CN114085665A - Perovskite cluster solution, preparation method thereof and photoelectric device - Google Patents
Perovskite cluster solution, preparation method thereof and photoelectric device Download PDFInfo
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- CN114085665A CN114085665A CN202111276301.3A CN202111276301A CN114085665A CN 114085665 A CN114085665 A CN 114085665A CN 202111276301 A CN202111276301 A CN 202111276301A CN 114085665 A CN114085665 A CN 114085665A
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- perovskite
- cluster
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- rare earth
- acid
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- 239000002243 precursor Substances 0.000 claims abstract description 47
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- 150000001412 amines Chemical class 0.000 claims abstract description 36
- 239000003446 ligand Substances 0.000 claims abstract description 36
- 239000002994 raw material Substances 0.000 claims abstract description 14
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
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- C—CHEMISTRY; METALLURGY
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- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- 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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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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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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Abstract
The application belongs to the technical field of photoelectricity, and particularly relates to a perovskite cluster solution, a preparation method of the perovskite cluster solution, and a photoelectric device. The preparation method of the perovskite cluster solution comprises the following steps: preparing lanthanide series rare earth metal salt hydrate, organic carboxylic acid, organic amine ligand and perovskite raw material into precursor solution; and mixing the precursor solution and an anti-solvent, and purifying to obtain the perovskite cluster solution. According to the preparation method of the perovskite cluster solution, through the synergistic effect among lanthanide rare earth salt hydrate, organic carboxylic acid and organic amine ligand, the surface defect of the perovskite cluster is effectively passivated, the aggregation growth rate of the perovskite cluster is regulated, the stability of the perovskite cluster in the solution environment is improved, and the perovskite cluster with small size, strong stability and high fluorescence quantum yield is obtained.
Description
Technical Field
The application belongs to the technical field of photoelectricity, and particularly relates to a perovskite cluster solution, a preparation method of the perovskite cluster solution, and a photoelectric device.
Background
Nanoclusters are relatively stable microscopic or submicroscopic aggregates of atoms or molecules that are bonded together by physical or chemical forces. Due to its small size and surface plasticity, it has become a hot point of research in the fields of self-assembly materials, optoelectronic devices, biomarkers, medical treatment, solar cells, etc. The shape of the nanocluster has great influence on the electronic structure and the optical property of the nanocluster, and a material with specific performance can be designed by adjusting the microstructure of the semiconductor nanocluster. Meanwhile, the nanoclusters can be used as building units, superstructure materials with good symmetry and geometric shapes can be prepared through a conventional chemical route or other self-assembly strategies, and the superstructure materials can be further converted into nano materials with special structures.
Perovskite clusters, as multi-core aggregates between the microstructure (atoms, molecules) and macroscopic species (quantum dots, thin films and blocks) of perovskite materials, are ideal models for correlating the two. The perovskite cluster has unique physicochemical properties of quantum effect, high specific surface area (S/V), adjustable size and components, easy functionalization treatment on surface defects and the like, and is receiving attention. The perovskite cluster shows unique photoelectric properties of quantum materials, has 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 applied to aspects of biological imaging, blue Light Emitting Diodes (LEDs), sensors and the like. Therefore, understanding the new optical properties and the evolution process mechanism of the perovskite material in the process of evolution from the perovskite cluster can provide reference and theoretical basis for designing and manufacturing perovskite quantum functional devices with excellent performance.
At present, in the design of an experimental scheme, a perovskite raw material, a surface passivation organic ligand, a solvent and an anti-solvent are selected and regulated, a reaction system is controlled to generate a perovskite cluster in the process of molecular aggregation integrated bonds, but the generated perovskite cluster is easy to cause the agglomeration of the perovskite cluster due to a large number of defects on the surface and ligand dangling bonds, and is not beneficial to the reaction to generate the perovskite cluster with uniform components. The perovskite cluster synthesized at present cannot stably exist in a solvent for a long timeAnd the perovskite nano-crystal is easy to agglomerate and degrade or continuously grow into the perovskite nano-crystal with larger size. In addition, perovskite clusters are highly sensitive to the environment and are very unstable in the natural environment, especially for H2O has strong instability. Resulting in a low photoluminescence quantum yield of the 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 cluster is easy to agglomerate and degrade, poor in stability and incapable of being stably existed in a solvent for a long time to a certain extent.
In order to achieve the purpose of the application, the technical scheme adopted by the application is as follows:
in a first aspect, the present application provides a method for preparing a perovskite cluster solution, comprising the steps of:
preparing lanthanide series rare earth metal salt hydrate, organic carboxylic acid, organic amine ligand and perovskite raw material into precursor solution;
and mixing the precursor solution and an anti-solvent, and purifying to obtain the 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 layer formed of a lanthanide rare earth metal salt hydrate.
In a third aspect, the present application provides a photovoltaic device comprising the perovskite cluster solution prepared by the above method, or the above perovskite cluster solution.
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 added into the prepared perovskite precursor solution at the same time, wherein strong coordination action of carbonyl and octahedral central cation in the organic carboxylic acid and intermolecular action force between carboxylic acid alkyl chains can be reduced, and [ BX ] can be reduced6]The driving force of octahedron aggregation, the inhibition of the fast octahedron aggregation and the passivation of the positive ions on the surface of the perovskite clusterAnd (5) a defect. Organic amine ligand capable of bonding with anion at octahedral edge by electrostatic attraction to passivate anion defect on surface of perovskite cluster to form organic spacer layer, so that dielectric constant of spacer layer is mismatched with octahedral sheet layer to make [ BX6]The octahedral layer forms a natural quantum well, and the migration efficiency of carriers in the perovskite cluster is improved. 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 cluster, acid radical ions can be combined with metal ion defects on the surface of the perovskite cluster, and a planar molecular coating layer with lanthanide rare earth metal ions, acid radical ions, water molecules and hydroxide ions is formed on the surface of the perovskite cluster. Not only further passivates the surface defects of the perovskite clusters, but also inhibits the aggregation growth of the perovskite clusters; and the formed molecular coating layer can effectively block the invasion of external water molecules through crystallizing the water molecules. Therefore, the aggregation phenomenon of the perovskite clusters is improved, the perovskite clusters are inhibited from being rapidly aggregated and grown into perovskite materials such as perovskite quantum dots, thin films or blocks with larger sizes, and the resistance of the perovskite clusters to inherent instability factors such as water, oxygen, illumination and the like in the environment is improved.
In the perovskite cluster solution provided by the second aspect of the application, organic carboxylic acid and organic amine ligand are combined on the surface of the perovskite cluster, and a molecular coating layer is formed by lanthanide rare earth metal salt hydrate; the organic carboxylic acid passivates cation defects on the surface of the perovskite cluster, the organic amine ligand passivates anion defects on the surface of the perovskite cluster, lanthanide rare earth metal ions in lanthanide rare earth metal salt hydrate can be combined with halogen ion defects on the surface of the perovskite cluster, acid radical ions can be combined with metal ion defects on the surface of the perovskite cluster, and a planar molecular coating layer with lanthanide rare earth metal ions, acid radical ions, water molecules and hydroxide radical ions is formed on the surface of the perovskite cluster. Through the synergistic effect among lanthanide series rare earth metal salt hydrate, organic carboxylic acid and organic amine ligand, the surface defect of the perovskite cluster is effectively passivated, the aggregation growth rate of the perovskite cluster is regulated, the stability of the perovskite cluster in a solution environment is improved, and the perovskite cluster with small size, strong stability and high fluorescence quantum yield is obtained.
The photoelectric device provided by the third aspect of the present application, because the solution of the perovskite cluster is included, wherein organic carboxylic acid and organic amine ligand are combined on the surface of the perovskite cluster, and the molecular coating layer is formed by lanthanide rare earth salt hydrate, 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 stably existing in the solution has small size and highly uniform size distribution, the small perovskite cluster has a discrete energy level structure, the color purity and 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 in the embodiments of the present application, the drawings needed to be used in the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
Fig. 1 is a schematic flow diagram of a method for preparing a perovskite cluster solution provided in an embodiment of the present application;
FIG. 2 is a schematic structural diagram of a perovskite cluster in a perovskite cluster solution provided by an embodiment of the present application;
fig. 3 is an ultraviolet absorption spectrum and a fluorescence emission spectrum of the perovskite cluster solution provided in example 1 of the present application;
fig. 4 is an electron microscope topography (left) and a 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 intensity for a perovskite cluster solution provided in example 3 of the present application and a perovskite material provided in comparative example 1;
fig. 6 is a graph of fluorescence quantum yield for the perovskite cluster solution provided in example 1 of the present application and the perovskite material provided in comparative example 1.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present application more clearly apparent, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.
In this application, the term "and/or" describes an association relationship of associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
In the present application, "at least one" means one or more, "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one (one) of a, b, or c," or "at least one (one) 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, and c may be single or plural, respectively.
It should be understood that, in various embodiments of the present application, the sequence numbers of the above-mentioned processes do not mean the execution sequence, 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 function and inherent logic, and should not constitute any limitation to the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the examples of 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 amount of the related component mentioned in the description of the embodiment of the present application may not only refer to the specific content of each component, but also represent the proportional relationship of the amount between each component, and therefore, it is within the scope of the disclosure of the embodiment of the present application as long as the content of the related component is scaled up or down according to the description of the embodiment of the present application.
The terms "first" and "second" are used for descriptive purposes only and are used for distinguishing purposes such as substances from one another, and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. 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 present application. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature.
As shown in fig. 1, a first aspect of the embodiments of the present application provides a method for preparing a perovskite cluster solution, including the following steps:
s10, preparing a lanthanide series rare earth salt hydrate, organic carboxylic acid, an organic amine ligand and a perovskite raw material into a precursor solution;
and S20, mixing the precursor solution with an anti-solvent, and purifying to obtain the 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 added into the perovskite precursor solution at the same time, wherein the strong coordination action of carbonyl and octahedral central cation in the organic carboxylic acid and the intermolecular action force between carboxylic acid alkyl chains can be reduced by the aid of the strong coordination action of carbonyl and octahedral central cation in the organic carboxylic acid6]The driving force of octahedron aggregation inhibits the fast aggregation of octahedron and passivates the cation defects on the surface of the perovskite cluster. Organic amine ligand capable of bonding with anion at octahedral edge by electrostatic attraction to passivate anion defect on surface of perovskite cluster to form organic spacer layer, so that dielectric constant of spacer layer is mismatched with octahedral sheet layer to make [ BX6]The octahedral layer forms a natural quantum well, and the migration efficiency of carriers in the perovskite cluster is improved. Lanthanide rare earth metal ions in lanthanide rare earth metal salt hydrate can be separated from the halogen on the surface of the perovskite clusterAnd (3) combining the sub defects, wherein acid radical ions can be combined with metal ion defects on the surface of the perovskite cluster, and a planar molecular coating layer with lanthanide rare earth metal ions, acid radical ions, water molecules and hydroxide ions is formed on the surface of the perovskite cluster. Not only further passivates the surface defects of the perovskite clusters, but also inhibits the aggregation growth of the perovskite clusters; and the formed molecular coating layer can effectively block the invasion of external water molecules through crystallizing the water molecules. Therefore, the aggregation phenomenon of the perovskite clusters is improved, the perovskite clusters are inhibited from being rapidly aggregated and grown into perovskite materials such as perovskite quantum dots, thin films or blocks with larger sizes, and the resistance of the perovskite clusters to inherent instability factors such as water, oxygen, illumination and the like in the environment is improved. According to the perovskite cluster solution prepared by the embodiment of the application, through the synergistic effect among lanthanide rare earth salt hydrate, organic carboxylic acid and organic amine ligand, the surface defect of the perovskite cluster is effectively passivated, the aggregation growth rate of the perovskite cluster is regulated, and the stability of the perovskite cluster in the solution environment is improved. The perovskite clusters in the perovskite cluster solution can stably exist in a solution system, the size of the perovskite clusters is small and is about 1-3 nm, and the size distribution height is uniform. Compared with large-size perovskite materials, the small-size perovskite cluster has a discrete energy level structure, can show unique photoelectric properties such as blue-shifted 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 applications in the fields of ultramicro photoelectric devices, biological imaging, fluorescent labeling, new-generation high-property catalysts and the like.
In some embodiments, in step S10 above, the lanthanide rare earth metal salt hydrate, the organic carboxylic acid, the organic amine ligand, and the perovskite starting material are configured 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 is composed of A, B and X ions in perovskite raw materials participating in synthesis, wherein A site is at least one of inorganic or organic cations, such as Cs+Or Rb+Monovalent inorganic cationAnd as Methylamine (MA)+，CH3NH3 +) Ethylamine (EA)+，CH3CH2NH3 +) Or Formamidine (FA)+，CH(NH2)2 +) At least one of ionic monovalent organic cations; the B site usually being a divalent metal cation, e.g. Pb2+、Sn2+、Ge2+、Ga2+、Cu2 +、Ni2+、Co2+And Mn2+Etc.; the X position usually being a monovalent halogen, e.g. I-、Br-、Cl-、F-Etc., and may also be pseudohalogen anions, e.g. SCN-And BF4 -Etc., the precise structural composition of the perovskite clusters is not yet clear. The divalent metal cation at the B site is coordinated with the halogen ion at the X site to form [ BX6]Octahedron, A site inorganic or organic cation is distributed in the space generated by octahedron co-apical connection, and coordination number is 12.
In some embodiments, the lanthanide rare earth salt hydrate is selected from: hydrated nitrate of rare earth metal of trivalent lanthanide series, available in the general formula M (NO)3)3·XH2O 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 binding performance with halogen defects on the surface of the perovskite cluster, nitrate ions have better binding performance with metal ion defects on the surface of the perovskite cluster, and monovalent, divalent and other metal ions and other acid radical ions have poor passivation effect on the perovskite cluster, so that the cluster is aggregated and agglomerated to form perovskite quantum dots.
In some embodiments, the trivalent lanthanide rare earth metal hydrous nitrate includes ytterbium (III) nitrate pentahydrate Yb (NO)3)3·5H2Dy (NO) hexahydrate of O and dysprosium (III) nitrate3)3·6H2O, europium (III) nitrate hexahydrate Eu (NO)3)3·5H2O, samarium (III) nitrate hexahydrate Sm (OH)3·6H2O, praseodymium (III) nitrate hexahydrate Pr (NO)3)3·6H2At least one of O, more preferably ytterbium (III) pentanitrateHydrate Yb (NO)3)3·5H2O, europium (III) nitrate hexahydrate Eu (NO)3)3·5H2O, samarium (III) nitrate hexahydrate Sm (OH)3·6H2O, and the like. Of these trivalent lanthanide rare earth metal hydrous nitrates, Yb3+、Dy3+、Eu3+、Sm3+、Pr3+I of iso-trivalent lanthanide series rare earth metal ion capable of being mixed with surface of perovskite cluster-、Br-、Cl-、F-Halogen ions or SCN-And BF4 -The pseudo-halogen anion defect is combined, and nitrate ions can be combined with Pb on the surface of the perovskite cluster2+、Sn2+、Ge2+、Ga2+、Cu2+、Ni2+、Co2+And Mn2+And combining the defects of the metal ions, and forming a planar molecular coating layer with trivalent lanthanide rare earth metal ions, nitrate ions, water molecules and hydroxide ions on the surface of the perovskite cluster. Not only further passivates the surface defects of the perovskite clusters, but also inhibits the aggregation growth of the perovskite clusters; and the formed molecular coating layer can effectively block the invasion of external water molecules through crystallizing the water molecules. Therefore, the aggregation phenomenon of the perovskite clusters is improved, the perovskite clusters are inhibited from being rapidly aggregated and grown into perovskite materials such as perovskite quantum dots, thin films or blocks with larger sizes, and the resistance of the perovskite clusters to inherent instability factors such as water, oxygen, illumination and the like in the environment is improved.
In some embodiments, 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), the addition amount effectively ensures the passivation and stabilization of lanthanide rare earth 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 salt hydrate is too low, the lanthanide rare earth salt hydrate is not beneficial to passivating and stabilizing the perovskite cluster, the perovskite cluster is easy to agglomerate into large-size perovskite materials such as perovskite quantum dots, thin films or blocks, and the like, and the perovskite cluster is poor in stability and 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 can be introduced into the system, so that the perovskite cluster is not favorably generated, and in addition, the excessive lanthanide rare earth metal salt hydrate cannot be completely dissolved in a precursor solvent, so that the perovskite cluster with high purity is not favorably obtained. In some embodiments, the molar ratio of the amount of lanthanide rare earth salt hydrate added to the divalent metal halide includes, but is not limited to, 1: (3-10) and 1: (4-9) and 1: (5-8) and 1: (6-7) and 2: (3-10) and 2: (4-9) and 2: (5-8) and 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, octadecanoic acid, octadecenoic acid, benzoic acid, phenylacetic acid, and further preferably octadecenoic acid or phenylacetic acid, or octadecenoic acid and phenylacetic acid. The organic carboxylic acid added in the precursor solution contains carbonyl, can form strong coordination with octahedral central cations, and intermolecular force also exists among carboxylic acid alkyl chains, so that [ BX ] can be reduced6]The driving force of octahedron aggregation inhibits the fast aggregation of octahedron, passivates the cation defects on the surface of the perovskite cluster, and inhibits the fast aggregation of the perovskite cluster from growing into perovskite materials such as perovskite quantum dots, thin films or blocks with larger sizes.
In some embodiments, the ratio of the amount of the organic carboxylic acid added to the molar amount of the halogenated divalent metal in the perovskite raw material in the precursor solution is (2-10): 1, the proportion not only can effectively passivate the surface of the perovskite cluster, and regulate the agglomeration rate of the perovskite cluster, so that the perovskite in the solution maintains the cluster form; and the solution system has a proper pH value which is about 5, so that lanthanide rare earth metal salt hydrate can form a planar molecular coating layer of lanthanide rare earth metal ions, acid radical ions, water molecules and hydroxide ions on the surface of the perovskite cluster. If the addition amount of the organic carboxylic acid in the precursor solution is too large, the acid-base balance of a reaction system can be damaged, and the formation of perovskite clusters is excessively inhibited, so that the perovskite clusters are difficult to generate in the reaction, and the perovskite material in the solution is maintained in a molecular or atomic microstructure; 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 passivate, and the perovskite cluster is easy to quickly aggregate and grow into macroscopic structures such as large-size perovskite quantum dots, thin films or blocks, 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 raw 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 octadecylamine, octadecenylamine, benzylamine, phenethylamine, further preferably octadecenylamine or phenethylamine, or preferably octadecenylamine and phenethylamine. The organic ligands added into the precursor solution in the embodiment of the application can be bonded with anions on the edge of an octahedron through electrostatic attraction to passivate the anion defects on the surface of the perovskite cluster, further regulate and control the aggregation growth rate of the perovskite cluster, and simultaneously form an organic spacing layer to ensure that the dielectric constant of the spacing layer is mismatched with the octahedron sheet layer, so that [ BX ] is enabled to be mismatched with the octahedron sheet layer6]The octahedral layer forms a natural quantum well, and the migration efficiency of carriers in the perovskite cluster is improved.
In some embodiments, the molar ratio of organic amine ligand to halogenated divalent metal is (1-10): 1; 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 adjustment of the perovskite structure and the aggregation rate of the clusters is not facilitated; if the addition amount of the organic amine ligand in the precursor solution is too high, the perovskite cluster formation is also not facilitated. 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., preferably (2-8): 1.
In some embodiments, the halogenated divalent metal comprises at least one of a lead halide, a tin halide, a germanium halide, a gallium halide, a nickel halide, a manganese halide, a cobalt halide, a copper halide; these divalent metals halides can self-assemble with organic ammonium halides or alkali halides, introducing divalent metal ions such as lead, tin, germanium, gallium, nickel, cobalt, manganese, copper, etc. into the perovskite cluster structure. In some preferred embodiments, the halogenated divalent metal is selected from at least one of lead halides and 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 comprises CH3NH3Cl、CH3NH3Br、CH3NH3I、CH2(NH3)2Cl、CH2(NH3)2Br、CH2(NH3)2I、CH3CH2NH3Cl、CH3CH2NH3Br、CH3CH2NH3At least one of I; the organic halogenated ammonium salt can form a perovskite material after self-assembly with halogenated divalent metal, and CH is introduced into the perovskite material3NH3 +、CH2(NH3)2 +、CH2CH2NH3 +And the thermal stability of the perovskite material can be effectively improved by organic ammonium ions.
In some embodiments, the alkali halide comprises at least one of CsCl, CsBr, CsI, RbCl, RbBr, RbI; the alkali metal halide can form a perovskite material after self-assembly with the divalent metal halide, and Cs is introduced into the perovskite material+、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 organic solvents have good dissolving and dispersing effects on organic carboxylic acids, organic amine ligands, perovskite raw materials and the like. In some embodiments, the organic solvent comprises dimethyl sulfoxide and N, N-dimethylformamide, and further the volume ratio of dimethyl sulfoxide to N, N-dimethylformamide is (1-9): (1-9). The mixed organic solvent adopted in the embodiment of the application has a good dissolving effect on the raw material components, and is beneficial to the mutual contact reaction among the components; but also is beneficial to regulating the growth rate and orientation of the perovskite. In particular, the amount of the solvent to be used,the S ═ O bond in dimethyl sulfoxide is easy to coordinate with the B site cation in perovskite to form intermediate to prevent perovskite [ BX-6]Octahedra such as [ PbI ]6]Etc. are rapidly aggregated. N, N-dimethylformamide is a good solvent for perovskite precursors, and has a similar action to dimethyl sulfoxide, but C ═ O has a weak action on B site cations, and has a low boiling point, and thus the perovskite clusters are not well formed. Therefore, a mixed solvent of dimethyl sulfoxide and N, N-dimethylformamide is used. In some 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 comprises: dissolving a perovskite raw material in an organic solvent, mixing and stirring for 10-30 minutes at room temperature, adding a lanthanide rare earth salt hydrate, an organic carboxylic acid and an organic amine ligand, stirring for 0.5-2 hours at 30-55 ℃, and fully dissolving to obtain a precursor solution. In some embodiments, the ratio of the amounts of divalent metal halide and organic ammonium halide or alkali metal halide species in the perovskite raw material when formulating the precursor solution may be 1: (0.2-5), more preferably 1: (0.5 to 3). In some embodiments, the initial concentration of the halogenated divalent metal in the organic solvent is preferably 0.03 to 0.1 mol/L.
In some embodiments, in step S20, the precursor solution and the anti-solvent are mixed for 1-3 minutes, and the aggregation rate of the perovskite cluster is synergistically controlled by the organic carboxylic acid, the organic amine ligand and the lanthanide rare earth salt hydrate, that is, the perovskite cluster with small size and high uniformity of particle size distribution is generated in the solution.
In some embodiments, the anti-solvent comprises at least one of n-hexane, toluene, dichloromethane, chloroform, further preferably toluene or chloroform, or preferably toluene and chloroform; the anti-solvent can promote 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 a perovskite cluster of a multi-core aggregate, the surface of the cluster is combined with a planar molecular coating layer which is formed by organic ligands, organic carboxylic acids and lanthanide rare earth salt hydrates and has lanthanide rare earth metal ions, acid radical ions, water molecules and hydroxide ions, and the perovskite cluster has good stability.
In some embodiments, the volume ratio of the precursor solution to the antisolvent is (0.2-4): (5-35); further, (0.5-3): (10-20). Different supersaturation degrees are realized through the volume ratios of different precursor solutions and anti-solvents, so that the size and the number of the generated perovskite material are changed, and the reaction system is controlled to slowly generate the 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 components, organic amine, organic carboxylic acid and lanthanide rare earth salt hydrate, and collecting supernatant to obtain perovskite cluster solution. In some embodiments, the mixed solution after the mixing treatment is centrifuged 3-4 times at a centrifugal separation rotation speed of 2000-12000 r/min, the collected product is a supernatant liquid each time of centrifugation, and further preferably at a rotation speed of 6000-10000 r/min, and the obtained perovskite cluster solution is stored in a refrigerator at a low temperature (0-5 ℃).
As shown in fig. 2, a second aspect of the embodiments of the present application provides a perovskite cluster solution in which organic carboxylic acid and organic amine ligand are bonded to the surface of a perovskite cluster, and 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 a molecular coating layer formed by organic carboxylic acid, organic amine ligand and lanthanide rare earth metal salt hydrate; the organic carboxylic acid passivates cation defects on the surface of the perovskite cluster, the organic amine ligand passivates anion defects on the surface of the perovskite cluster, lanthanide rare earth metal ions in lanthanide rare earth metal salt hydrate can be combined with halogen ion defects on the surface of the perovskite cluster, acid radical ions can be combined with metal ion defects on the surface of the perovskite cluster, and a planar molecular coating layer with lanthanide rare earth metal ions, acid radical ions, water molecules and hydroxide radical ions is formed on the surface of the perovskite cluster. Through the synergistic effect among lanthanide series rare earth metal salt hydrate, organic carboxylic acid and organic amine ligand, the surface defect of the perovskite cluster is effectively passivated, the aggregation growth rate of the perovskite cluster is regulated, the stability of the perovskite cluster in a solution environment is improved, and the perovskite cluster with small size, strong stability and high fluorescence quantum yield is obtained.
The perovskite cluster solution of the embodiment of the present application can be prepared by the method of the embodiment.
In some embodiments, the particle size of the perovskite clusters in the perovskite cluster solution is 1-3 nm, the size range can be determined to be substantially pure perovskite clusters, and if the size is too small, quantum dots with large sheet or spherical sizes can be easily generated. According to the embodiment of the application, the perovskite clusters in the perovskite cluster solution can stably exist in the solution system, the perovskite clusters are small in size and highly uniform in size distribution, and the optical characteristics of the perovskite clusters, such as strong ionicity, high surface energy and high quantum effect, are ensured. Compared with large-size perovskite materials, the small-size perovskite clusters have discrete energy level structures, can show unique photoelectric properties such as blue-shifted absorption and emission spectra, improve the color purity and the optical stability of the perovskite clusters, and are expected to develop potential applications in the fields of ultramicro 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, or the like.
In some embodiments, the organic ligand comprises at least one of octadecylamine, octadecenylamine, benzylamine and phenethylamine, and by selecting a proper organic ligand, the passivation can reduce halogen anion defects on the surface of the perovskite cluster, inhibit the aggregation growth of the perovskite cluster, and maintain the perovskite cluster state in the solution.
In some embodiments, the lanthanide rare earth salt hydrate comprises Yb (NO)3)3·5H2O、Dy(NO3)3·6H2O、Eu(NO3)3·5H2O、Sm(OH)3·6H2O、Pr(NO3)3·6H2At least one trivalent lanthanide rare earth metal hydrous nitrate in O; in the lanthanide rare earth 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, octadecanoic acid, octadecenoic acid, benzoic acid, phenylacetic acid; the organic carboxylic acid can form strong coordination with octahedral central cation, and intermolecular force also exists between alkyl chains of the carboxylic acid, so that [ BX ] can be reduced6]The driving force of octahedron aggregation inhibits the fast aggregation of octahedron, passivates the cation defects on the surface of the perovskite cluster, and inhibits the fast aggregation of the perovskite cluster from growing into perovskite materials such as perovskite quantum dots, thin films or blocks with larger sizes.
In a third aspect of the embodiments of the present application, there is provided a photovoltaic device including the perovskite cluster solution prepared by the above method, or the above perovskite cluster solution.
According to the photoelectric device provided by the third aspect of the embodiment of the application, the solution of the perovskite cluster is included, wherein the surface of the perovskite cluster is combined with the organic carboxylic acid and the organic amine ligand, and the molecular coating layer is formed by the lanthanide rare earth salt hydrate, so that the stability and the 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 stably existing in the solution has a small size and a highly uniform size distribution, the small 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, so that the photoelectric performance of the photoelectric device is improved.
In some embodiments, 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 to make the above implementation details and operations of the present application clearly understood by those skilled in the art, and to make the progress of the perovskite cluster solution and the preparation method thereof remarkably apparent in the examples of the present application, the above technical solution is illustrated by a plurality of examples below.
Example 1
A perovskite cluster solution, the preparation of which comprises the steps of:
the weight ratio of substances is 1:1 reacting 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 the volume of solvent being 1.0 mL; then, Yb (NO) was added3)3·5H2O, octadecenoic acid and octadecenylamine and stirring at 30 deg.C for 1h, wherein Yb (NO)3)3·5H2The addition amount of O and the amount ratio of the lead bromide substances are 1:1, and the addition amount of octadecenylamine and the amount ratio of the lead bromide substances are 2: 1, preparing a precursor solution of the perovskite cluster, wherein the quantity ratio of the addition amount of octadecenoic acid to the lead bromide substance is 4: 1;
injecting the perovskite cluster precursor solution into toluene according to the volume ratio of 0.5:10, rapidly stirring for about 2 minutes at room temperature, centrifuging the mixed solution at the speed of 10000r/min for 10 minutes for 3 times, collecting the supernatant liquid after centrifugation each time to obtain the perovskite cluster solution, and finally storing the obtained perovskite cluster solution in a refrigerator at low temperature (0-5 ℃) for later use, wherein the particle size of the perovskite cluster is 1.5-2.5 nm.
Example 2
A perovskite cluster solution, the preparation of which comprises the steps of:
the weight ratio of substances is 1:1 reacting cesium bromide (CsBr) and lead bromide (PbBr)2) Dissolving in N, N-Dimethylformamide (DMF) solvent, and stirring to dissolve completely; the initial concentration of lead bromide was 0.04mol/L, with the volume of solvent being 1.0 mL; then, Yb (NO) was added3)3·5H2O, phenylacetic acid and phenethylamine and stirring at 30 ℃ for 1h, wherein Yb (NO)3)3·5H2Addition amount of OThe quantity ratio of the lead bromide to the phenethylamine is 1:1, and the quantity ratio of the phenethylamine to the lead bromide is 2: 1, preparing a precursor solution of the perovskite cluster, wherein the quantity ratio of the addition amount of phenylacetic acid to the lead bromide substance is 4: 1;
injecting the perovskite cluster precursor solution into toluene according to the volume ratio of 0.5:10, rapidly stirring for about 2 minutes at room temperature, centrifuging the mixed solution at the speed of 10000r/min for 10 minutes for 3 times, collecting the supernatant liquid after centrifugation each time to obtain the perovskite cluster solution, and finally storing the obtained perovskite cluster solution in a refrigerator at low temperature (0-5 ℃) for later use, wherein the particle size of the perovskite cluster is 1.7-2.1 nm.
Example 3
A perovskite cluster solution, the preparation of which comprises the steps of:
the weight ratio of substances is 1:1 reacting 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 the volume of solvent being 1.0 mL; then, Yb (NO) was added3)3·5H2O, octadecenoic acid and octadecenylamine and stirring at 30 deg.C for 1h, wherein Yb (NO)3)3·5H2The addition amount of O and the amount ratio of the lead bromide substances are 1:1, and the addition amount of octadecenylamine and the amount ratio of the lead bromide substances are 2: 1, preparing a precursor solution of the perovskite cluster, wherein the quantity ratio of the addition amount of octadecenoic acid to the lead bromide substance is 4: 1;
injecting the perovskite cluster precursor solution into trichloromethane according to the volume ratio of 3:20, rapidly stirring for about 2 minutes at room temperature, centrifuging the mixed solution at the speed of 10000r/min for 10 minutes for 3 times, centrifuging the mixed solution to collect a supernatant liquid, obtaining the perovskite cluster solution, and finally storing the obtained perovskite cluster solution in a refrigerator at low temperature (0-5 ℃) for later use, wherein the particle size of the perovskite cluster is 2.0-3.0 nm.
Example 4
A perovskite cluster solution, the preparation of which comprises the steps of:
the weight ratio of substances is 1:1 reacting 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 the volume of solvent being 1.0 mL; then, Eu (NO) is added3)3·5H2O, octadecenoic acid and octadecenylamine and stirring at 30 deg.C for 1h, wherein Eu (NO)3)3·5H2The addition amount of O and the amount ratio of the lead bromide substances are 8:1, and the addition amount of octadecenylamine and the amount ratio of the lead bromide substances are 2: 1, preparing a precursor solution of the perovskite cluster, wherein the quantity ratio of the addition amount of octadecenoic acid to the lead bromide substance is 4: 1;
injecting the perovskite cluster precursor solution into toluene according to the volume ratio of 0.5:10, rapidly stirring for about 2 minutes at room temperature, centrifuging the mixed solution at the speed of 10000r/min for 10 minutes and 3 times, wherein the product collected by each centrifugation is supernatant to obtain the perovskite cluster solution, and finally storing the obtained perovskite cluster solution in a refrigerator at low temperature (0-5 ℃) for later use, wherein the particle size of the perovskite cluster is 1.0-2.0 nm.
Comparative example 1
A perovskite material solution, the preparation of which comprises the steps of:
the weight ratio of substances is 1:1 reacting 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 the volume of solvent being 0.4 mL; then adding octadecenoic acid and octadecenylamine, stirring and dissolving, wherein the amount ratio of the addition amount of the octadecenylamine to the lead bromide substance is 0.6-1, and the amount ratio of the addition amount of the octadecenylamine to the lead bromide substance is 0.3:1, so as to prepare a precursor solution of the perovskite cluster;
injecting the perovskite cluster precursor solution into toluene according to the volume ratio of 0.5:10, rapidly stirring for about 2 minutes at room temperature, centrifuging the mixed solution at the speed of 10000r/min for 10 minutes, centrifuging for 3 times, collecting the product by centrifuging each time, wherein the product is supernatant, and the perovskite cluster cannot be formed in the solution.
Comparative example 2
A perovskite material solution, the preparation of which comprises the steps of:
the weight ratio of substances is 1:1 reacting 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 the volume of solvent being 1.0 mL; then, Yb (NO) was added3)3·5H2O and octadecenylamine and stirred at 30 ℃ for 1h, wherein Yb (NO)3)3·5H2The addition amount of O and the amount ratio of the lead bromide substances are 1:1, and the addition amount of octadecenylamine and the amount ratio of the lead bromide substances are 2: 1, preparing a precursor solution of the perovskite cluster;
injecting the perovskite cluster precursor solution into toluene according to the volume ratio of 0.5:10, rapidly stirring for about 2 minutes at room temperature, centrifuging the mixed solution at the speed of 10000r/min for 10 minutes, centrifuging for 3 times, collecting the product by centrifuging each time, wherein the product is supernatant, and the perovskite cluster cannot be formed in the solution.
Comparative example 3
A perovskite material solution, the preparation of which comprises the steps of:
the weight ratio of substances is 1:1 reacting 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 the volume of solvent being 1.0 mL; then, Yb (NO) was added3)3·5H2O and octadecenoic acid and stirring at 30 deg.C for 1h, wherein Yb (NO)3)3·5H2The quantity ratio of the addition amount of O to the lead bromide substance is 1:1, and the quantity ratio of the addition amount of octadecenoic acid to the lead bromide substance is 4:1, so as to prepare a precursor solution of the perovskite cluster;
injecting the perovskite cluster precursor solution into toluene according to the volume ratio of 0.5:10, rapidly stirring for about 2 minutes at room temperature, centrifuging the mixed solution at the speed of 10000r/min for 10 minutes, centrifuging for 3 times, collecting the product by centrifuging each time, wherein the product is supernatant, and the perovskite cluster cannot be formed in the solution.
Comparative example 4
A perovskite material solution, the preparation of which comprises the steps of:
the weight ratio of substances is 1:1 reacting 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 the volume of solvent being 1.0 mL; then, Yb (NO) was added3)3·5H2O and stirring at 30 ℃ for 1h, wherein Yb (NO)3)3·5H2The quantity ratio of the addition amount of O to the lead bromide substance is 1:1, and precursor solution of the perovskite cluster is prepared;
injecting the perovskite cluster precursor solution into toluene according to the volume ratio of 0.5:10, rapidly stirring for about 2 minutes at room temperature, centrifuging the mixed solution at the speed of 10000r/min for 10 minutes, centrifuging for 3 times, collecting the product by centrifuging each time, wherein the product is supernatant, and the perovskite cluster cannot be formed in the solution.
Further, in order to verify the advancement of the embodiments of the present application, the following performance tests were performed on the embodiments:
1. characteristic peaks of the ultraviolet absorption spectrum and the fluorescence emission spectrum of the perovskite cluster solution prepared in example 1 were measured by an ultraviolet-visible spectrophotometer and a fluorescence spectrophotometer test instrument, and the test results are shown in fig. 3, in which the corresponding characteristic peaks are 393nm and 397nm, respectively.
2. The perovskite cluster solution prepared in example 2 was tested for morphology and size by a high-resolution transmission electron microscope test instrument, and the test results are shown in fig. 4, which shows that the perovskite cluster is spherical and the average size is 1.90 ± 0.2 nm.
3. Example 3 was supplemented with Yb (NO) by a spectrofluorometer3)3·5H2Perovskite cluster solution prepared from O and comparative example 1 with NO addition of lanthanide rare earth salt hydrate (M (NO)3)3·XH2O) the perovskite material prepared by the method is compared with the fluorescence emission spectrum intensity, the test result is shown in the attached figure 5, and the test result shows that the perovskite material prepared by the method of the example 1 (with M (NO)3)3·XH2O) addition of M (NO)3)3·XH2Perovskite mass of OThe fluorescence emission spectrum intensity of the cluster is obviously enhanced, and the luminescence property is improved. And comparative example 1 (NO M (NO)3)3·XH2O) without addition of M (NO)3)3·XH2The fluorescence emission spectrum intensity of the perovskite material of O is weak.
4. Stability test was carried out at 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 tester3)3·5H2Perovskite cluster solution prepared from O and comparative example 1 with NO addition of lanthanide rare earth salt hydrate (M (NO)3)3·XH2O) the perovskite material prepared was tested for fluorescence quantum yield and the results are shown in table 1 below. As can be seen, examples 1 to 4 of examples contain Yb (NO)3)3·5H2The perovskite cluster prepared by O has a high initial fluorescence quantum yield value, and still has a high fluorescence quantum yield after 72 hours, and shows good stability. While comparative example 1 did not add lanthanide rare earth salt hydrate (M (NO)3)3·XH2O) prepared perovskite material has low fluorescence quantum yield and is easy to quench.
Wherein the test pattern of example 1 is shown in FIG. 6, the test results show that with the fluorescence quantum yield test of 72 hours, example 1 (with M (NO)3)3·XH2The fluorescence quantum yield of the O) perovskite cluster is reduced from 91% to 87%, and the O) perovskite cluster shows good stability and luminescence performance. And comparative example 1 (NO M (NO)3)3·XH2O) without addition of M (NO)3)3·XH2The fluorescence quantum yield of the perovskite material of O is reduced from the original 65% to 0%, and the perovskite material should be basically quenched.
TABLE 1
| Initial value of fluorescence quantum yield% | Fluorescence quantum yield after 72 hours% | |
| Example 1 | 91％ | 87％ |
| Example 2 | 87％ | 82％ |
| Example 3 | 89％ | 84％ |
| Example 4 | 90％ | 84％ |
| Comparative example 1 | 65％ | 0 |
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. A preparation method of perovskite cluster solution is characterized in that: the method comprises the following steps:
preparing lanthanide series rare earth metal salt hydrate, organic carboxylic acid, organic amine ligand and perovskite raw material into precursor solution;
and mixing the precursor solution and an anti-solvent, and purifying to obtain the perovskite cluster solution.
2. The method for preparing a perovskite cluster solution according to claim 1, characterized in that: the perovskite starting material comprises a divalent metal halide and an organic ammonium halide or alkali metal halide;
and/or the step of preparing the precursor solution comprises: dissolving the perovskite raw material in an organic solvent, mixing for 10-30 minutes, adding the lanthanide rare earth 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. The method for preparing a perovskite cluster solution according to claim 2, characterized in that: the lanthanide rare earth salt hydrate is selected from: trivalent lanthanide rare earth metal hydrous nitrates;
and/or 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. The method for producing a perovskite cluster solution according to claim 3, characterized in that: the trivalent lanthanide rare earth metal hydrous nitrate comprises Yb (NO)3)3·5H2O、Dy(NO3)3·6H2O、Eu(NO3)3·5H2O、Sm(OH)3·6H2O、Pr(NO3)3·6H2At least one of O.
5. The method for producing a perovskite cluster solution according to any one of claims 2 to 4, characterized by: the volume ratio of the precursor solution to the anti-solvent is (0.2-4): (5-35);
and/or the antisolvent comprises at least one of n-hexane, toluene, dichloromethane and trichloromethane;
and/or the mixing treatment time is 1-3 minutes.
6. The method for producing a perovskite cluster solution according to any one of claims 2 to 4, characterized by: the molar ratio of the organic carboxylic acid to the halogenated divalent metal is (2-10): 1;
and/or the molar ratio of the organic amine ligand to the halogenated divalent metal is (1-10): 1;
and/or, the step of purifying comprises: and centrifuging the mixed solution after the mixing treatment, and collecting supernatant to obtain the perovskite cluster solution.
7. The method of preparing a perovskite cluster solution according to claim 6, characterized in that: the organic carboxylic acid comprises at least one of propionic acid, n-butyric acid, n-valeric acid, octadecanoic acid, octadecenoic acid, benzoic acid and phenylacetic acid;
and/or the organic amine ligand comprises at least one of octadecylamine, octadecenylamine, benzylamine and phenethylamine;
and/or the halogenated divalent metal comprises at least one of lead halide, tin halide, germanium halide, gallium halide, nickel halide, manganese halide, cobalt halide and copper halide;
and/or the organic ammonium halide comprises CH3NH3Cl、CH3NH3Br、CH3NH3I、CH2(NH3)2Cl、CH2(NH3)2Br、CH2(NH3)2I、CH3CH2NH3Cl、CH3CH2NH3Br、CH3CH2NH3At least one of I;
and/or the alkali halide comprises at least one of CsCl, CsBr, CsI, RbCl, RbBr and RbI;
and/or the organic solvent comprises at least one of dimethyl sulfoxide and N, N-dimethylformamide.
8. A perovskite cluster solution characterized by: organic carboxylic acid and organic amine ligand are combined on the surface of the perovskite cluster in the perovskite cluster solution, and a molecular coating layer is formed by lanthanide rare earth metal salt hydrate.
9. The perovskite cluster solution of claim 8, wherein: the particle size of the perovskite clusters in the perovskite cluster solution is 1-3 nm;
and/or, the lanthanide rare earth salt hydrate comprises Yb (NO)3)3·5H2O、Dy(NO3)3·6H2O、Eu(NO3)3·5H2O、Sm(OH)3·6H2O、Pr(NO3)3·6H2At least one trivalent lanthanide rare earth metal hydrous nitrate in O;
and/or the organic carboxylic acid comprises at least one of propionic acid, n-butyric acid, n-valeric acid, octadecanoic acid, octadecenoic acid, benzoic acid and phenylacetic acid;
and/or the organic amine ligand comprises at least one of octadecylamine, octadecenylamine, benzylamine and phenethylamine.
10. An optoelectronic device, characterized by: the photoelectric device comprises the perovskite cluster solution prepared by the method according to any one of claims 1 to 7 or the perovskite cluster solution according to any one of claims 8 to 9.
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| CN116904187B (en) * | 2023-07-21 | 2024-06-28 | 重庆邮电大学 | Preparation method of benzoic acid modified lead-free metal halide perovskite micro-crystal material, and product and application thereof |
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