CN114195650A - Perovskite metal halide zero-dimensional quantum dot composite material, preparation method thereof and application of organic amine salt - Google Patents

Perovskite metal halide zero-dimensional quantum dot composite material, preparation method thereof and application of organic amine salt Download PDF

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CN114195650A
CN114195650A CN202111522151.XA CN202111522151A CN114195650A CN 114195650 A CN114195650 A CN 114195650A CN 202111522151 A CN202111522151 A CN 202111522151A CN 114195650 A CN114195650 A CN 114195650A
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zero
metal halide
quantum dot
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dimensional quantum
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袁明鉴
姜源植
孙长久
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Nankai University
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
    • C07C211/26—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing at least one six-membered aromatic ring
    • C07C211/27—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing at least one six-membered aromatic ring having amino groups linked to the six-membered aromatic ring by saturated carbon chains
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
    • C07C211/26—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing at least one six-membered aromatic ring
    • C07C211/29—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by halogen atoms or by nitro or nitroso groups
    • C—CHEMISTRY; METALLURGY
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    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/54—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton
    • C07C217/56—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton with amino groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by carbon chains not further substituted by singly-bound oxygen atoms
    • C07C217/58—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton with amino groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by carbon chains not further substituted by singly-bound oxygen atoms with amino groups and the six-membered aromatic ring, or the condensed ring system containing that ring, bound to the same carbon atom of the carbon chain
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/66—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing germanium, tin or lead
    • C09K11/664—Halogenides

Abstract

The invention provides a preparation method of a perovskite metal halide zero-dimensional quantum dot composite material, which comprises the following steps: mixing a first precursor, a second precursor, a third precursor and a solvent to obtain a precursor solution, wherein the first precursor is at least one of methylamine halide, formamidine halide, cesium trifluoroacetate, cesium stearate and cesium acetate, the second precursor is at least one of lead halide, stannous halide, lead stearate and lead acetate, the third precursor is an organic amine salt, and cations of the third precursor comprise an aliphatic ring framework structure, an aromatic ring framework structure or a thiophene ring framework structure, and an amino bonding head and a steric hindrance group which are bonded on the framework structure; spin coating the precursor solution to obtain the perovskite quantum dot active material; and carrying out annealing treatment on the perovskite quantum dot active material. The invention also provides a perovskite metal halide zero-dimensional quantum dot composite material and application of organic amine salt in preparation of the perovskite metal halide zero-dimensional quantum dot composite material.

Description

Perovskite metal halide zero-dimensional quantum dot composite material, preparation method thereof and application of organic amine salt
Technical Field
The invention relates to the technical field of new material preparation, in particular to a preparation method of a perovskite metal halide zero-dimensional quantum dot composite material, the perovskite metal halide zero-dimensional quantum dot composite material prepared by the method and application of organic amine salt in preparation of the perovskite metal halide zero-dimensional quantum dot composite material.
Background
Quantum dots refer to zero-dimensional nanocrystals with particle sizes below the bohr diameter of the exciton, which are typically less than 15nm in diameter. Quantum dot materials have received much attention from researchers because they exhibit unique optical properties due to their quantum confinement effects. Compared with the traditional semiconductor quantum dot, the perovskite metal halide quantum dot (ABX3, A is methylamine, formamidine or cesium cation, B is lead or tin cation, and X is Cl, Br or I ion) has excellent optical properties such as high photoluminescence quantum yield, high color purity, wide color gamut and the like. In addition, the band gap can be changed by changing the components and the proportion of halogen elements in the perovskite structure, and continuous tunable emission from purple to near infrared is further realized. The excellent optoelectronic properties of perovskite metal halide quantum dots make them a very potential luminescent material. Perovskite metal halide quantum dots are currently available for use in active layers in light emitting diodes, backlight films in thin film display panels, active layers for photodetectors, light absorbing layers for solar cells, and emissive layers for lasers. Light emitting devices based on perovskite metal halide quantum dots achieve a wider color gamut and higher quantum efficiency.
At present, the preparation methods of perovskite metal halide quantum dots are mainly divided into solution methods (mainly divided into a thermal injection method and a ligand-assisted precipitation method) and high-temperature extrusion methods. The hot injection method was first reported by the Kovalenko team and comprises the following steps: dissolving cesium carbonate and an organic ligand in an octadecene solution at a high temperature to obtain a clear cesium oleate solution; rapidly injecting the cesium oleate solution into an octadecene solution dissolved with lead halide and an organic ligand at high temperature; and centrifuging and washing to obtain the final product. The ligand-assisted precipitation method is reported for the first time by the Messaging Haibop team and comprises the following steps: dissolving lead halide and lead cesium halide in polar N, N-dimethylformamide or dimethyl sulfoxide, and adding a ligand to obtain a precursor solution; rapidly adding the precursor solution into a non-polar solvent under vigorous stirring; and (4) centrifuging and purifying to obtain a final product. The steps of preparing the perovskite metal halide quantum dot/polymer composite material by a high-temperature extrusion method comprise: placing the perovskite precursor and the polymer material in an extruder for high-temperature blending to obtain a mixture; and carrying out injection molding on the mixture to obtain the perovskite metal halide zero-dimensional quantum dot composite material.
Although, higher quality perovskite metal halide quantum dots have been prepared based on thermal injection and ligand-assisted precipitation methods. However, the hot injection method has disadvantages of severe process conditions (e.g., requiring high temperature and severe anhydrous, and oxygen-free conditions), and complicated process (e.g., requiring post-treatment steps such as centrifugal purification). The ligand-assisted precipitation method has the defects of complex process (for example, the need of post-treatment steps such as centrifugal purification and the like) and difficulty in synthesizing the perovskite metal halide quantum dots with ultra-small particle size (the diameter is less than 15 nm). In addition, most of the perovskite metal halide zero-dimensional quantum dot composite materials prepared by the high-temperature extrusion method are lamellar phase materials with a large number of layers, so that the size confinement effect of the prepared perovskite metal halide zero-dimensional quantum dot composite materials is weak. Clearly, there are still many significant drawbacks and deficiencies with these three techniques, resulting in controllable particle size of perovskite metal halide quantum dots and still challenges in large scale production.
Further, the perovskite metal halide quantum dots can be prepared into a film shape by adopting a spin coating or blade coating process. During the spin coating or blade coating process, the rotational linear speed of the edge of the substrate and the central area of the substrate is greatly different, so that the particle size of the prepared perovskite metal halide quantum dot is not adjustable.
Disclosure of Invention
The invention mainly aims to provide a preparation method of a perovskite metal halide zero-dimensional quantum dot composite material, and aims to solve the defect that the particle size of the perovskite metal halide zero-dimensional quantum dot composite material prepared by the existing preparation method is not adjustable.
In order to solve the technical problems, the invention provides an application of an organic amine salt in preparation of a perovskite metal halide zero-dimensional quantum dot composite material, wherein cations of the organic amine salt comprise an aliphatic ring framework structure, an aromatic ring framework structure or a thiophene ring framework structure, and at least one amino bonding head and at least one steric hindrance group which are bonded on the aliphatic ring framework structure, the aromatic ring framework structure or the thiophene ring framework structure.
Cations of the organic amine salt can be coordinated with halogen elements on the surface of the perovskite through electrostatic and hydrogen bond interaction, and further the perovskite is inhibited from growing in the out-of-plane direction to form a layered structure. In addition, the organic amine cation comprises an aliphatic ring framework structure, an aromatic ring framework structure or a thiophene ring framework structure shown in figure 1, and at least one amino bonding head and at least one steric hindrance group bonded on the aliphatic ring framework structure, the aromatic ring framework structure or the thiophene ring framework structure. The number of the amino bonding heads is preferably 1, the number of the steric hindrance groups can be at least one, and the amino bonding heads and the steric hindrance groups are bonded at any position of an aliphatic ring framework structure, an aromatic ring framework structure or a thiophene ring framework structure. No matter in the preparation of the perovskite metal halide zero-dimensional quantum dot composite material by methods such as a spin coating method, a vacuum coating method, a high-temperature extrusion method and the like, the steric hindrance group can inhibit the perovskite from being generated into a layered structure and can promote the perovskite to be generated into the zero-dimensional quantum dot with a strong size confinement effect. Therefore, the organic amine salt is applied to the preparation of the perovskite metal halide zero-dimensional quantum dot composite material, and the particle size of the perovskite metal halide zero-dimensional quantum dot composite material can be regulated and controlled.
The invention also provides a preparation method of the perovskite metal halide zero-dimensional quantum dot composite material, which comprises the following steps:
providing a first precursor, a second precursor, a third precursor and a solvent, wherein the first precursor is selected from at least one of methylamine halide, formamidine halide, cesium trifluoroacetate, cesium stearate and cesium acetate, the second precursor is selected from at least one of lead halide, stannous halide, lead stearate and lead acetate, the third precursor is an organic amine salt, the anion of the organic amine salt is a halogen ion, and the cation of the organic amine salt comprises an aliphatic ring framework structure, an aromatic ring framework structure or a thiophene ring framework structure, and at least one amino head and at least one steric hindering group which are bonded on the aliphatic ring framework structure, the aromatic ring framework structure or the thiophene ring framework structure;
mixing the first precursor, the second precursor, the third precursor and a solvent to obtain a precursor solution;
adding the precursor solution onto a substrate, and performing spin coating film forming treatment on the precursor solution on the substrate to obtain a perovskite quantum dot active material; and
and annealing the perovskite quantum dot active material to obtain the perovskite metal halide zero-dimensional quantum dot composite material, wherein the perovskite metal halide zero-dimensional quantum dot composite material comprises perovskite metal halide zero-dimensional quantum dots and organic amine cations coated on the surfaces of the perovskite metal halide zero-dimensional quantum dots.
Further, at least one of the following conditions a-f is satisfied:
a. the particle size of the perovskite metal halide zero-dimensional quantum dot is 3-15 nm;
b. the steric hindrance group is at least one of methyl, methoxy and halogen;
c. the solvent is at least one of dimethyl sulfoxide, N-dimethylformamide, N-methylpyrrolidone and acetonitrile;
d. the perovskite metal halide zero-dimensional quantum dot composite material has a film-shaped structure, and the thickness of the perovskite metal halide zero-dimensional quantum dot composite material with the film-shaped structure is 10-500 nm;
e. the molar ratio of the first precursor to the second precursor is 0.1-0.9: 1;
f. the molar ratio of the third precursor to the second precursor is 0.2-1.4: 1.
further, the preparation method of the perovskite metal halide zero-dimensional quantum dot composite material further comprises the following steps:
providing a passivating agent; and
and mixing the first precursor, the second precursor, the third precursor, a passivating agent and a solvent to obtain a precursor solution, wherein the passivating agent is trimethyl ammonium bromide and/or tetrabutyl phosphonium chloride, and the molar ratio of the passivating agent to the second precursor is 0.05-0.1: 1.
further, the preparation method of the perovskite metal halide zero-dimensional quantum dot composite material further comprises the following steps:
providing an anti-solvent; and
in the spin coating film forming process, adding the anti-solvent to the substrate to obtain the perovskite quantum dot active material, wherein the anti-solvent is at least one of toluene, chlorobenzene and chloroform, and the volume ratio of the anti-solvent to the precursor solution on the substrate is 1-2: 1.
the invention also provides a perovskite metal halide zero-dimensional quantum dot composite material which comprises perovskite metal halide zero-dimensional quantum dots and organic amine cations coated on the surfaces of the perovskite metal halide zero-dimensional quantum dots, wherein the organic amine cations comprise an alicyclic ring skeleton structure, an aromatic ring skeleton structure or a thiophene ring skeleton structure, and at least one amino bonding head and at least one steric hindrance group which are bonded on the alicyclic ring skeleton structure, the aromatic ring skeleton structure or the thiophene ring skeleton structure.
Further, the perovskite metal halide zero-dimensional quantum dot composite material further comprises a passivating agent bonded on the surface of the perovskite metal halide zero-dimensional quantum dot, wherein the passivating agent is trimethyl ammonium bromide and/or tetrabutyl phosphonium chloride.
Further, the steric hindrance group is at least one of methyl, methoxy and halogen; and/or the perovskite metal halide zero-dimensional quantum dot composite material has a film-like structure, and the thickness of the perovskite metal halide zero-dimensional quantum dot composite material with the film-like structure is 10-500 nm; and/or the particle size of the perovskite metal halide zero-dimensional quantum dot is 3-15 nm.
According to the technical scheme, the first precursor, the second precursor, the third precursor and a solvent are mixed to obtain a precursor solution, the precursor solution is arranged on a substrate, the precursor solution on the substrate is subjected to spin coating film forming treatment to obtain a perovskite quantum dot active material, and the perovskite quantum dot active material is subjected to annealing treatment to obtain the perovskite metal halide zero-dimensional quantum dot composite material. The perovskite metal halide zero-dimensional quantum dot composite material comprises perovskite metal halide zero-dimensional quantum dots and organic amine salts coated on the surfaces of the perovskite metal halide zero-dimensional quantum dots. The organic amine cation of the organic amine salt can be coordinated with the halogen element on the surface of the perovskite through electrostatic and hydrogen bond interaction, so that the perovskite is inhibited from growing in the out-of-plane direction to form a layered structure. In addition, the organic amine cation comprises an aliphatic ring framework structure, an aromatic ring framework structure or a thiophene ring framework structure shown in figure 1, and at least one amino bonding head and at least one steric hindrance group bonded on the aliphatic ring framework structure, the aromatic ring framework structure or the thiophene ring framework structure. The number of the amino bonding heads is preferably 1, the number of the steric hindrance groups can be at least one, and the amino bonding heads and the steric hindrance groups are bonded at any position of an aliphatic ring framework structure, an aromatic ring framework structure or a thiophene ring framework structure. The steric hindrance group can inhibit the perovskite from being generated into a layered structure, and can promote the perovskite to be generated into the zero-dimensional quantum dot with the strong size confinement effect. Therefore, the preparation method of the perovskite metal halide zero-dimensional quantum dot composite material has the advantage of controllable particle size. Moreover, the preparation method of the perovskite metal halide zero-dimensional quantum dot composite material does not need to adopt harsh conditions such as high temperature, strict anhydrous oxygen-free condition and the like, and also does not need to adopt post-treatment steps such as centrifugal purification and the like, so that the preparation method of the perovskite metal halide zero-dimensional quantum dot composite material has the advantages of low process condition requirement, low cost and simple process.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the structures shown in the drawings without creative efforts.
FIG. 1 is a molecular structure diagram of the backbone structure, amine-based linker and steric hindrance group of the organic amine cation employed in the present invention.
FIG. 2 is a molecular structure diagram of several organic amine cations employed in the present invention.
Fig. 3 is a fluorescence spectrum of the perovskite metal halide zero-dimensional quantum dot composite material of embodiment 1 of the invention.
Fig. 4 is a transmission electron micrograph of the perovskite metal halide zero-dimensional quantum dot composite of example 1 of the present invention.
Fig. 5 is a fluorescence spectrum of the perovskite metal halide zero-dimensional quantum dot composite material of embodiment 2 of the invention.
Fig. 6 is a transmission electron micrograph of the perovskite metal halide zero-dimensional quantum dot composite of example 2 of the present invention.
Fig. 7 is a fluorescence spectrum of the bulk perovskite metal halide composite of comparative example 1 of the present invention.
FIG. 8 is a transmission electron micrograph of a bulk perovskite metal halide composite of comparative example 1 of the present invention.
Fig. 9 is a fluorescence spectrum of the perovskite metal halide zero-dimensional quantum dot/polymer composite material of embodiment 3 of the invention.
Fig. 10 is a transmission electron micrograph of the perovskite metal halide zero-dimensional quantum dot/polymer composite of example 3 of the present invention.
Fig. 11 is a fluorescence spectrum of the perovskite metal halide zero-dimensional quantum dot/polymer composite material of embodiment 4 of the invention.
Fig. 12 is a transmission electron micrograph of the perovskite metal halide zero-dimensional quantum dot/polymer composite of example 4 of the present invention.
FIG. 13 is a fluorescence spectrum of the perovskite metal halide zero-dimensional quantum dot/polymer composite material of comparative example 2 of the present invention.
FIG. 14 is a transmission electron micrograph of a perovskite metal halide zero-dimensional quantum dot/polymer composite of comparative example 2 of the present invention.
Fig. 15 is a fluorescence spectrum of the perovskite metal halide zero-dimensional quantum dot composite material of embodiment 5 of the present invention.
Fig. 16 is a transmission electron micrograph of the perovskite metal halide zero-dimensional quantum dot composite of example 5 of the present invention.
Fig. 17 is a scanning electron micrograph of the perovskite metal halide zero-dimensional quantum dot composite of example 5 of the present invention.
FIG. 18 is a fluorescence spectrum of the perovskite metal halide zero-dimensional quantum dot composite material of comparative example 3 of the present invention.
Fig. 19 is a scanning electron micrograph of a perovskite metal halide zero-dimensional quantum dot composite of comparative example 3 of the present invention.
The implementation, functional features and advantages of the objects of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In addition, the descriptions related to "first", "second", etc. in the present invention are for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In addition, technical solutions between various embodiments may be combined with each other, but must be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention.
The invention provides an application of organic amine salt in preparation of a perovskite metal halide zero-dimensional quantum dot composite material, wherein cations of the organic amine salt comprise an aliphatic ring framework structure, an aromatic ring framework structure or a thiophene ring framework structure, and at least one amino bonding head and at least one steric hindering group which are bonded on the aliphatic ring framework structure, the aromatic ring framework structure or the thiophene ring framework structure.
Cations of the organic amine salt can be coordinated with halogen elements on the surface of the perovskite through electrostatic and hydrogen bond interaction, and further the perovskite is inhibited from growing in the out-of-plane direction to form a layered structure. In addition, the organic amine cation comprises an aliphatic ring framework structure, an aromatic ring framework structure or a thiophene ring framework structure shown in figure 1, and at least one amino bonding head and at least one steric hindrance group bonded on the aliphatic ring framework structure, the aromatic ring framework structure or the thiophene ring framework structure. The number of the amino bonding heads is preferably 1, the number of the steric hindrance groups can be at least one, and the amino bonding heads and the steric hindrance groups are bonded at any position of an aliphatic ring framework structure, an aromatic ring framework structure or a thiophene ring framework structure. No matter in the preparation of the perovskite metal halide zero-dimensional quantum dot composite material by methods such as a spin coating method, a vacuum coating method, a high-temperature extrusion method and the like, the steric hindrance group can inhibit the perovskite from being generated into a layered structure and can promote the perovskite to be generated into the zero-dimensional quantum dot with a strong size confinement effect. Therefore, the organic amine salt is applied to the preparation of the perovskite metal halide zero-dimensional quantum dot composite material, and the particle size of the perovskite metal halide zero-dimensional quantum dot composite material can be regulated and controlled.
The first embodiment of the invention provides a preparation method of a perovskite metal halide zero-dimensional quantum dot composite material. The preparation method of the perovskite metal halide zero-dimensional quantum dot composite material comprises the following steps:
providing a first precursor, a second precursor, a third precursor and a solvent, wherein the first precursor is selected from at least one of methylamine halide, formamidine halide, cesium trifluoroacetate, cesium stearate and cesium acetate, the second precursor is selected from at least one of lead halide, stannous halide, lead stearate and lead acetate, the third precursor is an organic amine salt, the anion of the organic amine salt is a halogen ion, and the cation of the organic amine salt comprises an aliphatic ring framework structure, an aromatic ring framework structure or a thiophene ring framework structure, and at least one amino head and at least one steric hindering group which are bonded on the aliphatic ring framework structure, the aromatic ring framework structure or the thiophene ring framework structure;
mixing the first precursor, the second precursor, the third precursor and a solvent to obtain a precursor solution;
adding the precursor solution onto a substrate, and performing spin coating film forming treatment on the precursor solution on the substrate to obtain a perovskite quantum dot active material; and
and annealing the perovskite quantum dot active material to obtain the perovskite metal halide zero-dimensional quantum dot composite material, wherein the perovskite metal halide zero-dimensional quantum dot composite material comprises perovskite metal halide zero-dimensional quantum dots and organic amine salts coated on the surfaces of the perovskite metal halide zero-dimensional quantum dots.
In at least one embodiment, the perovskite metal halide zero-dimensional quantum dot composite material has a film-like structure, and the thickness of the perovskite metal halide zero-dimensional quantum dot composite material with the film-like structure is 10-500 nm. For example, 10nm, 50nm, 100nm, 200nm, 300nm, 400nm or 500 nm.
In at least one embodiment, the particle size of the perovskite metal halide zero-dimensional quantum dot is 3-15 nm, for example, 3nm, 5nm, 7nm, 10nm, or 15 nm.
In at least one embodiment, the organic amine salt may be a bulky organic amine salt (see fig. 2), which may be a bulky organic amine salt containing 3 or more carbon atoms. Due to the fact that the size of the organic amine salt is too large, the organic amine salt with large size cannot enter the interior of crystal lattices of the perovskite, and can be coordinated with halogen elements on the surface of the perovskite through electrostatic and hydrogen bond interaction, and therefore growth of the perovskite is inhibited.
In at least one embodiment, the molar ratio of the first precursor to the second precursor is 0.1-0.9: 1. for example, 0.1: 1. 0.3: 1. 0.45: 1. 0.5: 1. 0.6: 1. 0.7: 1. 0.8: 1. or 0.9: 1.
in at least one embodiment, the molar ratio of the second precursor to the third precursor is 0.2-1.4: 1. for example, 0.2: 1. 0.5: 1. 0.7: 1. 0.9: 1. 1.1: 1. 1.3: 1. or 1.4: 1.
the size of the micelle in the precursor liquid is controlled by changing the ratio of the third precursor to the second precursor in the precursor liquid, so that the particle size of the perovskite metal halide zero-dimensional quantum dot is adjusted.
The low-concentration bulky organic amine salt is used for manufacturing perovskite metal halide zero-dimensional quantum dots with larger grain sizes and longer emission wavelengths, and the high-concentration bulky organic amine salt is used for manufacturing perovskite metal halide zero-dimensional quantum dots with smaller grain sizes and shorter emission wavelengths. This is because, as the content of the bulky organic amine salt increases, the growth inhibitory effect of the bulky organic amine salt on the perovskite metal halide zero-dimensional quantum dot becomes gradually apparent. Therefore, perovskite metal halide zero-dimensional quantum dots with different particle sizes and different emission wavelengths can be prepared by adjusting the content of the large-volume organic amine salt in the precursor liquid.
In at least one embodiment, the steric hindrance group is at least one of methyl, methoxy, and halogen.
In at least one embodiment, for Br system perovskite metal halide zero-dimensional quantum dots, the bulky organic amine salt used is 4-fluoro-alpha-phenylethylamine hydrogen bromide, 4-chloro-alpha-phenylethylamine hydrogen bromide, 4-bromo-alpha-phenylethylamine hydrogen bromide, 4-iodo-alpha-phenylethylamine hydrogen bromide, 4-methyl-alpha-phenylethylamine hydrogen bromide, or 4-methoxy-alpha-phenylethylamine hydrogen bromide.
In at least one embodiment, for the perovskite metal halide zero-dimensional quantum dots of system I, the bulky organic amine salt used is 1- (4-fluorophenyl) -1-methylethylamine hydroiodide, 1- (4-iodophenyl) -1-methylethylamine hydroiodide, 1- (4-chlorophenyl) -1-methylethylamine hydroiodide, 1- (4-methylbenzene) -1-methylethylamine hydroiodide, 1- (4-bromophenyl) -1-methylethylamine hydroiodide, or 1- (4-methoxyphenyl) -1-methylethylamine hydroiodide.
In at least one embodiment, the solvent is at least one of dimethylsulfoxide, N-dimethylformamide, N-methylpyrrolidone, and acetonitrile.
In at least one embodiment, the concentration of the second precursor in the precursor solution is 0.15-0.25 mol/L, preferably 0.2 mol/L.
In at least one embodiment, the substrate is a transparent substrate, and is made of ordinary soda-lime glass, nano indium-tin metal oxide, fluorine-doped tin dioxide, quartz, or flexible polyethylene terephthalate.
In at least one embodiment, the precursor solution may be filtered by a filter with a pore size of 0.22 μm to filter out insoluble impurities in the precursor solution, and then stored in a nitrogen environment for use.
In at least one embodiment, the spin coating film forming process can be performed by a spin coater, the rotation speed of the spin coater can be set to 2000-8000 r.p.m., and the spin coating time can be 1-2 min.
In at least one embodiment, the annealing temperature is 60-80 ℃ and the annealing time is 5-10 min.
In at least one embodiment, the substrate may be pre-placed in a plasma cleaning machine and high power treated for 10-15 min to plasma surface activate the substrate.
In the technical scheme of the first embodiment of the invention, the first precursor, the second precursor, the third precursor and a solvent are mixed to obtain a precursor solution, the precursor solution is arranged on a substrate, the precursor solution on the substrate is subjected to spin coating film forming treatment to obtain a perovskite quantum dot active material, and the perovskite quantum dot active material is subjected to annealing treatment to obtain the perovskite metal halide zero-dimensional quantum dot composite material. The perovskite metal halide zero-dimensional quantum dot composite material comprises perovskite metal halide zero-dimensional quantum dots and organic amine salts coated on the surfaces of the perovskite metal halide zero-dimensional quantum dots. The organic amine cation of the organic amine salt can be coordinated with the halogen element on the surface of the perovskite through electrostatic and hydrogen bond interaction, so that the perovskite is inhibited from growing in the out-of-plane direction to form a layered structure. In addition, the organic amine cation comprises an aliphatic ring framework structure, an aromatic ring framework structure or a thiophene ring framework structure shown in figure 1, and at least one amino bonding head and at least one steric hindrance group bonded on the aliphatic ring framework structure, the aromatic ring framework structure or the thiophene ring framework structure. The number of the amino bonding heads is preferably 1, the number of the steric hindrance groups can be at least one, and the amino bonding heads and the steric hindrance groups are bonded at any position of an aliphatic ring framework structure, an aromatic ring framework structure or a thiophene ring framework structure. The steric hindrance group can inhibit the perovskite from being generated into a layered structure, and can promote the perovskite to be generated into the zero-dimensional quantum dot with the strong size confinement effect. Therefore, the preparation method of the perovskite metal halide zero-dimensional quantum dot composite material has the advantage of controllable particle size. Moreover, the preparation method of the perovskite metal halide zero-dimensional quantum dot composite material does not need to adopt harsh conditions such as high temperature, strict anhydrous oxygen-free condition and the like, and also does not need to adopt post-treatment steps such as centrifugal purification and the like, so that the preparation method of the perovskite metal halide zero-dimensional quantum dot composite material has the advantages of low process condition requirement, low cost and simple process.
The preparation method of the perovskite metal halide zero-dimensional quantum dot composite material further comprises the following steps:
providing a passivating agent;
and mixing the first precursor, the second precursor, the third precursor, the passivating agent and the solvent to obtain precursor liquid.
In at least one embodiment, the passivating agent is trimethyl ammonium bromide and/or tetrabutyl phosphonium chloride.
In at least one embodiment, the molar ratio of the passivating agent to the second precursor is 0.05-0.1: 1. for example 0.0.5: 1. 0.06: 1. or 0.1: 1.
after the annealing treatment, the passivating agent is combined on the surface of the perovskite metal halide zero-dimensional quantum dot in the form of a surface ligand. The perovskite metal halide zero-dimensional quantum dot composite material comprises perovskite metal halide zero-dimensional quantum dots, organic amine salt and a passivating agent, wherein the organic amine salt and the passivating agent are coated on the surfaces of the perovskite metal halide zero-dimensional quantum dots.
In the technical solution of the first embodiment of the present invention, a passivating agent may be further mixed with the first precursor, the second precursor, the third precursor, and a solvent to obtain the precursor solution. The passivating agent can further reduce the defect state density of the perovskite metal halide zero-dimensional quantum dot and improve the optical performance of the perovskite metal halide zero-dimensional quantum dot, so that the perovskite metal halide zero-dimensional quantum dot has high photoluminescence quantum yield.
The preparation method of the perovskite metal halide zero-dimensional quantum dot composite material further comprises the following steps:
providing an anti-solvent; and
and in the spin coating film forming process, adding the anti-solvent to the substrate to obtain the perovskite metal halide zero-dimensional quantum dot composite material.
In at least one embodiment, the anti-solvent is at least one of toluene, chlorobenzene, and chloroform.
In at least one embodiment, the volume ratio of the anti-solvent to the precursor solution on the substrate is 1-2: 1. preferably, the ratio of 2: 1.
in at least one embodiment, the anti-solvent can be added to the substrate 5 to 20 seconds after the spin-on film formation process.
The anti-solvent is gradually removed during the annealing process.
In the technical solution of the first embodiment of the present invention, an anti-solvent may be added to the substrate during the spin-coating film-forming process to achieve the purpose of rapidly saturating the precursor solution, so as to accelerate the nucleation and crystallization process of the perovskite metal halide zero-dimensional quantum dot.
The first embodiment of the invention also provides a perovskite metal halide zero-dimensional quantum dot composite material which can be used in an active layer in a light emitting diode, a backlight film in a display panel, an active layer of a photoelectric detector, a light absorption layer of a solar cell and an emitting layer of a laser.
The perovskite metal halide zero-dimensional quantum dot composite material comprises perovskite metal halide zero-dimensional quantum dots and organic amine cations coated on the surfaces of the perovskite metal halide zero-dimensional quantum dots, wherein the organic amine cations comprise an aliphatic ring skeleton structure, an aromatic ring skeleton structure or a thiophene ring skeleton structure shown in figure 1, and at least one amino group binding head and at least one steric hindrance group which are combined on the aliphatic ring skeleton structure, the aromatic ring skeleton structure or the thiophene ring skeleton structure. The number of the amine-group binding heads is preferably one, the number of the steric hindrance groups is at least one, and the amine-group binding heads and the steric hindrance groups are bound at any position of the skeleton structure.
In at least one embodiment, the particle size of the perovskite metal halide zero-dimensional quantum dot is 3-15 nm, for example, 3nm, 5nm, 7nm, 10nm, or 15 nm.
In at least one embodiment, the steric hindrance group is at least one of methyl, methoxy, and halogen.
In at least one embodiment, the perovskite metal halide zero-dimensional quantum dot composite material has a film-like structure, and the thickness of the perovskite metal halide zero-dimensional quantum dot composite material with the film-like structure is 10-500 nm. For example, 10nm, 50nm, 100nm, 200nm, 300nm, 400nm or 500 nm.
In the technical solution of the first embodiment of the present invention, the perovskite metal halide zero-dimensional quantum dot composite material includes perovskite metal halide zero-dimensional quantum dots and organic amine cations coated on the surfaces of the perovskite metal halide zero-dimensional quantum dots. The organic amine cations can coordinate with halogen elements on the surface of the perovskite through electrostatic and hydrogen bond interaction, and further inhibit the perovskite from growing in the out-of-plane direction to form a layered structure. In addition, the organic amine cation comprises an aliphatic ring framework structure, an aromatic ring framework structure or a thiophene ring framework structure as shown in fig. 1, and at least one amino bonding head and at least one steric hindrance group which are bonded on the aliphatic ring framework structure, the aromatic ring framework structure or the thiophene ring framework structure, wherein the number of the amino bonding heads is preferably one, the number of the steric hindrance groups is at least one, and the amino bonding head and the steric hindrance group are bonded at any position of the framework structure. The steric hindrance group can inhibit the perovskite from being generated into a layered structure, and can promote the perovskite to be generated into the zero-dimensional quantum dot with the strong size confinement effect.
The perovskite metal halide zero-dimensional quantum dot composite material also comprises a passivating agent which is combined on the surface of the perovskite metal halide zero-dimensional quantum dot in the form of surface ligands.
In at least one embodiment, the passivating agent is trimethyl ammonium bromide and/or tetrabutyl phosphonium chloride.
In the technical scheme of the first embodiment of the invention, the passivating agent is combined on the surface of the perovskite metal halide zero-dimensional quantum dot in the form of a surface ligand, and the passivating agent reduces the defect state density of the perovskite metal halide zero-dimensional quantum dot and improves the optical performance of the perovskite metal halide zero-dimensional quantum dot, so that the perovskite metal halide zero-dimensional quantum dot has higher photoluminescence quantum yield.
The technical solution of the first embodiment of the present invention is specifically described below by specific examples.
Example 1
Providing cesium bromide (0.0596g), lead bromide (0.2936g), 4-bromo-alpha-phenylethylamine hydrogen bromide (0.3147g), trimethylammonium bromide (0.0056g), tetrabutylphosphonium chloride (0.0114g), and dimethyl sulfoxide (2 mL);
dissolving the cesium bromide, the lead bromide, the 4-bromo-alpha-phenylethylamine hydrogen bromide, the trimethyl ammonium bromide and the tetrabutyl phosphonium chloride in dimethyl sulfoxide, and oscillating for 4 hours under a sealed condition to fully dissolve the cesium bromide, the lead bromide, the 4-bromo-alpha-phenylethylamine hydrogen bromide, the trimethyl ammonium bromide and the tetrabutyl phosphonium chloride to obtain a precursor solution;
filtering the precursor solution by using a filter with the pore diameter of 0.22 mu m, and storing the precursor solution in a nitrogen environment for later use;
providing a transparent glass substrate subjected to plasma surface activation treatment, a spin coater and chlorobenzene (200 mu L);
taking 100 mu L of precursor liquid and dropwise adding the precursor liquid on the transparent glass substrate subjected to the plasma surface activation treatment, carrying out spin coating treatment on the precursor liquid through the spin coater at the rotating speed of 6000r.p.m, and dropwise adding chlorobenzene on the transparent glass substrate after the start of the spin coating for 15s to obtain the perovskite quantum dot active material, wherein the spin coating treatment time is 1 min; and
and annealing the perovskite quantum dot active material to obtain the perovskite metal halide zero-dimensional quantum dot composite material of the embodiment 1, wherein the annealing time is 10min, and the temperature is 80 ℃.
Referring to fig. 3, the fluorescence spectrum of the perovskite metal halide zero-dimensional quantum dot composite material of example 1 shows bright blue fluorescence, the light-emitting peak is 466nm, and the half-peak width is 26 nm. This demonstrates that the perovskite metal halide zero-dimensional quantum dot composite of example 1 emits fluorescence in the deep blue region with high color purity.
Referring to fig. 4, a transmission electron micrograph of the perovskite metal halide zero-dimensional quantum dot composite material of the embodiment 1 shows that the particle size of the perovskite metal halide zero-dimensional quantum dot composite material of the embodiment 1 is 3 to 4nm, and the particle size distribution is narrow.
Example 2
Cesium bromide (0.0681g), cesium chloride (0.0067g), lead bromide (0.2936g), 4-bromo-alpha-phenylethylamine hydrogen bromide (0.2248g), trimethylammonium bromide (0.0056g), tetrabutylphosphonium chloride (0.0114g), and dimethyl sulfoxide (2 mL);
dissolving the cesium bromide, cesium chloride, lead bromide, 4-bromo-alpha-phenylethylamine hydrogen bromide, trimethyl ammonium bromide and tetrabutyl phosphonium chloride in dimethyl sulfoxide, and oscillating for 4 hours under a sealed condition to fully dissolve the cesium bromide, the cesium chloride, the lead bromide, the 4-bromo-alpha-phenylethylamine hydrogen bromide, the trimethyl ammonium bromide and the tetrabutyl phosphonium chloride to obtain a precursor solution;
filtering the precursor solution by using a filter with the pore diameter of 0.22 mu m, and storing the precursor solution in a nitrogen environment for later use;
providing a transparent glass substrate subjected to plasma surface activation treatment, a spin coater and chlorobenzene (200 mu L);
taking 100 mu L of precursor liquid and dropwise adding the precursor liquid on the transparent glass substrate subjected to the plasma surface activation treatment, carrying out spin coating treatment on the precursor liquid through the spin coater at the rotating speed of 6000r.p.m, and dropwise adding chlorobenzene on the transparent glass substrate after the start of the spin coating for 15s to obtain the perovskite quantum dot active material, wherein the spin coating treatment time is 1 min; and
and annealing the perovskite quantum dot active material to obtain the perovskite metal halide zero-dimensional quantum dot composite material of the embodiment 2, wherein the annealing time is 10min, and the temperature is 80 ℃.
Referring to fig. 5, the fluorescence spectrum of the perovskite metal halide zero-dimensional quantum dot composite material of example 2 shows bright blue fluorescence, the light emission peak is 465nm, and the half-peak width is 23 nm. This demonstrates that the perovskite metal halide zero-dimensional quantum dot composite of example 2 emits fluorescence in the deep blue region with high color purity.
Referring to fig. 6, a transmission electron micrograph of the perovskite metal halide zero-dimensional quantum dot composite material of the embodiment 2 shows that the particle size of the perovskite metal halide zero-dimensional quantum dot composite material of the embodiment 2 is 3 to 4nm, and the particle size distribution is narrow.
Comparative example 1
Providing cesium bromide (0.0596g), lead bromide (0.2936g), trimethylammonium bromide (0.0056g), tetrabutylphosphonium chloride (0.0114g), and dimethyl sulfoxide (2 mL);
dissolving the cesium bromide, the lead bromide, the trimethyl ammonium bromide and the tetrabutyl phosphonium chloride in dimethyl sulfoxide, and oscillating for 4 hours under a sealed condition to fully dissolve the cesium bromide, the lead bromide, the trimethyl ammonium bromide and the tetrabutyl phosphonium chloride to obtain a precursor solution;
filtering the precursor solution by using a filter with the pore diameter of 0.22 mu m, and storing the precursor solution in a nitrogen environment for later use;
providing a transparent glass substrate subjected to plasma surface activation treatment, a spin coater and chlorobenzene (200 mu L);
taking 100 mu L of precursor liquid and dropwise adding the precursor liquid on the transparent glass substrate subjected to the plasma surface activation treatment, carrying out spin coating treatment on the precursor liquid through the spin coater at the rotating speed of 6000r.p.m, and dropwise adding chlorobenzene on the transparent glass substrate after the start of the spin coating for 15s to obtain the perovskite quantum dot active material, wherein the spin coating treatment time is 1 min; and
and annealing the perovskite quantum dot active material to obtain the perovskite metal halide zero-dimensional quantum dot composite material of the comparative example 1, wherein the annealing time is 10min, and the temperature is 80 ℃.
Referring to fig. 7, the perovskite metal halide zero-dimensional quantum dot composite material of the comparative example 1 shows green fluorescence in the fluorescence spectrum, the light-emitting peak is 520nm, and the half-peak width is 20 nm. This illustrates that the perovskite metal halide in comparative example 1 does not have a significant size confinement effect.
Referring to fig. 8, a transmission electron micrograph of the perovskite metal halide zero-dimensional quantum dot composite material of the comparative example 1 shows that the particle size of the perovskite metal halide zero-dimensional quantum dot composite material of the comparative example 1 is 30-50 nm, the particle size of the perovskite metal halide zero-dimensional quantum dot composite material is far larger than the bohr diameter of an exciton, and the perovskite metal halide zero-dimensional quantum dot composite material does not have a size-limited domain effect.
The second embodiment of the invention provides a preparation method of a perovskite metal halide zero-dimensional quantum dot/polymer composite material. The preparation method of the perovskite metal halide zero-dimensional quantum dot/polymer composite material comprises the following steps:
providing a first precursor, a second precursor, a third precursor and a polymer, wherein the first precursor is selected from at least one of methylamine halide, formamidine halide, cesium trifluoroacetate, cesium stearate and cesium acetate, the second precursor is selected from at least one of lead halide, stannous halide, lead stearate and lead acetate, the third precursor is an organic amine salt, the anion of the organic amine salt is a halogen ion, and the cation of the organic amine salt comprises an aliphatic ring framework structure, an aromatic ring framework structure or a thiophene ring framework structure, and at least one amino head and at least one steric hindering group which are bonded on the aliphatic ring framework structure, the aromatic ring framework structure or the thiophene ring framework structure;
mixing the first precursor, the second precursor, the third precursor and a polymer to obtain a mixture; and
and carrying out high-temperature extrusion treatment on the mixture to obtain the perovskite metal halide zero-dimensional quantum dot/polymer composite material, wherein the perovskite metal halide zero-dimensional quantum dot/polymer composite material comprises a polymer, perovskite metal halide zero-dimensional quantum dots uniformly dispersed in the polymer and organic amine cations coated on the surfaces of the perovskite metal halide zero-dimensional quantum dots.
In at least one embodiment, the particle size of the perovskite metal halide zero-dimensional quantum dot is 3-15 nm, for example, 3nm, 5nm, 7nm, 10nm, or 15 nm.
In at least one embodiment, the organic amine salt may be a bulky organic amine salt (see fig. 2), which may be a bulky organic amine salt containing 3 or more carbon atoms. Due to the fact that the size of the organic amine salt is too large, the organic amine salt with large size cannot enter the interior of crystal lattices of the perovskite, and can be coordinated with halogen elements on the surface of the perovskite through electrostatic and hydrogen bond interaction, and therefore growth of the perovskite is inhibited.
In at least one embodiment, the molar ratio of the first precursor to the second precursor is 0.2-2: 1. for example, 0.2: 1. 0.5: 1. 1: 1. 1.5: 1. or 2: 1.
in at least one embodiment, the molar ratio of the second precursor to the third precursor is 1: 0.2 to 2. For example, 1: 0.2, 1: 0.5, 1: 1. 1: 1.5, or 1: 2.
the size of the micelle in the precursor liquid is controlled by changing the ratio of the third precursor to the second precursor in the precursor liquid, so that the particle size of the perovskite metal halide zero-dimensional quantum dot is adjusted.
By adjusting the content of the organic amine salt, perovskite metal halide zero-dimensional quantum dot/polymer composite materials with different emission wavelengths are prepared.
In at least one embodiment, the steric hindrance group is at least one of methyl, methoxy, and halogen.
The low-concentration bulky organic amine salt is used for manufacturing perovskite metal halide zero-dimensional quantum dots with larger grain sizes and longer emission wavelengths, and the high-concentration bulky organic amine salt is used for manufacturing perovskite metal halide zero-dimensional quantum dots with smaller grain sizes and shorter emission wavelengths. This is because, as the content of the bulky organic amine salt increases, the growth inhibitory effect of the bulky organic amine salt on the perovskite metal halide zero-dimensional quantum dot becomes gradually apparent. Therefore, perovskite metal halide zero-dimensional quantum dots with different particle sizes and different emission wavelengths can be prepared by adjusting the content of the large-volume organic amine salt in the precursor.
In at least one embodiment, for Br system perovskite metal halide zero-dimensional quantum dots, the bulky organic amine salt used is 4-fluoro-alpha-phenylethylamine hydrogen bromide, 4-chloro-alpha-phenylethylamine hydrogen bromide, 4-bromo-alpha-phenylethylamine hydrogen bromide, 4-iodo-alpha-phenylethylamine hydrogen bromide, 4-methyl-alpha-phenylethylamine hydrogen bromide, or 4-methoxy-alpha-phenylethylamine hydrogen bromide.
In at least one embodiment, for the perovskite metal halide zero-dimensional quantum dots of system I, the bulky organic amine salt used is 1- (4-fluorophenyl) -1-methylethylamine hydroiodide, 1- (4-iodophenyl) -1-methylethylamine hydroiodide, 1- (4-chlorophenyl) -1-methylethylamine hydroiodide, 1- (4-methylbenzene) -1-methylethylamine hydroiodide, 1- (4-bromophenyl) -1-methylethylamine hydroiodide, or 1- (4-methoxyphenyl) -1-methylethylamine hydroiodide.
In at least one embodiment, in the perovskite metal halide zero-dimensional quantum dot/polymer composite material, the mass ratio of the polymer to the perovskite metal halide zero-dimensional quantum dot is 100: 0.1 to 10. For example, 100: 0.1, 100: 1. 100, and (2) a step of: 5. or 100: 10.
in at least one embodiment, the polymer is at least one of thermoplastic polyethylene, polypropylene, polystyrene, polymethylmethacrylate, polyvinyl chloride, nylon, polycarbonate, polyurethane, polyethylene terephthalate, and polyoxymethylene.
In at least one embodiment, the high-temperature extrusion treatment may be performed by using a single-screw extrusion film blowing machine, wherein the temperature of the feeding section of the single-screw extrusion film blowing machine is 150 to 180 ℃, the temperature of the compression section of the single-screw extrusion film blowing machine is 180 to 200 ℃, the temperature of the homogenization section of the single-screw extrusion film blowing machine is 200 to 220 ℃, and the temperature of the film at the mouth of the single-screw extrusion film blowing machine is 190 to 220 ℃. The rotating speed of the single-screw extruder is 200-1500 rpm, so that the perovskite precursor and the polymer are uniformly mixed. The time of the high-temperature extrusion treatment is 10-100 min. After the high temperature extrusion process, the perovskite precursor may crystallize in situ in the polymer as the temperature is reduced.
The rotating speed, the temperature of each section and the time of high-temperature extrusion treatment of the single-screw extruder can be properly adjusted according to the melting points of the perovskite precursor and the polymer.
In the technical scheme of the second embodiment of the invention, the first precursor, the second precursor, the third precursor and the polymer are mixed to obtain a mixture, and the mixture is subjected to high-temperature extrusion treatment to obtain the perovskite metal halide zero-dimensional quantum dot/polymer composite material. The perovskite metal halide zero-dimensional quantum dot/polymer composite material comprises a polymer, perovskite metal halide zero-dimensional quantum dots uniformly dispersed in the polymer, and organic amine cations coated on the surfaces of the perovskite metal halide zero-dimensional quantum dots. The organic amine cation of the organic amine salt can be coordinated with the halogen element on the surface of the perovskite through electrostatic and hydrogen bond interaction, so that the perovskite is inhibited from growing in the out-of-plane direction to form a layered structure. In addition, the organic amine cation comprises an aliphatic ring framework structure, an aromatic ring framework structure or a thiophene ring framework structure shown in figure 1, and at least one amino bonding head and at least one steric hindrance group bonded on the aliphatic ring framework structure, the aromatic ring framework structure or the thiophene ring framework structure. The number of the amino bonding heads is preferably 1, the number of the steric hindrance groups can be at least one, and the amino bonding heads and the steric hindrance groups are bonded at any position of an aliphatic ring framework structure, an aromatic ring framework structure or a thiophene ring framework structure. The steric hindrance group can inhibit the perovskite from being generated into a layered structure, and can promote the perovskite to be generated into the zero-dimensional quantum dot with the strong size confinement effect. Therefore, the preparation method of the perovskite metal halide zero-dimensional quantum dot/polymer composite material has the advantage of controllable particle size. Furthermore, the preparation method of the perovskite metal halide zero-dimensional quantum dot/polymer composite material does not need to adopt a large amount of organic solvents, strict anhydrous and oxygen-free conditions and other harsh conditions, and does not need to adopt post-treatment steps such as centrifugal purification and the like, so that the preparation method of the perovskite metal halide zero-dimensional quantum dot/polymer composite material has the advantages of low process condition requirement, low cost, simple process, difficult environmental pollution and mass production.
The preparation method of the perovskite metal halide zero-dimensional quantum dot/polymer composite material further comprises the step of molding the perovskite metal halide zero-dimensional quantum dot/polymer composite material to obtain a film-shaped perovskite metal halide zero-dimensional quantum dot/polymer composite material with the thickness of 0-2 mm.
The film-shaped perovskite metal halide zero-dimensional quantum dot/polymer composite material can be 0.1mm, 0.2mm, 0.3mm, 0.5mm, 1mm and 2mm in thickness.
In at least one embodiment, the molding process is injection molding, blow molding, or hot press molding. The temperature of the injection molding treatment is 180-220 ℃, and the pressure maintaining time is 5-15 min. The hot-press forming treatment temperature is 180-220 ℃, the pressure is 4-10 MPa, and the time is 4-10 min. The blow molding may be performed by connecting a film blowing tower to a single screw extruder. The film blowing tower is characterized in that the film blowing temperature is 180-220 ℃.
In the technical solution of the second embodiment of the present invention, the perovskite metal halide zero-dimensional quantum dot/polymer composite material may be subjected to a molding process to obtain a film-like perovskite metal halide zero-dimensional quantum dot/polymer composite material.
The preparation method of the perovskite metal halide zero-dimensional quantum dot/polymer composite material further comprises the following steps:
providing a passivating agent; and
and mixing the first precursor, the second precursor, the third precursor, the passivating agent and the polymer to obtain the mixture.
In at least one embodiment, the passivating agent is trimethyl ammonium bromide and/or tetrabutyl phosphonium chloride.
In at least one embodiment, the molar ratio of the passivating agent to the second precursor is 0.05-0.1: 1. for example 0.0.5: 1. 0.06: 1. or 0.1: 1.
the passivating agent is combined on the surface of the perovskite metal halide zero-dimensional quantum dot in the form of a surface ligand. The perovskite metal halide zero-dimensional quantum dot/polymer composite material comprises a polymer, perovskite metal halide zero-dimensional quantum dots uniformly dispersed in the polymer, organic amine cations and a passivating agent, wherein the organic amine cations and the passivating agent are coated on the surfaces of the perovskite metal halide zero-dimensional quantum dots.
In the technical solution of the second embodiment of the present invention, a passivation agent may be further mixed with the first precursor, the second precursor, the third precursor, and the polymer to obtain the mixture. The passivating agent can further reduce the defect state density of the perovskite metal halide zero-dimensional quantum dot and improve the optical performance of the perovskite metal halide zero-dimensional quantum dot, so that the perovskite metal halide zero-dimensional quantum dot has high photoluminescence quantum yield.
The second embodiment of the invention also provides a perovskite metal halide zero-dimensional quantum dot/polymer composite material. The perovskite metal halide zero-dimensional quantum dot/polymer composite material is used for an active layer in a light-emitting diode, a backlight film in a display panel, an active layer of a photoelectric detector, a light absorption layer of a solar cell and an emitting layer of a laser.
The perovskite metal halide zero-dimensional quantum dot/polymer composite material comprises a polymer, perovskite metal halide zero-dimensional quantum dots uniformly dispersed in the polymer, and organic amine cations coated on the surfaces of the perovskite metal halide zero-dimensional quantum dots. The organic amine cation comprises an alicyclic skeleton structure, an aromatic ring skeleton structure, or a thiophene ring skeleton structure, and at least one amine group bonding head and at least one steric hindrance group bonded to the alicyclic skeleton structure, the aromatic ring skeleton structure, or the thiophene ring skeleton structure.
In at least one embodiment, the particle size of the perovskite metal halide zero-dimensional quantum dot is 3-15 nm, for example, 3nm, 5nm, 7nm, 10nm, or 15 nm.
In at least one embodiment, the steric hindrance group is at least one of methyl, methoxy, and halogen.
In at least one embodiment, in the perovskite metal halide zero-dimensional quantum dot/polymer composite material, the mass ratio of the polymer to the perovskite metal halide zero-dimensional quantum dot is 100: 0.1 to 10. For example, 100: 0.1, 100: 1. 100, and (2) a step of: 5. or 100: 10.
in at least one embodiment, the perovskite metal halide zero-dimensional quantum dot/polymer composite material has a film-like structure, and the thickness of the perovskite metal halide zero-dimensional quantum dot/polymer composite material with the film-like structure can be 0.1mm, 0.2mm, 0.3mm, 0.5mm, 1mm and 2 mm.
In the technical solution of the second embodiment of the present invention, the perovskite metal halide zero-dimensional quantum dot/polymer composite material includes a polymer, perovskite metal halide zero-dimensional quantum dots uniformly dispersed in the polymer, and organic amine cations coated on the surface of the perovskite metal halide zero-dimensional quantum dots. The organic amine cation of the organic amine salt can be coordinated with the halogen element on the surface of the perovskite through electrostatic and hydrogen bond interaction, so that the perovskite is inhibited from growing in the out-of-plane direction to form a layered structure. In addition, the organic amine cation comprises an aliphatic ring framework structure, an aromatic ring framework structure or a thiophene ring framework structure shown in figure 1, and at least one amino bonding head and at least one steric hindrance group bonded on the aliphatic ring framework structure, the aromatic ring framework structure or the thiophene ring framework structure. The number of the amino bonding heads is preferably 1, the number of the steric hindrance groups can be at least one, and the amino bonding heads and the steric hindrance groups are bonded at any position of an aliphatic ring framework structure, an aromatic ring framework structure or a thiophene ring framework structure. The steric hindrance group can inhibit the perovskite from being generated into a layered structure, and can promote the perovskite to be generated into the zero-dimensional quantum dot with the strong size confinement effect.
The perovskite metal halide zero-dimensional quantum dot/polymer composite material also comprises a passivating agent which is combined on the surface of the perovskite metal halide zero-dimensional quantum dot in the form of surface ligands.
In at least one embodiment, the passivating agent is trimethyl ammonium bromide and/or tetrabutyl phosphonium chloride.
In the technical scheme of the second embodiment of the invention, the passivating agent is combined on the surface of the perovskite metal halide zero-dimensional quantum dot in the form of a surface ligand, and the passivating agent reduces the defect state density of the perovskite metal halide zero-dimensional quantum dot and improves the optical performance of the perovskite metal halide zero-dimensional quantum dot, so that the perovskite metal halide zero-dimensional quantum dot has higher photoluminescence quantum yield.
The technical solution of the second embodiment of the present invention is specifically described below by specific examples.
Example 3
Providing cesium bromide (0.596g), lead bromide (2.936g), 4-bromo-alpha-phenylethylamine hydrogen bromide (3.147g), trimethylammonium bromide (0.056g), tetrabutylphosphonium chloride (0.114g), and polystyrene (74.04 g);
mixing the cesium bromide, lead bromide, 4-bromo-alpha-phenylethylamine hydrogen bromide, trimethyl ammonium bromide, tetrabutyl phosphonium chloride and polystyrene to obtain a mixture;
putting the mixture into a single-screw extrusion film blowing machine, and heating and melting to melt the mixture, wherein in the heating and melting treatment, the temperature of a feeding section of the single-screw extruder is 180 ℃, the temperature of a compression section of the single-screw extruder is 190 ℃, the temperature of a homogenizing section of the single-screw extruder is 200 ℃, and the rotating speed of the single-screw extruder is 900 revolutions per minute; and
and extruding the molten mixture from a single-screw extrusion film blowing machine, performing injection molding treatment, and cooling to obtain the perovskite metal halide zero-dimensional quantum dot/polymer composite material of the embodiment 3, wherein the film opening temperature of the single-screw extrusion film blowing machine is 190 ℃, the injection molding treatment temperature is 200 ℃, and the pressure holding time is 10 min.
The perovskite metal halide zero-dimensional quantum dot/polymer composite material of example 3 has a film-like structure with a thickness of 0.3 mm.
Referring to fig. 9, the fluorescence spectrum of the perovskite metal halide zero-dimensional quantum dot/polymer composite material of example 3 shows bright blue fluorescence, the luminescence peak of which is 473nm, and the half-width of which is 26 nm. This demonstrates that the perovskite metal halide zero-dimensional quantum dot/polymer composite of example 3 emits fluorescence in the deep blue region with high color purity. Tests show that the PLQY of the perovskite metal halide zero-dimensional quantum dot/polymer composite material of the example 3 can reach 70%.
Referring to fig. 10, a transmission electron micrograph of the perovskite metal halide zero-dimensional quantum dot/polymer composite material of the example 3 shows that the particle size of the perovskite metal halide zero-dimensional quantum dot/polymer composite material of the example 3 is 4 to 5nm, and the particle size distribution is narrow. This demonstrates the strong size-limiting effect of the perovskite metal halide zero-dimensional quantum dot/polymer composite of example 3.
Example 4
Providing cesium iodide (0.596g), lead iodide (2.936g), 1- (4-bromophenyl) -1-methylethylamine hydroiodide (3.147g), trimethylammonium bromide (0.056g), tetrabutylphosphonium chloride (0.114g), and polystyrene (74.04 g);
mixing the cesium iodide, lead iodide, 1- (4-bromophenyl) -1-methylethylamine hydroiodide, trimethyl ammonium bromide, tetrabutyl phosphonium chloride, and polystyrene to obtain a mixture;
putting the mixture into a single-screw extrusion film blowing machine, and heating and melting to melt the mixture, wherein in the heating and melting treatment, the temperature of a feeding section of the single-screw extruder is 180 ℃, the temperature of a compression section of the single-screw extruder is 190 ℃, the temperature of a homogenizing section of the single-screw extruder is 200 ℃, and the rotating speed of the single-screw extruder is 900 revolutions per minute; and
and extruding the molten mixture from a single-screw extrusion film blowing machine, performing hot-press molding treatment, and cooling to obtain the perovskite metal halide zero-dimensional quantum dot/polymer composite material of the embodiment 4, wherein the film opening temperature of the single-screw extrusion film blowing machine is 190 ℃, the hot-press molding treatment temperature is 200 ℃, the pressure is 5MPa, and the time is 5 min.
The perovskite metal halide zero-dimensional quantum dot/polymer composite material of example 4 has a film-like structure with a thickness of 0.2 mm.
Referring to fig. 11, the fluorescence spectrum of the perovskite metal halide zero-dimensional quantum dot/polymer composite material of example 4 shows bright blue fluorescence, the light-emitting peak is at 652nm, and the half-peak width is 36 nm. This demonstrates that the perovskite metal halide zero-dimensional quantum dot/polymer composite of example 4 emits fluorescence in the deep blue region with high color purity. Tests show that the PLQY of the perovskite metal halide zero-dimensional quantum dot/polymer composite material of the example 4 can reach 80%.
Referring to fig. 12, a transmission electron micrograph of the perovskite metal halide zero-dimensional quantum dot/polymer composite material of the example 4 shows that the particle size of the perovskite metal halide zero-dimensional quantum dot/polymer composite material of the example 4 is 5 to 6nm, and the particle size distribution is narrow. This demonstrates the strong size-limiting effect of the perovskite metal halide zero-dimensional quantum dot/polymer composite of example 4.
Comparative example 2
Providing cesium bromide (0.596g), lead bromide (2.936g), trimethylammonium bromide (0.056g), tetrabutylphosphonium chloride (0.114g), and polystyrene (74.04 g);
mixing the cesium bromide, lead bromide, 4-bromo-alpha-phenylethylamine hydrogen bromide, trimethyl ammonium bromide, tetrabutyl phosphonium chloride and polystyrene to obtain a mixture;
putting the mixture into a single-screw extrusion film blowing machine, and heating and melting to melt the mixture, wherein in the heating and melting treatment, the temperature of a feeding section of the single-screw extruder is 180 ℃, the temperature of a compression section of the single-screw extruder is 190 ℃, the temperature of a homogenizing section of the single-screw extruder is 200 ℃, and the rotating speed of the single-screw extruder is 900 revolutions per minute; and
and extruding the molten mixture from a single-screw extrusion film blowing machine, performing injection molding treatment, and cooling to obtain the perovskite metal halide zero-dimensional quantum dot/polymer composite material of the comparative example 2, wherein the film opening temperature of the single-screw extrusion film blowing machine is 190 ℃, the injection molding treatment temperature is 200 ℃, and the pressure holding time is 10 min.
The perovskite metal halide zero-dimensional quantum dot/polymer composite of comparative example 2 has a film-like structure with a thickness of 0.2 mm.
Referring to fig. 13, the fluorescence spectrum of the perovskite metal halide zero-dimensional quantum dot/polymer composite material of the comparative example 2 shows bright green fluorescence, the light-emitting peak is 520nm, and the half-peak width is 20 nm. This demonstrates that the perovskite metal halide zero-dimensional quantum dot/polymer composite of comparative example 2 does not have a significant size-limiting effect.
Referring to fig. 14, a transmission electron micrograph of the perovskite metal halide zero-dimensional quantum dot/polymer composite material of the comparative example 2 shows that the particle size of the perovskite metal halide zero-dimensional quantum dot/polymer composite material of the comparative example 2 is 30 to 50nm, and the particle size of the perovskite metal halide zero-dimensional quantum dot/polymer composite material of the comparative example 2 is much larger than the bohr diameter of an exciton. This demonstrates that the perovskite metal halide zero-dimensional quantum dot/polymer composite of comparative example 2 does not have a size-limiting domain effect.
The third embodiment of the invention provides a preparation method of the perovskite metal halide zero-dimensional quantum dot composite material. The preparation method of the perovskite metal halide zero-dimensional quantum dot composite material comprises the following steps:
providing a first precursor, a second precursor, a third precursor and a polymer, wherein the first precursor is selected from at least one of methylamine halide, formamidine halide, cesium trifluoroacetate, cesium stearate and cesium acetate, the second precursor is selected from at least one of lead halide, stannous halide, lead stearate and lead acetate, the third precursor is an organic amine salt, the anion of the organic amine salt is a halogen ion, and the cation of the organic amine salt comprises an aliphatic ring framework structure, an aromatic ring framework structure or a thiophene ring framework structure, and at least one amino head and at least one steric hindering group which are bonded on the aliphatic ring framework structure, the aromatic ring framework structure or the thiophene ring framework structure;
mixing the first precursor, the second precursor and the third precursor to obtain a perovskite quantum dot precursor; and
carrying out vacuum coating treatment on the perovskite quantum dot precursor to obtain the perovskite quantum dot active layer;
and annealing the perovskite quantum dot active layer to obtain the perovskite metal halide zero-dimensional quantum dot composite material, wherein the perovskite metal halide zero-dimensional quantum dot composite material comprises perovskite metal halide zero-dimensional quantum dots and organic amine cations coated on the surfaces of the perovskite metal halide zero-dimensional quantum dots.
In at least one embodiment, the particle size of the perovskite metal halide zero-dimensional quantum dot is 3-15 nm, for example, 3nm, 5nm, 7nm, 10nm, or 15 nm.
In at least one embodiment, the organic amine salt may be a bulky organic amine salt (see fig. 2), which may be a bulky organic amine salt containing 3 or more carbon atoms. Due to the fact that the size of the organic amine salt is too large, the organic amine salt with large size cannot enter the interior of crystal lattices of the perovskite, and can be coordinated with halogen elements on the surface of the perovskite through electrostatic and hydrogen bond interaction, and therefore growth of the perovskite is inhibited.
In at least one embodiment, the molar ratio of the first precursor to the second precursor is 0.2-2: 1. for example, 0.2: 1. 0.5: 1. 1: 1. 1.5: 1. or 2: 1.
in at least one embodiment, the molar ratio of the second precursor to the third precursor is 1: 0.2 to 2. For example, 1: 0.2, 1: 0.5, 1: 1. 1: 1.5, or 1: 2.
the particle size of the perovskite metal halide zero-dimensional quantum dots is adjusted by changing the ratio of the third precursor to the second precursor.
In at least one embodiment, the steric hindrance group is at least one of methyl, methoxy, and halogen.
The low-concentration bulky organic amine salt is used for manufacturing perovskite metal halide zero-dimensional quantum dots with larger grain sizes and longer emission wavelengths, and the high-concentration bulky organic amine salt is used for manufacturing perovskite metal halide zero-dimensional quantum dots with smaller grain sizes and shorter emission wavelengths. This is because, as the content of the bulky organic amine salt increases, the growth inhibitory effect of the bulky organic amine salt on the perovskite metal halide zero-dimensional quantum dot becomes gradually apparent. Therefore, perovskite metal halide zero-dimensional quantum dots with different particle sizes and different emission wavelengths can be prepared by adjusting the content of the large-volume organic amine salt in the precursor liquid.
In at least one embodiment, for Br system perovskite metal halide zero-dimensional quantum dots, the bulky organic amine salt used is 4-fluoro-alpha-phenylethylamine hydrogen bromide, 4-chloro-alpha-phenylethylamine hydrogen bromide, 4-bromo-alpha-phenylethylamine hydrogen bromide, 4-iodo-alpha-phenylethylamine hydrogen bromide, 4-methyl-alpha-phenylethylamine hydrogen bromide, or 4-methoxy-alpha-phenylethylamine hydrogen bromide.
In at least one embodiment, for the perovskite metal halide zero-dimensional quantum dots of system I, the bulky organic amine salt used is 1- (4-fluorophenyl) -1-methylethylamine hydroiodide, 1- (4-iodophenyl) -1-methylethylamine hydroiodide, 1- (4-chlorophenyl) -1-methylethylamine hydroiodide, 1- (4-methylbenzene) -1-methylethylamine hydroiodide, 1- (4-bromophenyl) -1-methylethylamine hydroiodide, or 1- (4-methoxyphenyl) -1-methylethylamine hydroiodide.
The perovskite metal halide zero-dimensional quantum dot composite material with different emission wavelengths can be prepared by adjusting the content of the organic amine salt.
In at least one embodiment, the perovskite metal halide zero-dimensional quantum dot composite material has a film-like structure, and the thickness of the perovskite metal halide zero-dimensional quantum dot composite material with the film-like structure is 10-500 nm. For example 10nm, 50nm, 100nm, 200nm, 300nm, 400nm or 500 nm.
In at least one embodiment, the annealing temperature is 100-150 ℃ and the annealing time is 5-30 min.
In the technical scheme of the third embodiment of the invention, the first precursor, the second precursor and the third precursor are mixed to obtain a perovskite quantum dot precursor, and the perovskite quantum dot precursor is subjected to vacuum coating treatment and annealing treatment to obtain the perovskite metal halide zero-dimensional quantum dot composite material. The perovskite metal halide zero-dimensional quantum dot composite material comprises perovskite metal halide zero-dimensional quantum dots and organic amine cations coated on the surfaces of the perovskite metal halide zero-dimensional quantum dots. The organic amine cation of the organic amine salt can be coordinated with the halogen element on the surface of the perovskite through electrostatic and hydrogen bond interaction, so that the perovskite is inhibited from growing in the out-of-plane direction to form a layered structure. In addition, the organic amine cation comprises an aliphatic ring framework structure, an aromatic ring framework structure or a thiophene ring framework structure shown in figure 1, and at least one amino bonding head and at least one steric hindrance group bonded on the aliphatic ring framework structure, the aromatic ring framework structure or the thiophene ring framework structure. The number of the amino bonding heads is preferably 1, the number of the steric hindrance groups can be at least one, and the amino bonding heads and the steric hindrance groups are bonded at any position of an aliphatic ring framework structure, an aromatic ring framework structure or a thiophene ring framework structure. The steric hindrance group can inhibit the perovskite from being generated into a layered structure, and can promote the perovskite to be generated into the zero-dimensional quantum dot with the strong size confinement effect. Therefore, the preparation method of the perovskite metal halide zero-dimensional quantum dot composite material has the advantage of controllable particle size. Moreover, the vacuum coating treatment of the invention is compatible with the industrialized display panel preparation process, and can overcome the defects of nonuniform crystallization, raw material waste, difficulty in preparing large-area thin films and difficulty in realizing multilayer coating of the existing spin coating or blade coating process, and obtain the perovskite metal halide zero-dimensional quantum dot/polymer composite material with large area, uniform film formation, high PLQY and compact surface. In addition, the preparation method of the perovskite metal halide zero-dimensional quantum dot composite material does not need to adopt a large amount of organic solvents, strict anhydrous and oxygen-free conditions and other harsh conditions, and does not need to adopt post-treatment steps such as centrifugal purification and the like, so that the preparation method of the perovskite metal halide zero-dimensional quantum dot composite material has the advantages of low process condition requirement, low cost, simple process, difficult environmental pollution, mass production, high precision and high repeatability.
The step of carrying out vacuum coating treatment on the perovskite quantum dot precursor comprises the following steps:
providing a substrate;
and placing the perovskite quantum dot precursor in a vacuum coating machine, and depositing the perovskite quantum dot precursor on a substrate to obtain the perovskite quantum dot active layer.
In at least one embodiment, the vacuum coater comprises a heating table and an inorganic evaporation source. The substrate can be arranged on a heating table, and the heating table can heat the temperature of the substrate to 60-100 ℃. The inorganic evaporation source can be used for evaporating and escaping atoms or molecules of the perovskite quantum dot precursor and then depositing the atoms or molecules on the surface of the substrate.
In at least one embodiment, the heating stage is preferably a rotary heating stage.
In at least one embodiment, the temperature of the vacuum coating treatment is 60 to 100 ℃, and the evaporation rate is 0.5 to 10 angstroms/s.
In at least one embodiment, the temperature of the heating table can be adjusted to 100-150 ℃ to perform annealing treatment on the perovskite quantum dot active layer on the substrate, so as to obtain the perovskite metal halide zero-dimensional quantum dot composite material.
In at least one embodiment, the substrate is a transparent glass substrate, a flexible polyethylene terephthalate substrate, nano indium tin metal oxide conductive glass, or fluorine doped tin dioxide conductive glass.
In the technical scheme of the third embodiment of the invention, a vacuum coating machine can be adopted to deposit the perovskite quantum dot precursor on the substrate to obtain the perovskite quantum dot active layer. The vacuum evaporation process is the main preparation method of Organic Light Emitting Diodes (OLEDs) that have been commercialized. Under the assistance of a high-precision metal mask, the vacuum evaporation process can easily obtain parallel red, green and blue three-primary-color light-emitting pixel points, so that the mass and high-quality production of OLED devices is realized. In the vacuum evaporation treatment process, the perovskite quantum dot precursor is firstly evaporated or sublimated into gaseous particles, and then the gaseous particles are attached to the surface of the substrate to form nuclei and grow into a solid film. The vacuum evaporation process gets rid of the limitation of uneven coating of a liquid phase method, and is particularly suitable for depositing large-size perovskite metal halide zero-dimensional quantum dot composite materials.
The preparation method of the perovskite metal halide zero-dimensional quantum dot composite material further comprises the following steps:
providing a passivating agent; and
and mixing the first precursor, the second precursor, the third precursor and the passivating agent to obtain the perovskite quantum dot precursor.
In at least one embodiment, the passivating agent is trimethyl ammonium bromide and/or tetrabutyl phosphonium chloride.
In at least one embodiment, the molar ratio of the passivating agent to the second precursor is 0.05-0.1: 1. for example 0.0.5: 1. 0.06: 1. or 0.1: 1.
the passivating agent is combined on the surface of the perovskite metal halide zero-dimensional quantum dot in the form of a surface ligand. The perovskite metal halide zero-dimensional quantum dot composite material comprises perovskite metal halide zero-dimensional quantum dots, organic amine cations and a passivating agent, wherein the organic amine cations and the passivating agent are coated on the surfaces of the perovskite metal halide zero-dimensional quantum dots.
In the technical solution of the third embodiment of the present invention, a passivating agent may be further mixed with the first precursor, the second precursor, and the third precursor to obtain the perovskite quantum dot precursor. The passivating agent can further reduce the defect state density of the perovskite metal halide zero-dimensional quantum dot and improve the optical performance of the perovskite metal halide zero-dimensional quantum dot, so that the perovskite metal halide zero-dimensional quantum dot has high photoluminescence quantum yield.
After the first precursor, the second precursor and the third precursor are mixed and before the perovskite quantum dot precursor is obtained, the preparation method of the perovskite metal halide zero-dimensional quantum dot composite material further comprises the following steps:
and grinding the mixture of the first precursor, the second precursor and the third precursor.
The grinding process may be performed on the mixture by a grinder, or the first precursor, the second precursor, and the third precursor may be manually ground by placing them in a mortar, so that the precursors are uniformly mixed.
During the milling process, the perovskite quantum dot precursor is pre-crystallized and shows bright fluorescence at different wavelengths.
In the technical solution of the third embodiment of the present invention, a mixture of the first precursor, the second precursor, and the third precursor is ground to uniformly mix the first precursor, the second precursor, and the third precursor.
The third embodiment of the invention also provides a perovskite metal halide zero-dimensional quantum dot composite material. The perovskite metal halide zero-dimensional quantum dot composite material comprises perovskite metal halide zero-dimensional quantum dots and organic amine cations coated on the surfaces of the perovskite metal halide zero-dimensional quantum dots, wherein the organic amine cations comprise an alicyclic ring skeleton structure, an aromatic ring skeleton structure or a thiophene ring skeleton structure, and at least one amino bonding head and at least one steric hindrance group which are bonded on the alicyclic ring skeleton structure, the aromatic ring skeleton structure or the thiophene ring skeleton structure.
In at least one embodiment, the particle size of the perovskite metal halide zero-dimensional quantum dot is 3-15 nm, for example, 3nm, 5nm, 7nm, 10nm, or 15 nm.
In at least one embodiment, the steric hindrance group is at least one of methyl, methoxy, and halogen.
In at least one embodiment, the perovskite metal halide zero-dimensional quantum dot composite material has a film-like structure, and the thickness of the perovskite metal halide zero-dimensional quantum dot composite material with the film-like structure is 10-500 nm. For example, 10nm, 50nm, 100nm, 200nm, 300nm, 400nm or 500 nm.
In the technical scheme of the third embodiment of the invention, the perovskite metal halide zero-dimensional quantum dot composite material comprises a polymer, perovskite metal halide zero-dimensional quantum dots uniformly dispersed in the polymer, and organic amine cations coated on the surfaces of the perovskite metal halide zero-dimensional quantum dots, wherein the particle size of the perovskite metal halide zero-dimensional quantum dots is 3-15 nm. The organic amine cation of the organic amine salt can be coordinated with the halogen element on the surface of the perovskite through electrostatic and hydrogen bond interaction, so that the perovskite is inhibited from growing in the out-of-plane direction to form a layered structure. In addition, the organic amine cation comprises an aliphatic ring framework structure, an aromatic ring framework structure or a thiophene ring framework structure shown in figure 1, and at least one amino bonding head and at least one steric hindrance group bonded on the aliphatic ring framework structure, the aromatic ring framework structure or the thiophene ring framework structure. The number of the amino bonding heads is preferably 1, the number of the steric hindrance groups can be at least one, and the amino bonding heads and the steric hindrance groups are bonded at any position of an aliphatic ring framework structure, an aromatic ring framework structure or a thiophene ring framework structure. The steric hindrance group can inhibit the perovskite from being generated into a layered structure, and can promote the perovskite to be generated into the zero-dimensional quantum dot with the strong size confinement effect.
The perovskite metal halide zero-dimensional quantum dot composite material also comprises a passivating agent which is combined on the surface of the perovskite metal halide zero-dimensional quantum dot in the form of surface ligands.
In at least one embodiment, the passivating agent is trimethyl ammonium bromide and/or tetrabutyl phosphonium chloride.
In the technical solution of the third embodiment of the present invention, the passivating agent is combined on the surface of the perovskite metal halide zero-dimensional quantum dot in the form of a surface ligand, and the passivating agent reduces the defect state density of the perovskite metal halide zero-dimensional quantum dot, and improves the optical performance of the perovskite metal halide zero-dimensional quantum dot, so that the perovskite metal halide zero-dimensional quantum dot has a higher photoluminescence quantum yield.
The third embodiment of the present invention will be specifically described below with reference to specific examples.
Example 5:
providing cesium bromide (0.0596g), lead bromide (0.2936g), 4-bromo-alpha-phenylethylamine hydrogen bromide (0.3147g), trimethylammonium bromide (0.0056g), and tetrabutylphosphonium chloride (0.0114 g);
uniformly mixing cesium bromide, lead bromide, 4-bromo-alpha-phenylethylamine hydrogen bromide, trimethyl ammonium bromide and tetrabutyl phosphonium chloride, and grinding in a mortar for 30min to obtain a perovskite quantum dot precursor;
storing the perovskite quantum dot precursor in a nitrogen environment for later use;
providing a transparent glass substrate (the length and the width of which are both 10cm) with a cleaned surface, vacuum coating equipment and a heating table arranged in the vacuum coating equipment;
placing a proper amount of perovskite quantum dot precursor into an inorganic evaporation source in vacuum coating equipment, performing vacuum coating, and depositing a perovskite quantum dot active layer on the transparent glass substrate, wherein the deposition rate of the inorganic evaporation source is 1.5 angstroms/s, and the temperature in the vacuum coating equipment is 60 ℃; and
and annealing the perovskite quantum dot active layer in a nitrogen environment to obtain the perovskite metal halide zero-dimensional quantum dot thin film of the embodiment 1, wherein the annealing temperature is 100 ℃, the annealing time is 10min, the thickness of the perovskite metal halide zero-dimensional quantum dot thin film of the embodiment 1 is 100nm, and the length and the width are both 10 cm.
Referring to fig. 15, the fluorescence spectrum of the perovskite metal halide zero-dimensional quantum dot film of example 5 shows bright blue fluorescence, the light-emitting peak is 473nm, and the half-width is 26 nm. This demonstrates that the perovskite metal halide zero-dimensional quantum dot film of example 5 emits fluorescence in the deep blue region with high color purity. Tests prove that the PLQY of the perovskite metal halide zero-dimensional quantum dot composite material of the example 5 can reach 70 percent
Referring to fig. 16, a transmission electron micrograph of the perovskite metal halide zero-dimensional quantum dot of example 5 shows that the particle size of the perovskite metal halide zero-dimensional quantum dot of example 5 is 3 to 4nm and the particle size distribution is narrow.
Referring to fig. 17, a scanning electron micrograph of the perovskite metal halide zero-dimensional quantum dot of example 5 shows that the perovskite metal halide zero-dimensional quantum dot composite material of example 5 has a flat surface and uniform film formation.
Comparative example 3:
providing cesium bromide (0.0596g), lead bromide (0.2936g), trimethylammonium bromide (0.0056g), and tetrabutylphosphonium chloride (0.0114 g);
uniformly mixing the cesium bromide, the lead bromide, the trimethyl ammonium bromide and the tetrabutyl phosphonium chloride, and grinding in a mortar for 30min to obtain a perovskite quantum dot precursor;
storing the perovskite quantum dot precursor in a nitrogen environment for later use;
providing a transparent glass substrate (the length and the width of which are both 10cm) with a cleaned surface, vacuum coating equipment and a heating table arranged in the vacuum coating equipment;
placing a proper amount of perovskite quantum dot precursor into an inorganic evaporation source in vacuum coating equipment, performing vacuum coating, and depositing a perovskite quantum dot active layer on the transparent glass substrate, wherein the deposition rate of the inorganic evaporation source is 1.5 angstroms/s, and the temperature in the vacuum coating equipment is 60 ℃; and
and annealing the perovskite metal halide quantum dot active layer in a nitrogen environment to obtain the perovskite metal halide quantum dot thin film of the comparative example 1, wherein the annealing temperature is 100 ℃, the annealing time is 10min, the thickness of the perovskite metal halide zero-dimensional quantum dot thin film of the comparative example 3 is 100nm, and the length and the width are both 10 cm.
Referring to fig. 18, the bulk perovskite metal halide thin film of comparative example 3 exhibited green fluorescence in the fluorescence spectrum, with a light emission peak at 520nm and a half-width at 20 nm. This illustrates that the bulk perovskite metal halide of comparative example 3 does not have a significant size confinement effect.
Referring to fig. 19, a scanning electron micrograph of the bulk perovskite metal halide thin film of comparative example 3 shows that the perovskite metal halide thin film of comparative example 1 has a rough surface, the particle size of the perovskite metal halide is 100 to 300nm, and the particle size is much larger than the bohr diameter of the exciton. This demonstrates that the bulk perovskite metal halide thin film of comparative example 3 does not have a size-limiting effect.
The above description is only a preferred embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications and equivalents of the present invention, which can be directly or indirectly applied to other related technical fields without departing from the spirit of the present invention, are included in the scope of the present invention.

Claims (8)

1. A preparation method of a perovskite metal halide zero-dimensional quantum dot composite material is characterized by comprising the following steps:
providing a first precursor, a second precursor, a third precursor and a solvent, wherein the first precursor is selected from at least one of methylamine halide, formamidine halide, cesium trifluoroacetate, cesium stearate and cesium acetate, the second precursor is selected from at least one of lead halide, stannous halide, lead stearate and lead acetate, the third precursor is an organic amine salt, the anion of the organic amine salt is a halogen ion, and the cation of the organic amine salt comprises an aliphatic ring framework structure, an aromatic ring framework structure or a thiophene ring framework structure, and at least one amino head and at least one steric hindering group which are bonded on the aliphatic ring framework structure, the aromatic ring framework structure or the thiophene ring framework structure;
mixing the first precursor, the second precursor, the third precursor and a solvent to obtain a precursor solution;
adding the precursor solution onto a substrate, and performing spin coating film forming treatment on the precursor solution on the substrate to obtain a perovskite quantum dot active material; and
and annealing the perovskite quantum dot active material to obtain the perovskite metal halide zero-dimensional quantum dot composite material, wherein the perovskite metal halide zero-dimensional quantum dot composite material comprises perovskite metal halide zero-dimensional quantum dots and organic amine cations coated on the surfaces of the perovskite metal halide zero-dimensional quantum dots.
2. The method of preparing a perovskite metal halide zero-dimensional quantum dot composite material as claimed in claim 1, wherein at least one of the following conditions a-f is satisfied:
a. the particle size of the perovskite metal halide zero-dimensional quantum dot is 3-15 nm;
b. the steric hindrance group is at least one of methyl, methoxy and halogen;
c. the solvent is at least one of dimethyl sulfoxide, N-dimethylformamide, N-methylpyrrolidone and acetonitrile;
d. the perovskite metal halide zero-dimensional quantum dot composite material has a film-shaped structure, and the thickness of the perovskite metal halide zero-dimensional quantum dot composite material with the film-shaped structure is 10-500 nm;
e. the molar ratio of the first precursor to the second precursor is 0.1-0.9: 1;
f. the molar ratio of the third precursor to the second precursor is 0.2-1.4: 1.
3. the method of preparing a perovskite metal halide zero-dimensional quantum dot composite material as claimed in claim 1, wherein the method of preparing a perovskite metal halide zero-dimensional quantum dot composite material further comprises the steps of:
providing a passivating agent; and
and mixing the first precursor, the second precursor, the third precursor, a passivating agent and a solvent to obtain a precursor solution, wherein the passivating agent is trimethyl ammonium bromide and/or tetrabutyl phosphonium chloride, and the molar ratio of the passivating agent to the second precursor is 0.05-0.1: 1.
4. the method of preparing a perovskite metal halide zero-dimensional quantum dot composite material as claimed in claim 1, wherein the method of preparing a perovskite metal halide zero-dimensional quantum dot composite material further comprises the steps of:
providing an anti-solvent; and
in the spin coating film forming process, adding the anti-solvent to the substrate to obtain the perovskite quantum dot active material, wherein the anti-solvent is at least one of toluene, chlorobenzene and chloroform, and the volume ratio of the anti-solvent to the precursor solution on the substrate is 1-2: 1.
5. the perovskite metal halide zero-dimensional quantum dot composite material is characterized by comprising perovskite metal halide zero-dimensional quantum dots and organic amine cations coated on the surfaces of the perovskite metal halide zero-dimensional quantum dots, wherein the organic amine cations comprise an alicyclic ring skeleton structure, an aromatic ring skeleton structure or a thiophene ring skeleton structure, and at least one amino bonding head and at least one steric hindering group which are bonded on the alicyclic ring skeleton structure, the aromatic ring skeleton structure or the thiophene ring skeleton structure.
6. The perovskite metal halide zero-dimensional quantum dot composite of claim 5, further comprising a passivating agent bound to the surface of the perovskite metal halide zero-dimensional quantum dot, wherein the passivating agent is trimethyl ammonium bromide and/or tetrabutyl phosphonium chloride.
7. The perovskite metal halide zero-dimensional quantum dot composite material of claim 5, wherein the steric hindrance group is at least one of methyl, methoxy, and halogen; and/or the perovskite metal halide zero-dimensional quantum dot composite material has a film-like structure, and the thickness of the perovskite metal halide zero-dimensional quantum dot composite material with the film-like structure is 10-500 nm; and/or the particle size of the perovskite metal halide zero-dimensional quantum dot is 3-15 nm.
8. Use of an organic amine salt, wherein the cation of the organic amine salt comprises an aliphatic ring backbone structure, an aromatic ring backbone structure, or a thiophene ring backbone structure, and at least one amine group bonding head and at least one steric blocking group bonded to the aliphatic ring backbone structure, the aromatic ring backbone structure, or the thiophene ring backbone structure, for the preparation of the perovskite metal halide zero-dimensional quantum dot composite material as claimed in any one of claims 5 to 7.
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Cited By (1)

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Publication number Priority date Publication date Assignee Title
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109971457A (en) * 2017-12-27 2019-07-05 Tcl集团股份有限公司 A kind of perovskite quantum dot and preparation method thereof
CN111403607A (en) * 2020-03-25 2020-07-10 华东理工大学 Chelated perovskite material, film, device and preparation method and application thereof
CN111916571A (en) * 2020-06-24 2020-11-10 华南理工大学 Red perovskite light emitting diode based on mixed halogen and preparation method thereof
CN112216799A (en) * 2020-10-15 2021-01-12 江苏大学 Method for passivating perovskite and preparation process of perovskite solar cell
CN113193126A (en) * 2021-04-08 2021-07-30 电子科技大学 Preparation method for realizing surface reconstruction of non-methylamine perovskite thin film and application thereof
CN113629203A (en) * 2020-05-09 2021-11-09 中国科学院化学研究所 Electroluminescent laser display and construction method thereof
CN113644204A (en) * 2021-08-11 2021-11-12 华侨大学 Perovskite solar cell based on amino compound interface modification layer and preparation method thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109971457A (en) * 2017-12-27 2019-07-05 Tcl集团股份有限公司 A kind of perovskite quantum dot and preparation method thereof
CN111403607A (en) * 2020-03-25 2020-07-10 华东理工大学 Chelated perovskite material, film, device and preparation method and application thereof
CN113629203A (en) * 2020-05-09 2021-11-09 中国科学院化学研究所 Electroluminescent laser display and construction method thereof
CN111916571A (en) * 2020-06-24 2020-11-10 华南理工大学 Red perovskite light emitting diode based on mixed halogen and preparation method thereof
CN112216799A (en) * 2020-10-15 2021-01-12 江苏大学 Method for passivating perovskite and preparation process of perovskite solar cell
CN113193126A (en) * 2021-04-08 2021-07-30 电子科技大学 Preparation method for realizing surface reconstruction of non-methylamine perovskite thin film and application thereof
CN113644204A (en) * 2021-08-11 2021-11-12 华侨大学 Perovskite solar cell based on amino compound interface modification layer and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
孙长久: "有机无机杂化钙钛矿发光二级管的制备及性能研究", 《信息科技辑》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023109973A1 (en) * 2021-12-13 2023-06-22 南开大学 Perovskite metal halide zero-dimensional quantum dot composite material and preparation method therefor, and use of organic amine salt

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