CN114085665B - Perovskite cluster solution, preparation method thereof and photoelectric device - Google Patents

Perovskite cluster solution, preparation method thereof and photoelectric device Download PDF

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CN114085665B
CN114085665B CN202111276301.3A CN202111276301A CN114085665B CN 114085665 B CN114085665 B CN 114085665B CN 202111276301 A CN202111276301 A CN 202111276301A CN 114085665 B CN114085665 B CN 114085665B
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perovskite
cluster
solution
clusters
rare earth
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CN114085665A (en
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薛冬峰
徐珂
王晓明
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Shenzhen Institute of Advanced Technology of CAS
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    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7704—Halogenides
    • C09K11/7705—Halogenides with alkali or alkaline earth metals
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    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
    • C09K11/7732—Halogenides
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    • H10K85/351—Metal complexes comprising lanthanides or actinides, e.g. comprising europium
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Abstract

The application belongs to the technical field of photoelectricity, and particularly relates to a perovskite cluster solution and a preparation method thereof, and a photoelectric device. The preparation method of the perovskite cluster solution comprises the following steps: preparing a precursor solution from lanthanide rare earth metal salt hydrate, organic carboxylic acid, organic amine ligand and perovskite raw material; and mixing the precursor solution with an antisolvent, and purifying to obtain a perovskite cluster solution. According to the preparation method of the perovskite cluster solution, the surface defects of the perovskite clusters are effectively passivated through the synergistic effect among the lanthanide series rare earth metal salt hydrate, the organic carboxylic acid and the organic amine ligand, the aggregation growth rate of the perovskite clusters is regulated and controlled, the stability of the perovskite clusters in the solution environment is improved, and the perovskite clusters with small size, strong stability and high fluorescence quantum yield are obtained.

Description

Perovskite cluster solution, preparation method thereof and photoelectric device
Technical Field
The application belongs to the technical field of photoelectricity, and particularly relates to a perovskite cluster solution and a preparation method thereof, and a photoelectric device.
Background
Nanoclusters are relatively stable microscopic or sub-microscopic aggregates of atoms or molecules that are bonded together by physical or chemical forces. Because of its small size and surface plasticity, it is becoming a hot spot for research in the fields of self-assembled materials, optoelectronic devices, biomarkers, medical treatment, solar cells, etc. The morphology of nanoclusters has a great influence on the electronic structure and optical properties thereof, and materials with specific properties can be designed by adjusting the microstructure of semiconductor nanoclusters. Meanwhile, the nanoclusters can be used as building blocks, and the super-structure material with good symmetry and geometric shape can be prepared through a conventional chemical route or other self-assembly strategies and can be further converted into the nano-material with a special structure.
Perovskite clusters act as polynuclear aggregates between perovskite material microstructures (atoms, molecules) and macroscopic substances (quantum dots, films and blocks), and are ideal models for correlating the two. Perovskite clusters have unique physicochemical properties such as quantum effect, high specific surface area (S/V), adjustable size and composition, and easy functionalization of surface defects, and are of great interest. The perovskite clusters show unique photoelectric properties of quantum materials, have wide application prospects in basic research and application, and particularly can be used for manufacturing larger-size nano structures, such as perovskite quantum dots or perovskite nanocrystals, and the like, and are applied to the aspects of biological imaging, blue Light Emitting Diodes (LEDs), sensors and the like. Therefore, understanding the new optical properties and evolution process mechanism of perovskite materials from the perovskite cluster evolution process can provide reference and theoretical basis for designing and manufacturing perovskite quantum function devices with excellent performance.
At present, in the design of an experimental scheme, perovskite clusters are generated in the process of molecular aggregation and bonding of a reaction system by selecting and regulating perovskite raw materials, surface passivation organic ligands, solvents and antisolvents, but the generated perovskite clusters are easy to cause the aggregation of the perovskite clusters due to a large number of surface defects and ligand dangling bonds, so that the perovskite clusters with uniform components are not favorable for reaction. The perovskite clusters synthesized at present cannot exist stably in a solvent for a long time, and are easy to agglomerate and degrade or continuously grow into perovskite nanocrystals with larger sizes. In addition, perovskite clusters are highly sensitive to the environment, are very unstable in natural environments, especially to H 2 O has a strong instability. Resulting in lower photoluminescence quantum yields of perovskite clusters.
Disclosure of Invention
The application aims to provide a perovskite cluster solution, a preparation method thereof and a photoelectric device, and aims to solve the problems that the existing perovskite clusters are easy to agglomerate and degrade, have poor stability and cannot be stably in a solvent for a long time to a certain extent.
In order to achieve the purposes of the application, the technical scheme adopted by the application is as follows:
In a first aspect, the present application provides a method of preparing a perovskite cluster solution comprising the steps of:
preparing a precursor solution from lanthanide rare earth metal salt hydrate, organic carboxylic acid, organic amine ligand and perovskite raw material;
and mixing the precursor solution with an antisolvent, and purifying to obtain a perovskite cluster solution.
In a second aspect, the present application provides a perovskite cluster solution in which the perovskite cluster surface is bound with an organic carboxylic acid and an organic amine ligand, and a molecular coating formed by a lanthanide rare earth metal salt hydrate.
In a third aspect, the present application provides an optoelectronic device comprising a perovskite cluster solution prepared by the above method, or a perovskite cluster solution as described above.
According to the preparation method of the perovskite cluster solution provided by the first aspect of the application, lanthanide rare earth metal salt hydrate, organic carboxylic acid and organic amine ligand are simultaneously added into the prepared perovskite precursor solution, wherein strong coordination action of carbonyl groups and octahedral center cations in the organic carboxylic acid and intermolecular action force between carboxylic acid alkyl chains can be reduced, and the [ BX 6 ]The driving force of octahedral aggregation inhibits the rapid aggregation of the octahedron and passivates the cationic defects on the surface of perovskite clusters. The organic amine ligand can be bonded with anions at the edge of the octahedron through electrostatic attraction to passivate the anion defects on the surface of the perovskite cluster to form an organic spacing layer, so that the dielectric constant of the spacing layer is mismatched with that of the octahedral sheet, thereby leading [ BX 6 ]The octahedral layer forms a natural quantum well, and improves the migration efficiency of carriers in perovskite clusters. The lanthanide rare earth metal ions in the lanthanide rare earth metal salt hydrate can be combined with halogen ion defects on the surface of the perovskite clusters, the acid radical ions can be combined with metal ion defects on the surface of the perovskite clusters, and a planar molecular coating layer with the lanthanide rare earth metal ions, acid radical ions, water molecules and hydroxyl ions is formed on the surface of the perovskite clusters. Not only further passivates the surface defects of perovskite clusters, but also inhibits the aggregation growth of the perovskite clusters; and the formed molecular coating layer can effectively block the entry of external water molecules through crystallizing the water moleculesAnd (5) invasion. Thereby not only improving the aggregation phenomenon of the perovskite clusters, inhibiting the perovskite clusters from being quickly aggregated to grow into perovskite materials such as perovskite quantum dots, films or blocks with larger sizes, and the like, but also improving the resistance of the perovskite clusters to inherent instability factors such as water, oxygen, illumination, and the like in the environment.
In the perovskite cluster solution provided by the second aspect of the application, the surface of the perovskite cluster is combined with organic carboxylic acid and organic amine ligand, and a molecular coating layer formed by lanthanide rare earth metal salt hydrate; wherein the organic carboxylic acid passivates the cationic defect on the surface of the perovskite cluster, the organic amine ligand passivates the anionic defect on the surface of the perovskite cluster, the lanthanide rare earth metal ions in the lanthanide rare earth metal salt hydrate can be combined with the halogen ion defect on the surface of the perovskite cluster, the acid radical ions can be combined with the metal ion defect on the surface of the perovskite cluster, and a planar molecular coating layer with the lanthanide rare earth metal ions, acid radical ions, water molecules and hydroxyl ions is formed on the surface of the perovskite cluster. The surface defects of the perovskite clusters are effectively passivated through the synergistic effect among lanthanide rare earth metal salt hydrate, organic carboxylic acid and organic amine ligand, the aggregation growth rate of the perovskite clusters is regulated and controlled, the stability of the perovskite clusters in a solution environment is improved, and the perovskite clusters with small size, strong stability and high fluorescence quantum yield are obtained.
The photoelectric device provided by the third aspect of the application comprises the perovskite cluster solution, wherein the surface of the perovskite cluster is combined with the organic carboxylic acid and the organic amine ligand and the molecular coating layer formed by the lanthanide rare earth metal salt hydrate, so that the stability and fluorescence quantum yield of the perovskite cluster are improved, the agglomeration phenomenon is improved, the adaptability of the perovskite cluster in the solution storage environment is improved, the perovskite cluster which is stable in the solution is small in size and uniform in size distribution, the small-size perovskite cluster has a discrete energy level structure, the color purity and the optical stability of the perovskite cluster are improved, and the photoluminescence quantum yield of the perovskite cluster is improved, thereby improving the photoelectric performance of the photoelectric device.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments or the description of the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic flow chart of a method for preparing a perovskite cluster solution according to an embodiment of the application;
FIG. 2 is a schematic diagram of the structure of perovskite clusters in a perovskite cluster solution provided by an embodiment of the application;
FIG. 3 is an ultraviolet absorption spectrum and a fluorescence emission spectrum of a perovskite cluster solution provided in example 1 of the present application;
FIG. 4 is an electron microscopy morphology graph (left) and particle size distribution histogram (right) of the perovskite cluster solution provided in example 2 of the present application;
FIG. 5 is a graph of fluorescence emission spectral intensities of the perovskite cluster solution provided by example 3 of the application and the perovskite material provided by comparative example 1;
fig. 6 is a graph of fluorescence quantum yields of perovskite cluster solutions provided by example 1 of the application and perovskite materials provided by comparative example 1.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved more clear, the application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the application.
In the present application, the term "and/or" describes an association relationship of an association object, which means that three relationships may exist, for example, a and/or B may mean: a alone, a and B together, and B alone. Wherein A, B may be singular or plural. The character "/" generally indicates that the context-dependent object is an "or" relationship.
In the present application, "at least one" means one or more, and "a plurality" means two or more. "at least one of" or the like means any combination of these items, including any combination of single item(s) or plural items(s). For example, "at least one (individual) of a, b, or c," or "at least one (individual) of a, b, and c" may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, c may be single or multiple, respectively.
It should be understood that, in various embodiments of the present application, the sequence number of each process described above does not mean that the execution sequence of some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its functions and internal logic, and should not constitute any limitation on the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in this application and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The amounts of the related components mentioned in the description of the embodiments of the present application may refer not only to the specific contents of the components, but also to the proportional relation of the amounts of the components, and thus, it is within the scope of the disclosure of the embodiments of the present application as long as the amounts of the related components are scaled up or down according to the embodiments of the present application.
The terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated for distinguishing between objects such as substances from each other. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of embodiments of the application. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature.
As shown in fig. 1, a first aspect of the embodiment of the present application provides a method for preparing a perovskite cluster solution, which includes the following steps:
s10, preparing a lanthanide rare earth metal salt hydrate, organic carboxylic acid, an organic amine ligand and perovskite raw materials into a precursor solution;
s20, mixing the precursor solution with an antisolvent, and purifying to obtain a perovskite cluster solution.
According to the preparation method of the perovskite cluster solution provided by the first aspect of the embodiment of the application, lanthanide rare earth metal salt hydrate, organic carboxylic acid and organic amine ligand are simultaneously added into the perovskite precursor solution, wherein strong coordination effect of carbonyl groups and octahedral center cations in the organic carboxylic acid and intermolecular acting force between carboxylic acid alkyl chains can be reduced [ BX 6 ]The driving force of octahedral aggregation inhibits the rapid aggregation of the octahedron and passivates the cationic defects on the surface of perovskite clusters. The organic amine ligand can be bonded with anions at the edge of the octahedron through electrostatic attraction to passivate the anion defects on the surface of the perovskite cluster to form an organic spacing layer, so that the dielectric constant of the spacing layer is mismatched with that of the octahedral sheet, thereby leading [ BX 6 ]The octahedral layer forms a natural quantum well, and improves the migration efficiency of carriers in perovskite clusters. The lanthanide rare earth metal ions in the lanthanide rare earth metal salt hydrate can be combined with halogen ion defects on the surface of the perovskite clusters, the acid radical ions can be combined with metal ion defects on the surface of the perovskite clusters, and a planar molecular coating layer with the lanthanide rare earth metal ions, acid radical ions, water molecules and hydroxyl ions is formed on the surface of the perovskite clusters. Not only further passivates the surface defects of perovskite clusters, but also inhibits the aggregation growth of the perovskite clusters; and the formed molecular coating layer can effectively block invasion of external water molecules through crystallizing the water molecules. Thereby not only improving the aggregation phenomenon of the perovskite clusters, inhibiting the perovskite clusters from being quickly aggregated to grow into perovskite materials such as perovskite quantum dots, films or blocks with larger sizes, and the like, but also improving the resistance of the perovskite clusters to inherent instability factors such as water, oxygen, illumination, and the like in the environment. The perovskite cluster solution prepared by the embodiment of the application is effective through the synergistic effect among lanthanide rare earth metal salt hydrate, organic carboxylic acid and organic amine ligand Surface defects of the perovskite clusters are passivated, the aggregation growth rate of the perovskite clusters is regulated, and the stability of the perovskite clusters in a solution environment is improved. Perovskite clusters in the perovskite cluster solution can stably exist in the solution system, the perovskite clusters are small in size and about 1-3 nm, and the size distribution is highly uniform. Compared with a large-size perovskite material, the small-size perovskite cluster has a discrete energy level structure, can show unique photoelectric properties such as blue-shift absorption and emission spectrum, improves the color purity and optical stability of the perovskite cluster, improves the photoluminescence quantum yield of the perovskite cluster, and is expected to develop potential application in the fields of ultra-micro photoelectric devices, biological imaging, fluorescent labeling, new generation high-property catalysts and the like.
In some embodiments, in step S10 described above, the lanthanide rare earth metal salt hydrate, the organic carboxylic acid, the organic amine ligand, and the perovskite starting material are formulated into a precursor solution, wherein the perovskite starting material comprises a divalent metal halide and an organic ammonium halide or alkali metal halide. The perovskite cluster prepared by the embodiment of the application consists of A, B and X three ions in perovskite raw materials participating in synthesis, wherein the A position is usually at least one of inorganic or organic cations, such as Cs + Or Rb + Iso monovalent inorganic cations such as Methylamine (MA) + ，CH 3 NH 3 + ) Ethylamine (EA) + ，CH 3 CH 2 NH 3 + ) Or Formamidine (FA) + ，CH(NH 2 ) 2 + ) At least one kind of monovalent organic cations such as ion; the B-position is usually a divalent metal cation, e.g. Pb 2+ 、Sn 2+ 、Ge 2+ 、Ga 2+ 、Cu 2 + 、Ni 2+ 、Co 2+ And Mn of 2+ Etc.; the X position is typically a monovalent halogen, e.g. I - 、Br - 、Cl - 、F - Etc. can also be pseudohalogen anions, e.g. SCN - And BF 4 - Etc., the precise structural composition of the perovskite clusters is not yet known. The divalent metal cation at the B-position is coordinated with the halogen ion at the X-position to form [ BX ] 6 ]Octahedron, inorganic in A-position orThe organic cations are distributed in the gaps generated by the octahedral co-roof connection, and the coordination number is 12.
In some embodiments, the lanthanide rare earth metal salt hydrate is selected from: trivalent lanthanide rare earth metal hydrated nitrates, useful in the general chemical formula M (NO 3 ) 3 ·XH 2 O represents, wherein M is trivalent lanthanide rare earth metal, and X is the number of crystal water. The trivalent lanthanide rare earth metal ions have better combination property with halogen defects on the surface of the perovskite clusters, the nitrate ions have better combination property with metal ion defects on the surface of the perovskite clusters, and the monovalent, divalent and other metal ions have poor passivation effect on the perovskite clusters, so that the clusters are clustered to form perovskite quantum dots.
In some embodiments, the trivalent lanthanide rare earth metal hydrated nitrate includes ytterbium (III) nitrate pentahydrate Yb (NO) 3 ) 3 ·5H 2 Dy (NO) hexahydrate of O, dysprosium (III) nitrate 3 ) 3 ·6H 2 O, europium (III) nitrate hexahydrate Eu (NO) 3 ) 3 ·5H 2 O, samarium (III) nitrate hexahydrate Sm (OH) 3 ·6H 2 Praseodymium (III) nitrate hexahydrate Pr (NO) 3 ) 3 ·6H 2 At least one of O, further preferably ytterbium (III) nitrate pentahydrate Yb (NO) 3 ) 3 ·5H 2 O, europium (III) nitrate hexahydrate Eu (NO) 3 ) 3 ·5H 2 O, samarium (III) nitrate hexahydrate Sm (OH) 3 ·6H 2 O, etc. Yb in these trivalent lanthanide rare earth metal hydrated nitrates 3+ 、Dy 3+ 、Eu 3+ 、Sm 3+ 、Pr 3+ I of the trivalent lanthanide rare earth metal ion and perovskite cluster surface - 、Br - 、Cl - 、F - Halogen ions or SCN - And BF 4 - Pseudohalogen anion defects combine, nitrate ions can be combined with Pb on the surface of perovskite clusters 2+ 、Sn 2+ 、Ge 2+ 、Ga 2+ 、Cu 2+ 、Ni 2+ 、Co 2+ And Mn of 2+ Plasma metal ion defect combination and formation of rare earth with trivalent lanthanide series on the surface of perovskite clusterA planar molecular coating of earth metal ions, nitrate ions, water molecules and hydroxyl ions. Not only further passivates the surface defects of perovskite clusters, but also inhibits the aggregation growth of the perovskite clusters; and the formed molecular coating layer can effectively block invasion of external water molecules through crystallizing the water molecules. Thereby not only improving the aggregation phenomenon of the perovskite clusters, inhibiting the perovskite clusters from being quickly aggregated to grow into perovskite materials such as perovskite quantum dots, films or blocks with larger sizes, and the like, but also improving the resistance of the perovskite clusters to inherent instability factors such as water, oxygen, illumination, and the like in the environment.
In some embodiments, the lanthanide rare earth salt hydrate is added in a molar ratio to the halogenated divalent metal of (1-2): (3-10), the addition amount effectively ensures passivation and stabilization effects of lanthanide rare earth metal salt hydrate on the surface of the perovskite cluster, so that the perovskite cluster stably exists in a small-size form in the solution, and the subsequent application of the perovskite cluster is facilitated. If the addition amount of the lanthanide rare earth metal salt hydrate is too low, the perovskite clusters are unfavorable for passivation and stability, are easy to agglomerate into perovskite quantum dots, films or blocks and other large-size perovskite materials, have poor stability, and are easy to decompose and deteriorate under the influence of factors such as water, oxygen and the like in the environment. If the addition amount of the lanthanide rare earth metal salt hydrate is too high, a large amount of water molecules are introduced into the system, which is not beneficial to the generation of perovskite clusters, and in addition, too much lanthanide rare earth metal salt hydrate cannot be completely dissolved in the precursor solvent, which is also not beneficial to the obtaining of high-purity perovskite clusters. In some embodiments, the molar ratio of lanthanide rare earth metal salt hydrate added to halogenated divalent metal includes, but is not limited to, 1: (3-10), 1: (4-9), 1: (5-8), 1: (6-7), 2: (3-10), 2: (4-9), 2: (5-8), 2: (6-7), and the like.
In some embodiments, the organic carboxylic acid comprises at least one of propionic acid, n-butyric acid, n-valeric acid, octadecenoic acid, benzoic acid, phenylacetic acid, further preferably octadecenoic acid or phenylacetic acid, or octadecenoic acid and phenylacetic acid. Embodiments of the application the organic carboxylic acids added to the precursor solution contain carbonyl groupsCan form strong coordination with octahedral center cation, and intermolecular force is also present between carboxylic acid alkyl chains, so that [ BX can be reduced 6 ]The driving force of the octahedral aggregation inhibits the rapid aggregation of the octahedron, passivates the cationic defect on the surface of the perovskite cluster, and inhibits the rapid aggregation of the perovskite cluster to grow into perovskite quantum dots, films or blocks and other perovskite materials with larger sizes.
In some embodiments, the ratio of the amount of organic carboxylic acid added to the molar amount of halogenated divalent metal in the perovskite starting material in the precursor solution is (2-10): 1, the ratio can not only effectively passivate the surface of perovskite clusters, regulate and control the agglomeration rate of the perovskite clusters, and enable perovskite in the solution to maintain the cluster morphology; and the solution system has proper pH value, the pH value is about 5, and the lanthanide rare earth metal salt hydrate is favorable for forming a planar molecular coating layer of lanthanide rare earth metal ions, acid radical ions, water molecules and hydroxyl ions on the surface of the perovskite cluster. If the addition amount of the organic carboxylic acid in the precursor solution is excessive, the acid-base balance of a reaction system is destroyed, and the formation of perovskite clusters is excessively inhibited, so that the perovskite clusters are difficult to generate in the reaction, and the perovskite materials in the solution are maintained in the microstructure of molecules or atoms; if the addition amount of the organic carboxylic acid in the precursor solution is too small, the surface of the perovskite cluster is not easy to be passivated, and the perovskite cluster is easy to be quickly agglomerated and grown into a large-size perovskite quantum dot, a thin film or a block and other macroscopic structures, so that the perovskite cluster cannot be obtained. In some embodiments, the ratio of the amount of organic carboxylic acid added to the molar amount of halogenated divalent metal in the perovskite starting material in the precursor solution includes, but is not limited to (2-10): 1. (3-9): 1. (4-8): 1. (5-7): 1. (3-6): 1. ((6-9): 1, etc., preferably (4-8): 1).
In some embodiments, the organic amine ligand comprises at least one of stearylamine, benzylamine, phenethylamine, further preferably stearylamine or phenethylamine, or preferably stearylamine and phenethylamine. The organic ligands added in the precursor solution of the embodiment of the application can not only be bonded with anions of octahedral edges through electrostatic attraction to passivate the calcium titaniumAnion defects on the surface of the ore clusters further regulate the aggregation growth rate of the perovskite clusters, and simultaneously form an organic spacing layer, so that the dielectric constant of the spacing layer is mismatched with that of an octahedral sheet layer, thereby ensuring that [ BX 6 ]The octahedral layer forms a natural quantum well, and improves the migration efficiency of carriers in perovskite clusters.
In some embodiments, the molar ratio of organic amine ligand to halogenated divalent metal is (1-10): 1, a step of; the dosage proportion of the organic amine ligand can effectively regulate and control the perovskite structure and the cluster aggregation growth rate at the same time. If the addition amount of the organic amine ligand in the precursor solution is too low, the perovskite structure and the aggregation rate of clusters are not beneficial to be regulated; if the amount of organic amine ligand added in the precursor solution is too high, perovskite cluster formation is likewise not favored. In some embodiments, the molar ratio of organic amine ligand to halogenated divalent metal includes, but is not limited to (1-10): 1. (2-9): 1. (3-8): 1. (4-7): 1. (5-6): 1, etc. (2-8): 1 is preferable.
In some embodiments, the divalent metal halide comprises at least one of lead halide, tin halide, germanium halide, gallium halide, nickel halide, manganese halide, cobalt halide, copper halide; these divalent metal halides can self-assemble with organic ammonium halides or alkali halides, introducing divalent metal ions of lead, tin, germanium, gallium, nickel, cobalt, manganese, copper, etc., into the perovskite cluster structure. In some preferred embodiments, the divalent metal halide is selected from at least one of lead halides, tin halides, such as lead chloride, lead bromide, lead iodide, tin chloride, tin bromide, tin iodide, and the like.
In some embodiments, the organic ammonium halide includes CH 3 NH 3 Cl、CH 3 NH 3 Br、CH 3 NH 3 I、CH 2 (NH 3 ) 2 Cl、CH 2 (NH 3 ) 2 Br、CH 2 (NH 3 ) 2 I、CH 3 CH 2 NH 3 Cl、CH 3 CH 2 NH 3 Br、CH 3 CH 2 NH 3 At least one of I; these organic ammonium halides can form perovskite materials after self-assembly with divalent metal halides, perovskite materialsIntroduction of CH into the feed 3 NH 3 + 、CH 2 (NH 3 ) 2 + 、CH 2 CH 2 NH 3 + The organic ammonium ions can effectively improve the thermal stability of the perovskite material.
In some embodiments, the alkali halide comprises at least one of CsCl, csBr, csI, rbCl, rbBr, rbI; these alkali halides form perovskite materials by self-assembly with divalent halides, into which Cs are incorporated + 、Rb + The alkali metal ions can effectively improve the thermal stability of the perovskite material.
In some embodiments, the organic solvent comprises at least one of dimethyl sulfoxide and N, N-dimethylformamide, and the solvent has good dissolving and dispersing effects on organic carboxylic acid, organic amine ligand, perovskite raw materials and the like. In some embodiments, the organic solvent comprises dimethyl sulfoxide and N, N-dimethylformamide, further, the volume ratio of dimethyl sulfoxide to N, N-dimethylformamide is (1-9): (1-9). The mixed organic solvent adopted by the embodiment of the application has good dissolving effect on the raw material components, and is beneficial to mutual contact reaction between the components; but also is beneficial to regulating and controlling the growth rate and orientation of perovskite. Specifically, the s=o bond in dimethyl sulfoxide is easily coordinated with the B-site cation in perovskite to form an intermediate, preventing perovskite [ BX 6 ]Octahedron such as [ PbI ] 6 ]Etc. N, N-dimethylformamide is a good solvent for perovskite precursors, and its action is similar to that of dimethyl sulfoxide, but in which the c=o and B cations have weak action and low boiling point, and the effect on perovskite cluster formation is poor. Therefore, a mixed solvent of dimethyl sulfoxide and N, N-dimethylformamide is used. In some specific embodiments, the volume ratio of dimethyl sulfoxide to N, N-dimethylformamide includes, but is not limited to, 9:1, 4:1, 7:3, 3:2, 1:1, 2:3, 3:7, 1:4, 1:9, etc., preferably 2:3, 1:1 or 1:4.
In some embodiments, the step of configuring the precursor solution includes: after dissolving perovskite raw materials in an organic solvent, mixing and stirring for 10-30 minutes at room temperature, adding lanthanide rare earth metal salt hydrate, organic carboxylic acid and organic amine ligand, stirring for 0.5-2 hours at 30-55 ℃, and fully dissolving to obtain a precursor solution. In some embodiments, when preparing the precursor solution, the ratio of the amounts of the divalent metal halide and the organic ammonium halide or alkali metal halide species in the perovskite starting material may be 1: (0.2 to 5), more preferably 1: (0.5-3). In some embodiments, the initial concentration of the halogenated divalent metal in the organic solvent is preferably 0.03 to 0.1mol/L.
In some embodiments, in the step S20, the precursor solution and the antisolvent are mixed for 1-3 minutes, and the aggregation rate of the perovskite clusters is synergistically controlled by the organic carboxylic acid, the organic amine ligand and the lanthanide rare earth metal salt hydrate, that is, the perovskite clusters with small size and high uniformity of particle size distribution are generated in the solution.
In some embodiments, the antisolvent comprises at least one of n-hexane, toluene, dichloromethane, chloroform, further preferably toluene or chloroform, or preferably toluene and chloroform; the antisolvents can promote the perovskite raw material components in the precursor solution to react with each other to form a microscopic perovskite material, the microscopic perovskite material continues to grow to form perovskite clusters of polynuclear aggregates, and the surfaces of the clusters are combined with organic ligands, organic carboxylic acids and a planar molecular coating layer formed by lanthanide rare earth metal salt hydrate and provided with lanthanide rare earth metal ions, acid radical ions, water molecules and hydroxyl ions, so that the perovskite clusters have good stability.
In some embodiments, the volume ratio of precursor solution to antisolvent is (0.2-4): (5-35); further, (0.5 to 3): (10-20). Different supersaturation degrees are realized through the volume ratios of different precursor solutions and antisolvents, so that the generated size and number of perovskite materials are changed, and the reaction system is controlled to slowly generate small-size perovskite clusters.
In some embodiments, the step of purifying comprises: and (3) centrifuging the mixed solution after the mixing treatment, and removing a series of impurities in the solution by selecting a proper centrifugal rotating speed, such as: unreacted perovskite raw component, organic amine, organic carboxylic acid and lanthanide rare earth metal salt hydrate, and collecting supernatant to obtain perovskite cluster solution. In some embodiments, the mixed solution after the mixing treatment is centrifuged for 3 to 4 times under the condition that the rotational speed of centrifugal separation is 2000 to 12000r/min, the collected product is supernatant fluid after each centrifugation, and further preferably the rotational speed is 6000 to 10000r/min, and the obtained perovskite cluster solution is stored in a refrigerator at a low temperature (0 to 5 ℃).
As shown in fig. 2, a second aspect of the embodiment of the present application provides a perovskite cluster solution in which the perovskite cluster surface is combined with an organic carboxylic acid and an organic amine ligand, and a lanthanide rare earth metal salt hydrate forms a molecular coating layer.
In the perovskite cluster solution provided by the second aspect of the embodiment of the application, the surface of the perovskite cluster is combined with organic carboxylic acid, organic amine ligand and a molecular coating layer formed by lanthanide rare earth metal salt hydrate; wherein the organic carboxylic acid passivates the cationic defect on the surface of the perovskite cluster, the organic amine ligand passivates the anionic defect on the surface of the perovskite cluster, the lanthanide rare earth metal ions in the lanthanide rare earth metal salt hydrate can be combined with the halogen ion defect on the surface of the perovskite cluster, the acid radical ions can be combined with the metal ion defect on the surface of the perovskite cluster, and a planar molecular coating layer with the lanthanide rare earth metal ions, acid radical ions, water molecules and hydroxyl ions is formed on the surface of the perovskite cluster. The surface defects of the perovskite clusters are effectively passivated through the synergistic effect among lanthanide rare earth metal salt hydrate, organic carboxylic acid and organic amine ligand, the aggregation growth rate of the perovskite clusters is regulated and controlled, the stability of the perovskite clusters in a solution environment is improved, and the perovskite clusters with small size, strong stability and high fluorescence quantum yield are obtained.
The perovskite cluster solution of the embodiment of the present application can be prepared by the method of the above embodiment.
In some embodiments, the perovskite clusters in the perovskite cluster solution have a particle size of 1-3 nm, and the size range can be basically determined as pure perovskite clusters, and the perovskite clusters cannot be generated when the perovskite clusters are too small, and quantum dots with large flake or sphere sizes can be easily generated when the perovskite clusters are too large. The perovskite clusters in the perovskite cluster solution can stably exist in the solution system, the perovskite clusters are small in size and uniform in size distribution, and the optical characteristics of strong ionization, high surface energy, high quantum effect and the like of the perovskite clusters are ensured. Compared with a large-size perovskite material, the small-size perovskite cluster has a discrete energy level structure, can show blue-shift absorption and emission spectrum and other unique photoelectric properties, improves the color purity and optical stability of the perovskite cluster, and is expected to develop potential application in the fields of ultra-micro photoelectric devices, biological imaging, fluorescent labeling, new generation high-property catalysts and the like. In some embodiments, the particle size of the perovskite cluster solution may be 1nm to 2nm, 2 to 3nm, etc.
In some embodiments, the organic ligand comprises at least one of stearylamine, benzylamine, phenethylamine, and by selecting an appropriate organic ligand, it is possible to passivate and reduce the halogen anion defects on the surface of perovskite clusters, inhibit the growth of perovskite clusters, and maintain the perovskite clusters in solution.
In some embodiments, the lanthanide rare earth salt hydrate includes Yb (NO 3 ) 3 ·5H 2 O、Dy(NO 3 ) 3 ·6H 2 O、Eu(NO 3 ) 3 ·5H 2 O、Sm(OH) 3 ·6H 2 O、Pr(NO 3 ) 3 ·6H 2 At least one trivalent lanthanide rare earth metal hydrated nitrate in O; among the lanthanide rare earth metal salt hydrates, trivalent lanthanide rare earth metal ions have better binding performance with halogen defects on the surface of the perovskite cluster, and nitrate ions have better binding performance with metal ion defects on the surface of the perovskite cluster.
In some embodiments, the organic carboxylic acid comprises at least one of propionic acid, n-butyric acid, n-valeric acid, octadecenoic acid, benzoic acid, phenylacetic acid; these organic carboxylic acids can form strong coordination with octahedral center cations, and intermolecular forces exist between carboxylic acid alkyl chains, so that [ BX ] can be reduced 6 ]Driving force for octahedral aggregation, inhibiting rapid aggregation of octahedron, passivating perovskite cluster tableThe surface cation defect inhibits perovskite clusters from being quickly agglomerated and grown into perovskite materials such as perovskite quantum dots, films or blocks with larger sizes.
A third aspect of the embodiments of the present application provides an optoelectronic device comprising a perovskite cluster solution prepared by the above method, or a perovskite cluster solution as described above.
The photoelectric device provided by the third aspect of the embodiment of the application comprises the perovskite cluster solution, wherein the surface of the perovskite cluster is combined with the organic carboxylic acid and the organic amine ligand and the molecular coating layer formed by the lanthanide rare earth metal salt hydrate, so that the stability and fluorescence quantum yield of the perovskite cluster are improved, the agglomeration phenomenon is improved, the adaptability of the perovskite cluster in a solution storage environment is improved, the perovskite cluster which is stable in the solution is small in size and uniform in size distribution, the small-size perovskite cluster has a discrete energy level structure, the color purity and the optical stability of the perovskite cluster are improved, and the photoluminescence quantum yield of the perovskite cluster is improved, thereby improving the photoelectric performance of the photoelectric device.
In some embodiments, the optoelectronic devices include, but are not limited to, perovskite solar cells, light Emitting Diodes (LEDs), photodetectors, visible light communication devices, and the like.
In order that the details and operation of the above-described embodiments of the present application may be clearly understood by those skilled in the art, and that the improved performance of the perovskite cluster solution and the preparation method thereof according to the embodiments of the present application may be significantly embodied, the above-described embodiments are exemplified by the following examples.
Example 1
A perovskite cluster solution, the preparation of which comprises the steps of:
(1) the mass ratio of the materials is 1:1 cesium bromide (CsBr) and lead bromide (PbBr) 2 ) Dissolving in dimethyl sulfoxide (DMSO) solvent, and stirring to dissolve completely; the initial concentration of lead bromide was 0.04mol/L, with a volume of solvent of 1.0mL; then Yb (NO) 3 ) 3 ·5H 2 O, octadecenoic acid and octadecenamide and stirring at 30℃for 1h, wherein Yb (NO 3 ) 3 ·5H 2 The ratio of the addition amount of O to the amount of the lead bromide substance is 1:1, and the ratio of the addition amount of the octadecenamide to the amount of the lead bromide substance is 2:1, preparing a precursor solution of perovskite clusters, wherein the ratio of the addition amount of octadecenoic acid to the amount of lead bromide substance is 4:1;
(2) injecting the perovskite cluster precursor solution into toluene according to the volume ratio of 0.5:10, rapidly stirring at room temperature for about 2 minutes, centrifuging the mixed solution at the speed of 10000r/min for 10 minutes, centrifuging for 3 times, collecting the product as supernatant fluid after each centrifugation, obtaining the perovskite cluster solution, and finally storing the obtained perovskite cluster solution in a refrigerator at low temperature (0-5 ℃) for standby, wherein the particle size of the perovskite clusters is 1.5-2.5 nm.
Example 2
A perovskite cluster solution, the preparation of which comprises the steps of:
(1) The mass ratio of the materials is 1:1 cesium bromide (CsBr) and lead bromide (PbBr) 2 ) Dissolving in N, N-Dimethylformamide (DMF) solvent, and stirring to completely dissolve; the initial concentration of lead bromide was 0.04mol/L, with a volume of solvent of 1.0mL; then Yb (NO) 3 ) 3 ·5H 2 O, phenylacetic acid and phenethylamine and stirred at 30℃for 1h, wherein Yb (NO 3 ) 3 ·5H 2 The ratio of the addition amount of O to the amount of the lead bromide substance is 1:1, and the ratio of the addition amount of phenethylamine to the amount of the lead bromide substance is 2:1, preparing a precursor solution of perovskite clusters, wherein the ratio of the addition amount of phenylacetic acid to the amount of lead bromide substance is 4:1;
(2) injecting the perovskite cluster precursor solution into toluene according to the volume ratio of 0.5:10, rapidly stirring at room temperature for about 2 minutes, centrifuging the mixed solution at the speed of 10000r/min for 10 minutes, centrifuging for 3 times, collecting the product as supernatant fluid after each centrifugation, obtaining the perovskite cluster solution, and finally storing the obtained perovskite cluster solution in a refrigerator at low temperature (0-5 ℃) for standby, wherein the particle size of the perovskite clusters is 1.7-2.1 nm.
Example 3
A perovskite cluster solution, the preparation of which comprises the steps of:
(1) the mass ratio of the materials is 1:1 cesium bromide (CsBr)) And lead bromide (PbBr) 2 ) Dissolving in a mixed solvent of dimethyl sulfoxide (DMSO) and N, N-Dimethylformamide (DMF) in a volume ratio of 1:1, and stirring until the mixture is completely dissolved; the initial concentration of lead bromide was 0.04mol/L, with a volume of solvent of 1.0mL; then Yb (NO) 3 ) 3 ·5H 2 O, octadecenoic acid and octadecenamide and stirring at 30℃for 1h, wherein Yb (NO 3 ) 3 ·5H 2 The ratio of the addition amount of O to the amount of the lead bromide substance is 1:1, and the ratio of the addition amount of the octadecenamide to the amount of the lead bromide substance is 2:1, preparing a precursor solution of perovskite clusters, wherein the ratio of the addition amount of octadecenoic acid to the amount of lead bromide substance is 4:1;
(2) injecting the perovskite cluster precursor solution into chloroform according to the volume ratio of 3:20, rapidly stirring at room temperature for about 2 minutes, centrifuging the mixed solution at the speed of 10000r/min for 10 minutes, centrifuging for 3 times, collecting the supernatant fluid after each centrifugation, obtaining the perovskite cluster solution, and finally storing the obtained perovskite cluster solution in a refrigerator at low temperature (0-5 ℃) for standby, wherein the particle size of the perovskite clusters is 2.0-3.0 nm.
Example 4
A perovskite cluster solution, the preparation of which comprises the steps of:
(1) the mass ratio of the materials is 1:1 cesium bromide (CsBr) and lead bromide (PbBr) 2 ) Dissolving in dimethyl sulfoxide (DMSO) solvent, and stirring to dissolve completely; the initial concentration of lead bromide was 0.04mol/L, with a volume of solvent of 1.0mL; then, eu (NO) 3 ) 3 ·5H 2 O, octadecenoic acid and octadecenamide and stirring at 30deg.C for 1h, wherein Eu (NO 3 ) 3 ·5H 2 The ratio of the addition amount of O to the amount of the lead bromide substance is 8:1, and the ratio of the addition amount of the octadecenamide to the amount of the lead bromide substance is 2:1, preparing a precursor solution of perovskite clusters, wherein the ratio of the addition amount of octadecenoic acid to the amount of lead bromide substance is 4:1;
(2) injecting the perovskite cluster precursor solution into toluene according to the volume ratio of 0.5:10, rapidly stirring at room temperature for about 2 minutes, centrifuging the mixed solution at the speed of 10000r/min for 10 minutes, centrifuging for 3 times, collecting the product as supernatant fluid after each centrifugation, obtaining the perovskite cluster solution, and finally storing the obtained perovskite cluster solution in a refrigerator at low temperature (0-5 ℃) for standby, wherein the particle size of the perovskite clusters is 1.0-2.0 nm.
Comparative example 1
A perovskite material solution, the preparation of which comprises the steps of:
(1) the mass ratio of the materials is 1:1 cesium bromide (CsBr) and lead bromide (PbBr) 2 ) Dissolving in a mixed solvent of dimethyl sulfoxide (DMSO) and N, N-Dimethylformamide (DMF) in a volume ratio of 1:1, and stirring until the mixture is completely dissolved; the initial concentration of lead bromide was 0.5mol/L, with a solvent volume of 0.4mL; then adding octadecenoic acid and octadecenamide, stirring and dissolving, wherein the ratio of the addition amount of the octadecenamide to the lead bromide substance is 0.6-1, and the ratio of the addition amount of the octadecenoic acid to the lead bromide substance is 0.3:1, so as to prepare a precursor solution of perovskite clusters;
(2) Injecting the perovskite cluster precursor solution into toluene according to the volume ratio of 0.5:10, rapidly stirring at room temperature for about 2 minutes, centrifuging the mixed solution at the speed of 10000r/min for 10 minutes for 3 times, and collecting the supernatant as a product after each centrifugation, wherein perovskite clusters cannot be formed in the solution.
Comparative example 2
A perovskite material solution, the preparation of which comprises the steps of:
(1) the mass ratio of the materials is 1:1 cesium bromide (CsBr) and lead bromide (PbBr) 2 ) Dissolving in dimethyl sulfoxide (DMSO) solvent, and stirring to dissolve completely; the initial concentration of lead bromide was 0.04mol/L, with a volume of solvent of 1.0mL; then Yb (NO) 3 ) 3 ·5H 2 O and octadecenamide and stirring at 30℃for 1h, wherein Yb (NO 3 ) 3 ·5H 2 The ratio of the addition amount of O to the amount of the lead bromide substance is 1:1, and the ratio of the addition amount of the octadecenamide to the amount of the lead bromide substance is 2:1, preparing a precursor solution of perovskite clusters;
(2) injecting the perovskite cluster precursor solution into toluene according to the volume ratio of 0.5:10, rapidly stirring at room temperature for about 2 minutes, centrifuging the mixed solution at the speed of 10000r/min for 10 minutes for 3 times, and collecting the supernatant as a product after each centrifugation, wherein perovskite clusters cannot be formed in the solution.
Comparative example 3
A perovskite material solution, the preparation of which comprises the steps of:
(1) the mass ratio of the materials is 1:1 cesium bromide (CsBr) and lead bromide (PbBr) 2 ) Dissolving in dimethyl sulfoxide (DMSO) solvent, and stirring to dissolve completely; the initial concentration of lead bromide was 0.04mol/L, with a volume of solvent of 1.0mL; then Yb (NO) 3 ) 3 ·5H 2 O and octadecenoic acid and stirring at 30deg.C for 1h, wherein Yb (NO 3 ) 3 ·5H 2 The ratio of the addition amount of O to the amount of lead bromide substance is 1:1, and the ratio of the addition amount of octadecenoic acid to the amount of lead bromide substance is 4:1, so as to prepare a precursor solution of perovskite clusters;
(2) injecting the perovskite cluster precursor solution into toluene according to the volume ratio of 0.5:10, rapidly stirring at room temperature for about 2 minutes, centrifuging the mixed solution at the speed of 10000r/min for 10 minutes for 3 times, and collecting the supernatant as a product after each centrifugation, wherein perovskite clusters cannot be formed in the solution.
Comparative example 4
A perovskite material solution, the preparation of which comprises the steps of:
(1) the mass ratio of the materials is 1:1 cesium bromide (CsBr) and lead bromide (PbBr) 2 ) Dissolving in dimethyl sulfoxide (DMSO) solvent, and stirring to dissolve completely; the initial concentration of lead bromide was 0.04mol/L, with a volume of solvent of 1.0mL; then Yb (NO) 3 ) 3 ·5H 2 O and stirring at 30℃for 1h, wherein Yb (NO 3 ) 3 ·5H 2 The ratio of the addition amount of O to the amount of lead bromide substance is 1:1, and a precursor solution of perovskite clusters is prepared;
(2) injecting the perovskite cluster precursor solution into toluene according to the volume ratio of 0.5:10, rapidly stirring at room temperature for about 2 minutes, centrifuging the mixed solution at the speed of 10000r/min for 10 minutes for 3 times, and collecting the supernatant as a product after each centrifugation, wherein perovskite clusters cannot be formed in the solution.
Further, to verify the advancement of the present application examples were tested for performance as follows:
1. the characteristic peaks of the ultraviolet absorption spectrum and the fluorescence emission spectrum of the perovskite cluster solution prepared in example 1 were tested by an ultraviolet-visible spectrophotometer and a fluorescence spectrophotometer test instrument, and the test results are shown in fig. 3, wherein the corresponding characteristic peaks are 393nm and 397nm, respectively.
2. The perovskite cluster solution prepared in example 2 was tested for morphology size by a high resolution transmission electron microscope test instrument, and the test results are shown in fig. 4, and the test results show that the perovskite clusters are spherical and have an average size of 1.90 + -0.2 nm.
3. Yb (NO) was added to example 3 by a fluorescence spectrophotometer test instrument 3 ) 3 ·5H 2 Perovskite cluster solution prepared with O and comparative example 1 without addition of lanthanide rare earth salt hydrate (M (NO 3 ) 3 ·XH 2 The fluorescence emission spectrum intensity of the perovskite material prepared by O) was subjected to comparative test, the test results are shown in FIG. 5, and the test results show that the perovskite material prepared in example 1 (M (NO 3 ) 3 ·XH 2 O) adding M (NO 3 ) 3 ·XH 2 The fluorescence emission spectrum intensity of the perovskite cluster of O is obviously enhanced, and the luminous performance is improved. While comparative example 1 (NO M (NO) 3 ) 3 ·XH 2 O) without M (NO) 3 ) 3 ·XH 2 The perovskite material of O has a weak fluorescence emission spectrum intensity.
4. Stability test was performed under conditions of an air temperature of 25℃and a relative humidity of 60%, and Yb (NO) was added to examples 1 to 4 through an integrating sphere of a fluorescence spectrophotometer tester 3 ) 3 ·5H 2 Perovskite cluster solution prepared with O and comparative example 1 without addition of lanthanide rare earth salt hydrate (M (NO 3 ) 3 ·XH 2 The fluorescence quantum yield of the perovskite material prepared by O) is tested, and the test result diagram is shown in the table 1 below. As can be seen, yb (NO) was added in examples 1 to 4 3 ) 3 ·5H 2 Perovskite clusters prepared by O show higher fluorescenceInitial value of quantum yield, and after 72 hours, higher quantum yield of fluorescence still shows better stability. Comparative example 1 without the addition of lanthanide rare earth salt hydrate (M (NO) 3 ) 3 ·XH 2 O) the prepared perovskite material has low fluorescence quantum yield and is easy to quench.
The test chart of example 1 is shown in FIG. 6, and the test results show that the fluorescence quantum yield test of example 1 (with M (NO 3 ) 3 ·XH 2 O) the fluorescence quantum yield of the perovskite cluster is reduced to 87% from the original 91%, and the perovskite cluster has good stability and luminous performance. While comparative example 1 (NO M (NO) 3 ) 3 ·XH 2 O) without M (NO) 3 ) 3 ·XH 2 The fluorescence quantum yield of the perovskite material of O is reduced from 65% to 0% and should be substantially quenched.
TABLE 1
Initial value of fluorescence quantum yield% Fluorescence quantum yield%
Example 1 91％ 87％
Example 2 87％ 82％
Example 3 89％ 84％
Example 4 90％ 84％
Comparative example 1 65％ 0
The foregoing description of the preferred embodiments of the application is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the application.

Claims (8)

1. A method for preparing perovskite cluster solution, which is characterized in that: the method comprises the following steps:
preparing a precursor solution from lanthanide rare earth metal salt hydrate, organic carboxylic acid, organic amine ligand and perovskite raw material; the chemical general formula of the lanthanide rare earth metal salt hydrate is represented by M (NO 3 ) 3 ·XH 2 O, wherein M is trivalent lanthanide rare earth metal, and X is the number of crystal water; the perovskite raw material comprises a divalent metal halide and an alkali metal halide; the lanthanide rare earth metal salt hydrate is selected from Yb (NO 3 ) 3 ·5H 2 O、Dy(NO 3 ) 3 ·6H 2 O、Eu(NO 3 ) 3 ·5H 2 O、Sm(NO 3 ) 3 ·6H 2 O、Pr(NO 3 ) 3 ·6H 2 At least one of O; the organic carboxylic acid is at least one selected from propionic acid, n-butyric acid, n-valeric acid, octadecenoic acid, benzoic acid and phenylacetic acid; the organic amine ligand is at least one selected from octadecylamine, benzyl amine and phenethyl amine; the halogenated divalent metal is selected from at least one of lead halides;
mixing the precursor solution with an antisolvent, combining trivalent lanthanide rare earth metal ions in the lanthanide rare earth metal salt hydrate with halogen ion defects on the surface of a perovskite cluster, combining nitrate ions with metal ion defects on the surface of the perovskite cluster, forming a planar molecular coating layer on the surface of the perovskite cluster by the trivalent lanthanide rare earth metal ions, the nitrate ions, water molecules and hydroxide ions, and purifying to obtain a perovskite cluster solution; the antisolvent is at least one selected from n-hexane, toluene, methylene dichloride and chloroform.
2. The method of preparing a perovskite cluster solution as claimed in claim 1, wherein: the step of configuring the precursor solution includes: and dissolving the perovskite raw material in an organic solvent, mixing for 10-30 minutes, adding the lanthanide rare earth metal salt hydrate, the organic carboxylic acid and the organic amine ligand, and stirring at 30-55 ℃ for 0.5-2 hours to obtain the precursor solution.
3. A method of preparing a perovskite cluster solution as claimed in claim 2, wherein: the molar ratio of the addition amount of the lanthanide rare earth metal salt hydrate to the halogenated divalent metal is (1-2): (3-10).
4. A method for preparing a perovskite cluster solution according to any one of claims 2 to 3, characterized in that: the volume ratio of the precursor solution to the antisolvent is (0.2-4): (5-35);
and/or the mixing treatment time is 1-3 minutes.
5. A method for preparing a perovskite cluster solution according to any one of claims 2 to 3, characterized in that: the molar ratio of the organic carboxylic acid to the halogenated divalent metal is (2-10): 1, a step of;
and/or the molar ratio of the organic amine ligand to the halogenated divalent metal is (1-10): 1, a step of;
And/or, the step of purifying comprises: and (3) centrifuging the mixed solution after the mixing treatment, and collecting supernatant to obtain the perovskite cluster solution.
6. The method of preparing a perovskite cluster solution as claimed in claim 5, wherein: the alkali halide includes at least one of CsCl, csBr, csI, rbCl, rbBr, rbI;
and/or the organic solvent is selected from at least one of dimethyl sulfoxide and N, N-dimethylformamide.
7. The method of preparing a perovskite cluster solution as claimed in claim 1, wherein: the particle size of perovskite clusters in the perovskite cluster solution is 1-3 nm.
8. An optoelectronic device, characterized by: the photoelectric device comprises the perovskite cluster solution prepared by the method of any one of claims 1-7.
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