shell structure quantum dots are respectively selected from at least one of II-VI group compounds, IV-VI group compounds, III-V group compounds and I-III-VI group compounds; the II-VI group compounds are selected from at least one of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe and HgZnSTe; the IV-VI group compounds are selected from at least one of SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, SnPbSeTe, SnPbSTe;The III-V compound is selected from the group consisting of GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, GaNP, GaNAs, GaNSb, GaPAs, GaPSb, and AlN P, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInN P, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs and InAlPSb; the I-III-VI group compound is selected from at least one of CuInS2, CuInSe2 and AgInS2; the perovskite semiconductor material is selected from doped or undoped inorganic perovskite semiconductors, or organic-inorganic hybrid perovskite semiconductors; the inorganic perovskite semiconductor has a general structural formula of AMX3, wherein A is Cs; + ion, M is a divalent metal cation selected from Pb 2+ Sn 2+ , Cu 2+ 、Ni 2+ 、Cd 2+ Cr 2+ , Mn 2+ 、Co 2+ , Fe 2+ ,Ge 2+ , Yb 2+ 、Eu 2+ At least one of, X is a halogen anion selected from Cl - Br - ,I - At least one of the following; the general structural formula of the organic-inorganic hybrid perovskite semiconductor is BMX3, wherein B is an organic amine cation selected from CH3(CH2) n-2 NH 3+ or [NH3(CH2) n NH3] 2+ , where n≥2, M is a divalent metal cation selected from Pb 2+ Sn 2+ , Cu 2+ 、Ni 2+ 、Cd 2+ Cr 2+ , Mn 2+ 、Co 2+ , Fe 2+ ,Ge 2+ , Yb 2+ 、Eu 2+ at least one of, X is a halogen anion, selected from Cl - , Br - , I - at least one of; and / or, The anode and the cathode are each independently selected from doped metal oxide particle electrodes, composite electrodes of metal and metal oxide, graphene electrodes, carbon nanotube electrodes, metal electrodes, or alloy electrodes. The material of the doped metal oxide particle electrode is selected from one or more of indium-doped tin oxide, fluorine-doped tin oxide, antimony-doped tin oxide, aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, magnesium-doped zinc oxide, and aluminum-doped magnesium oxide. The composite electrode of metal and metal oxide is selected from AZO / Ag / AZO, AZO / Al / AZO, ITO / Ag / ITO, ITO / Al / ITO, ZnO / Ag / ZnO, ZnO / Al / ZnO, TiO2 / Ag / TiO2, TiO2 / Al / TiO2, ZnS / Ag / ZnS, ZnS / Al / ZnS. The material of the metal electrode is selected from one or more of Ag, Al, Cu, Mo, Au, Pt, Si, Ca, Mg, and Ba.

15. A display device, wherein, The display device includes the optoelectronic device according to claim 13 or 14.

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