Halide perovskite material with symbiotic structure, preparation method and application thereof
阅读说明：本技术 具有共生结构的卤化物钙钛矿材料、制备方法及其用途 (Halide perovskite material with symbiotic structure, preparation method and application thereof ) 是由 刘希涛 李霄琪 邬发发 罗军华 于 2021-11-05 设计创作，主要内容包括：本发明涉及一种具有共生结构的卤化物钙钛矿材料、制备方法及其用途,本发明的具有共生结构的卤化物钙钛矿材料,它的分子式为(X丙胺)-(4)CsPb-(3)Br-(11),其中X为Cl、或者Br。本发明制备出具有共生结构的卤化物钙钛矿材料,该材料具备优异的物理化学性能,如半导体特性、铁电性、压电性。本发明的制备方法,该材料可用溶液法、固相合成法制备得到,简单易行,成本低廉。该材料在光电、非线性光学、铁电、压电等领域具有潜在的应用价值。(The invention relates to a halide perovskite material with a symbiotic structure, a preparation method and application thereof 4 CsPb 3 Br 11 Wherein X is Cl or Br. The halide perovskite material with the intergrowth structure is prepared, and the material has excellent physicochemical properties such as semiconductor characteristics, ferroelectricity and piezoelectricity. The material can be prepared by a solution method and a solid-phase synthesis method, and is simple and easy to implement and low in cost. The material has potential application value in the fields of photoelectricity, nonlinear optics, ferroelectricity, piezoelectricity and the like.)
1. A halide perovskite material having a intergrowth structure, characterized by: its molecular formula is (X propylamine)4CsPb3Br11Wherein X is Cl or Br.
2. Halogenation according to claim 1 with intergrowthA perovskite material characterized by: when X is Cl, the reaction mixture is reacted with a catalyst,α＝90°，β＝90°，γ＝90°，belongs to orthorhombic system, mm2 point group, Pmc21A space group;
when the X is Br, the compound is,α＝90°，β＝90°，γ＝90°，belongs to orthorhombic system, mm2 point group, Pmc21And (4) space group.
3. The method for producing a halide perovskite material having an intergrowth structure according to claim 1 or 2, characterized in that: the method comprises the following steps: at room temperature, adding lead bromide, cesium bromide and 3-X propylamine hydrochloride into a ball mill according to the stoichiometric ratio, and carrying out ball milling for 20-30 minutes to obtain (X propylamine)4CsPb3Br11The powder of (4).
4. The method for producing a halide perovskite material having an intergrowth structure according to claim 1 or 2, characterized in that: the method comprises the following steps:
dissolving lead acetate trihydrate, cesium carbonate and 3-X propylamine hydrochloride in hydrobromic acid, and cooling the solution at the speed of 1-2 ℃/day by a solution cooling method to separate out the halide perovskite material with the symbiotic structure.
The molar ratio of the lead acetate trihydrate, the cesium carbonate and the 3-X propylamine hydrochloride is 1-2: 1: 3-3.5;
10mL of hydrobromic acid is added for dissolving every 1-2mmol of lead acetate trihydrate.
5. Use of a halide perovskite material having an intergrowth structure according to claim 1 or 2, wherein: the halide perovskite material with the intergrowth structure is used as a photoelectric functional device, a nonlinear optical device, a ferroelectric device, a pyroelectric device and a piezoelectric device.
Technical Field
The invention belongs to the field of functional materials, and particularly relates to a halide perovskite material with a symbiotic structure, a preparation method and application thereof.
Background
In recent years, halide perovskites attract extensive attention of researchers by virtue of excellent physical and chemical properties, and have wide application prospects in the fields of lasers, light-emitting diodes, solar cells, ferroelectric devices and the like. By selecting a proper organic amine cation template, the inorganic framework of the organic amine cation template can realize the regulation of dimensionality, thereby regulating and controlling the performance of the organic amine cation template. Wherein, the two-dimensional halide perovskite is widely researched by virtue of the adjustability and compatibility of the structure and the environmental stability. The thickness of the inorganic layer of the two-dimensional perovskite can be controlled through simple chemical synthesis, thereby realizing the regulation and control of the performance.
The bismuth layer structure ferroelectric has important application prospect in the fields of high temperature, high frequency, information storage and the like, the ferroelectric performance can be improved by constructing a symbiotic structure, namely the bismuth layer structure ferroelectrics with different layers can be alternately arranged along the crystallographic c axis to form a superlattice structure, and the ferroelectric performance, the piezoelectric performance and the like can be improved by utilizing the interaction between the two different structural units. However, such a structure has not been reported in the halide perovskite. Therefore, the exploration of the halide perovskite with the symbiotic structure has important scientific research value and wide application prospect.
Disclosure of Invention
The invention provides a halide perovskite material with a symbiotic structure, a preparation method and application thereof.
It is an object of the present invention to provide a halide perovskite material having a intergrowth structure, which has excellent physicochemical properties such as semiconductor characteristics, ferroelectricity, piezoelectricity.
The invention also aims to provide a preparation method of the halide perovskite material with the symbiotic structure, and the material can be prepared by a solution method and a solid-phase synthesis method, is simple and easy to implement and has low cost.
The invention also aims to provide application of the halide perovskite material with the intergrowth structure, and the material has potential application value in the fields of photoelectricity, nonlinear optics, ferroelectricity, piezoelectricity and the like.
The invention is realized by the following technical scheme:
a halide perovskite material with intergrowth structure has a molecular formula of (X propylamine)4CsPb3Br11Wherein X is Cl or Br.
Further, when X is Cl,α＝90°，β＝90°，γ＝90°，belongs to orthorhombic system, mm2 point group, Pmc21A space group;
when the X is Br, the compound is,α＝90°，β＝90°，γ＝90°，belongs to orthorhombic system, mm2 point group, Pmc21And (4) space group.
A preparation method of halide perovskite material with intergrowth structure comprises the following steps: at room temperature, adding lead bromide, cesium bromide and 3-X propylamine hydrochloride into a ball mill according to the stoichiometric ratio, and carrying out ball milling for 20-30 minutes to obtain (X propylamine)4CsPb3Br11The powder of (4).
A preparation method of halide perovskite material with intergrowth structure comprises the following steps:
dissolving lead acetate trihydrate, cesium carbonate and 3-X propylamine hydrochloride in hydrobromic acid, and cooling the solution at the speed of 1-2 ℃/day by a solution cooling method to separate out the halide perovskite material with the symbiotic structure.
The molar ratio of the lead acetate trihydrate, the cesium carbonate and the 3-X propylamine hydrochloride is 1-2: 1: 3-3.5;
10mL of hydrobromic acid is added for dissolving every 1-2mmol of lead acetate trihydrate.
Compared with the prior art, the invention has the following beneficial effects: the halide perovskite material with the intergrowth structure is prepared, and the material has excellent physicochemical properties such as semiconductor characteristics, ferroelectricity and piezoelectricity. The material can be prepared by a solution method and a solid-phase synthesis method, and is simple and easy to implement and low in cost. The material has potential application value in the fields of photoelectricity, nonlinear optics, ferroelectricity, piezoelectricity and the like.
Drawings
FIG. 1 is a schematic structural view of a halide perovskite having a intergrowth structure. 1 is divalent metal lead Pb; 2 is halogen ion bromine Br, 1 and 2 form an octahedron, and an inorganic layer is formed by combining in a common angle mode and the like; 3 is small cation Cs in octahedral cavity+(ii) a 4 is an organic amine cation X propylamine (X is Cl or Br).
FIG. 2 shows example 1 (chloropropylamine)4CsPb3Br11And (4) a structural stacking diagram of the crystal.
FIG. 3 is example 3 (bromopropylamine)4CsPb3Br11And (4) a structural stacking diagram of the crystal.
FIG. 4 shows (bromopropylamine) in example 34CsPb3Br11The photoconductive property of (1).
FIG. 5 shows (bromopropylamine) in example 44CsPb3Br11The non-linear multiplied frequency signal of (1).
FIG. 6 shows (bromopropylamine) in example 54CsPb3Br11The hysteresis loop of (3).
Detailed Description
The invention will be further elucidated with reference to the following embodiments:
example 1
Halide perovskite material (chloropropylamine) with intergrowth structure4CsPb3Br11Preparation of
(Chloropropylamine)4CsPb3Br11The preparation can be carried out by a solution method: lead acetate trihydrate (1mmol, 0.38g), cesium carbonate (1mmol, 0.17g), 3-chloropropylamine hydrochloride (3mmol,0.39g) were dissolved in 15mL of hydrogen at room temperatureCooling the solution to below room temperature in bromic acid to precipitate (chloropropylamine)4CsPb3Br11The crystallites of (2).
Example 2
Halide perovskite material (chloropropylamine) with intergrowth structure4CsPb3Br11Preparation of
(Chloropropylamine)4CsPb3Br11Can be prepared by a solid phase method: at room temperature, adding lead bromide, cesium bromide and 3-chloropropylamine hydrochloride into a ball mill according to the stoichiometric ratio, and carrying out ball milling for 20 minutes to obtain (chloropropylamine)4CsPb3Br11The powder of (4).
(Chloropropylamine) of examples 1 and 24CsPb3Br11The structure stacking diagram of the crystal is shown in figures 1 and 2.
As shown in fig. 1 and 2, the halide perovskite material with an intergrowth structure of the invention comprises a plurality of single-layer halide perovskite units and double-layer halide perovskite units which are alternately arranged along a certain crystallographic axis, wherein the halide perovskite units and the double-layer halide perovskite units extend along the direction; organic amine cations connected through hydrogen bonds exist between two adjacent halide perovskite units and the double-layer halide perovskite unit; the single-layer halide perovskite unit comprises an inorganic layer formed by connecting a plurality of lead-bromine octahedrons; the double-layer halide perovskite unit comprises two inorganic layers formed by connecting a plurality of lead-bromine octahedrons, and ions Cs with smaller sizes are distributed in holes of the two inorganic layers; the lead bromine octahedron is composed of one Pb matched with 6 bromine.
The unit cell parameters for this example are as follows: α＝90°，β＝90°，γ＝90°，crystallized in orthorhombic system, point group mm2, Pmc21And (4) space group.
Example 3
Halide perovskite material (bromopropylamine) with intergrowth structure4CsPb3Br11Preparation of
(Bromopropylamine)4CsPb3Br11The preparation can be carried out by a solution method: adding lead acetate trihydrate (2mmol), cesium carbonate (1mmol) and 3-bromopropylamine hydrobromide (3.5mmol) into 20mL of hydrobromic acid, heating and stirring until a clear solution is obtained, and slowly cooling the solution to room temperature to precipitate (bromopropylamine)4CsPb3Br11The crystal of (4).
Example 4
(Bromopropylamine)4CsPb3Br11Can be prepared by a solid phase method: at room temperature, adding lead bromide, cesium bromide and 3-bromopropylamine hydrobromide into a ball mill according to the stoichiometric ratio, and carrying out ball milling for 15 minutes to obtain (bromopropylamine)4CsPb3Br11The powder of (4).
The unit cell parameters for this example are as follows:α＝90°，β＝90°，γ＝90°，crystallized in orthorhombic system, point group mm2, Pmc21And (4) space group.
Example 3 and example 4 (bromopropylamine)4CsPb3Br11The structure stacking diagram of the crystals is shown in fig. 3.
Application of halide perovskite material with symbiotic structure in fields of photoelectric functional devices and the like
For the halide perovskite (bromopropylamine) having intergrowth structure obtained in example 34CsPb3Br11And (3) carrying out photoelectric performance test, drying, cutting and other pretreatment on the crystal, and then arranging the electrode material on the surface of the crystal by adopting an evaporation method to manufacture the photoelectric detection device.
The photoconductive test was performed using a 405nm laser as shown in figure 4. When the incident light intensity is 6.52mW/cm2And when the bias voltage is 5V, the ratio of the photocurrent to the dark current is about 240, and the excellent photoconductive performance is shown. The open-circuit voltage is about 2V, and the self-driven photoelectric detection performance is excellent. The method has great application potential in the fields of photoelectric functional devices and the like.
The halide perovskite material with a symbiotic structure is applied to the field of nonlinear optics.
For the halide perovskite (bromopropylamine) having intergrowth structure obtained in example 34CsPb3Br11A second order nonlinear signal test (SHG) was performed as shown in fig. 5. The material shows a strong second-order nonlinear signal at room temperature, which is about 0.4 times of that of a standard sample potassium dihydrogen phosphate (KDP), and shows that the material has great application potential in the fields of nonlinear optics and the like.
The halide perovskite material with a symbiotic structure is applied to the fields of ferroelectricity, pyroelectricity, piezoelectricity and the like.
For the halide perovskite (bromopropylamine) having intergrowth structure obtained in example 34CsPb3Br11The ferroelectric hysteresis loop test is carried out, and the typical ferroelectric hysteresis loop appears in the material before the phase change, as shown in figure 6. The material has great application potential in the fields of ferroelectricity, pyroelectricity, piezoelectricity and the like.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.