CN110655914B - Chiral perovskite nanowire crystal and preparation method thereof - Google Patents
Chiral perovskite nanowire crystal and preparation method thereof Download PDFInfo
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Abstract
The application relates to the field of chiral perovskite materials, in particular to a preparation method of a chiral perovskite nanowire crystal and the chiral perovskite nanowire crystal prepared by the preparation method. The preparation method of the chiral perovskite nanowire crystal comprises the steps of providing chiral organic amine and halogen acid, and enabling the chiral organic amine and the halogen acid to generate chiral ammonium salt; and dissolving the chiral ammonium salt and lead halide in a first solvent and preparing the chiral perovskite nanowire crystal by adopting an anti-solvent gas-phase auxiliary crystallization method. The preparation method has simple process steps, and can realize large-scale production of the chiral perovskite nanowire crystal.
Description
Technical Field
The application relates to the field of perovskite, in particular to a chiral perovskite nanowire crystal and a preparation method thereof.
Background
The organic-inorganic hybrid halide perovskite is used as a new generation of photoelectronic semiconductor material and has wide application in the fields of solar cells, light emitting diodes, lasers, photoelectric detectors, catalysis and the like. This is mainly due to its high carrier mobility, long carrier diffusion length and large light absorption coefficient. In addition, compared with polycrystalline thin films, perovskite crystals have lower trap density and no grain boundaries, and therefore have better photoelectric properties.
Haiming Zhu and Yongping Fu et al disclose a method for preparing perovskites. First step preparation of 100mg/mL PbAc 2 ·3H 2 An aqueous solution of O; the second step is to prepare the prepared PbAc 2 ·3H 2 Spin-coating O aqueous solution on a glass slide, and drying in an oven at 65 deg.C to obtain PbAc 2 A film; the third step is to prepare the prepared PbAc 2 Thin film (-1-2 cm) 2 ) Immersion in 1mL of 40mg/mL CH 3 NH 3 I/IPA solution, coated with PbAc 2 The face of the film is facing upward. The crystals were incubated in a quiet place. Due to the preparation of PbAc 2 The process of the thin film is complicated, resulting in a complicated process.
Disclosure of Invention
In order to solve the above problems, a first aspect of the present invention provides a method for preparing a chiral perovskite nanowire crystal, including providing a chiral organic amine and a halogen acid, and allowing the chiral organic amine and the halogen acid to generate a chiral ammonium salt; and dissolving the chiral ammonium salt and lead halide in a first solvent and preparing the chiral perovskite nanowire crystal by adopting an anti-solvent gas-phase auxiliary crystallization method.
The second aspect of the invention also provides the chiral perovskite nanowire crystal prepared by the preparation method of the chiral perovskite nanowire crystal.
The preparation method of the chiral perovskite nanowire crystal is simple in process and easy to control, and the chiral perovskite nanowire crystal can be produced in a large scale.
Drawings
The invention is described in further detail below with reference to the following figures and detailed description:
FIG. 1 is a synthetic scheme of an embodiment of the present application;
FIG. 2 is a schematic illustration of an anti-solvent vapor-phase assisted crystallization process according to an embodiment of the present application;
FIG. 3 is a common optical microscopy characterization of chiral perovskite nanowires of an embodiment of the present application;
FIG. 4 is a scanning electron microscopy characterization of chiral perovskite nanowires of an embodiment of the present application;
FIG. 5 is a crystal structure model diagram of a chiral perovskite nanowire resolved by single crystal X-ray diffraction in accordance with an embodiment of the present application;
fig. 6 is an ultraviolet visible absorption spectrum and a circular dichroism spectrum of a chiral perovskite nanowire of an embodiment of the present application.
Detailed Description
The present invention is further illustrated by the following examples and comparative examples, which are intended to be illustrative only and are not to be construed as limiting the invention. It is intended that all modifications and equivalents of the technical aspects of the present invention be included within the scope of the present invention without departing from the spirit and scope of the technical aspects of the present invention.
First, a method for preparing a chiral perovskite nanowire crystal provided according to a first aspect of the present invention will be described.
The preparation method of the chiral perovskite nanowire crystal comprises the steps of providing chiral organic amine and halogen acid, and enabling the chiral organic amine and the halogen acid to generate chiral ammonium salt; and dissolving the chiral ammonium salt and lead halide in a first solvent and preparing the chiral perovskite nanowire crystal by adopting an anti-solvent gas-phase auxiliary crystallization method.
The preparation method of the chiral perovskite nanowire crystal is simple in process and easy to control, and the chiral perovskite nanowire crystal can be produced in a large scale.
In addition, the Keton effect of the inherent exciton absorption band of the chiral perovskite nanowire crystal can generate a strong circular dichroism signal, and the circular dichroism signal corresponds to an absorption peak at an ultraviolet visible absorption spectrum diagram, so that the chiral perovskite material has a wide application prospect in the fields of nonlinear optics, ferroelectric piezoelectricity and the like.
According to the preparation method of the chiral perovskite nanowire crystal of the first aspect of the invention, the chiral organic amine comprises one or more of chiral alicyclic amines, chiral aromatic amines and chiral naphthylamines. Alternatively, the chiral alicyclic amines may be compounds of the following formulae IA1-IA 6; the chiral aromatic amine can be a compound shown as formulas IB1 and IB 2; the chiral naphthylamines may be compounds having the following formulae IC1-IC 2.
According to the preparation method of the chiral perovskite nanowire crystal of the first aspect of the invention, the hydrohalic acid comprises one or more of hydroiodic acid, hydrobromic acid and hydrochloric acid.
According to the preparation method of the chiral perovskite nanowire crystal of the first aspect of the invention, the anti-solvent gas-phase assisted crystallization method comprises the following steps: dissolving the chiral ammonium salt and lead halide in a first solvent and placing in a first container; and putting the first container containing the chiral ammonium salt into a second container containing a second solvent, sealing the second container and opening the first container, wherein the first solvent is a good solvent of the chiral ammonium salt, the second solvent is a poor solvent of the chiral ammonium salt, and crystallizing after a preset time to obtain the chiral perovskite nanowire.
Optionally, the first solvent is one or more of a mixed solvent of N, N-Dimethylformamide (DMF) and dimethyl sulfoxide (DMSO), a mixed solvent of DMSO and 1, 4-butyrolactone, DMSO, DMF and 1-4 butyrolactone; the poor solvent is one or more of chloroform, dichloromethane, diethyl ether, acetone and acetonitrile.
Alternatively, the volume ratio of DMF to DMSO is 2: 3.
Optionally, the solution is filtered to remove impurities after dissolving the chiral ammonium salt in the first solvent, for example, the solution can be filtered by a filter membrane with a pore size of less than or equal to 200nm, such as an organic syringe filter.
Next, the chiral perovskite nanowire crystal provided according to the second aspect of the present invention, which is prepared by the method of the first aspect of the present invention, will be described.
Next, examples of the method for producing a chiral perovskite nanowire crystal according to the present invention and a chiral perovskite nanowire crystal produced using the same will be explained.
The synthetic route of this example is shown in FIG. 1.
(1) Synthesis of ammonium salt precursor
6.32ml (0.0442mol) (R) - (+) -beta-methylphenethylamine (R-MPEA) or (S) - (-) -beta-methylphenethylamine (S-MPEA) was dissolved in 18.87ml (40%, mass fraction) of methanol; then 5ml HBr (48%, mass fraction, 0.0442mol) was slowly added dropwise thereto over 10 minutes; the mixture was stirred at 0 ℃ for 20 minutes. After the reaction is finished, the solvent is removed by rotary evaporation to obtain (R) - (+) -beta-methyl phenethyl ammonium bromide (R-MPEA) + Br - ) Or (S) - (-) -beta-methylphenylammonium bromide (S-MPEA) + Br - ) The product was a white powder with a yield of 99%.
(2) Method for preparing chiral perovskite nanowire crystal by anti-solvent gas-phase auxiliary crystallization method
Referring to FIG. 2, first, a mixed solvent of DMF and DMSO in a volume ratio of 2:3 is prepared; secondly, chiral ammonium salt precursor R-MPEA + Br - Or S-MPEA + Br - (143.4mg, 0.667mmol) and PbBr 2 (122.3mg, 0.333mmol) to 1ml of mixed solvent to obtain a chiral ammonium salt precursor mixed solution; then filtering the chiral ammonium salt precursor mixed solution by using an organic system syringe type filter membrane filter with the aperture of 200nm and pouring the filtered solution into a first container 10 with the volume of 20 ml; finally, the first container 10 is placed in a second container 20 of 50ml in an open manner; 20mL of CHCl as a poor solvent 3 Pouring into the space between the outer wall of the first container 10 and the inner wall of the second container 20, sealing the second container 20, and the whole system is kept free from vibration at room temperature. Poor solvent CHCl 3 The slow vapor diffuses into the precursor mixed solution in the first container 10. After 96 hours, the crystalline chiral perovskite white nanowire crystals were suspended in the first container 10.
And (3) morphology characterization:
referring to fig. 3 and 4, the chiral perovskite nanowire crystal is characterized by a common optical microscope and a scanning electron microscope, and fig. 3 shows the morphology of the chiral perovskite nanowire crystal characterized by the common electron microscope, which visually shows the size and shape of the chiral perovskite nanowire; FIG. 4 shows the morphology of the chiral perovskite nanowire crystal characterized by a scanning electron microscope, as shown in FIG. 4, it can be seen that the chiral perovskite nanowire crystal is a long and thin nanowire, and the diameter of the nanowire is approximately 200-600 nm. To further illustrate that the obtained nanowires are chiral perovskite materials, the structure of the nanowires is resolved through single crystal X-ray diffraction, and as shown in fig. 5, the obtained chiral nanowire crystals are (R) - (+) -beta-methylphenethylamine or (S) - (-) -beta-methylphenethylamine and octahedron with lead as a central bromine atom as a vertex to form ordered layered distribution; macroscopically, the two nanowire structures are in mirror symmetry and are chiral perovskite materials. The obtained chiral perovskite nanowire crystal material is non-centrosymmetric.
Optical properties:
referring to FIG. 6, the upper portion is the chiral perovskite nanowire crystalThe ultraviolet visible absorption spectrum of the body, the lower part is the circular dichroism spectrum of the chiral perovskite nanowire crystal, wherein the dark line corresponds to R- (MPEA) 1.5 PbBr 3.5 (DMSO) 0.5 The light lines of (1) correspond to S- (MPEA) 1.5 PbBr 3.5 (DMSO) 0.5 Of (c) is used. In the round two-color chromatogram, R- (MPEA) 1.5 PbBr 3.5 (DMSO) 0.5 And S- (MPEA) 1.5 PbBr 3.5 (DMSO) 0.5 The chiral perovskite nanowire crystals both showed strong circular dichromatic signals peaking at 345nm and 405nm and having opposite signs. Apparently, these circular dichroism responses are represented by R- (MPEA) 1.5 PbBr 3.5 (DMSO) 0.5 And S- (MPEA) 1.5 PbBr 3.5 (DMSO) 0.5 The Coriton effect of the intrinsic exciton absorption band of the chiral perovskite nanowire crystal is generated, and corresponds to an absorption peak at 390nm (3.18eV) of an ultraviolet visible absorption spectrogram. The chiral perovskite nanowire crystal is chiral and symmetric and is inevitably non-centrosymmetric, so that the chiral perovskite material has wide application prospect in the fields of nonlinear optics, ferroelectric piezoelectricity and the like.
Although the present application has been described with reference to the preferred embodiments, it is not intended to limit the scope of the claims, and many possible variations and modifications may be made by one skilled in the art without departing from the spirit of the present application.
Claims (7)
1. A preparation method of a chiral perovskite nanowire crystal comprises the steps of providing chiral organic amine and halogen acid, and enabling the chiral organic amine and the halogen acid to generate chiral ammonium salt; dissolving the chiral ammonium salt and lead halide in a first solvent and preparing the chiral perovskite nanowire crystal by adopting an anti-solvent gas-phase auxiliary crystallization method;
the chiral organic amine comprises one or more of chiral alicyclic amine, chiral aromatic amine and chiral naphthylamine;
the anti-solvent gas phase assisted crystallization method comprises the following steps: dissolving the chiral ammonium salt and lead halide in a first solvent and placing in a first container; putting the first container containing the chiral ammonium salt into a second container containing a second solvent, sealing the second container and opening the first container, wherein the first solvent is a good solvent of the chiral ammonium salt, the second solvent is a poor solvent of the chiral ammonium salt, and crystallizing after a preset time to obtain the chiral perovskite nanowire crystal, and the first solvent is one or more of a mixed solvent of N, N-dimethylformamide and dimethyl sulfoxide, a mixed solvent of dimethyl sulfoxide and 1, 4-butyrolactone, N-dimethylformamide, dimethyl sulfoxide and 1-4 butyrolactone; the second solvent is one or more of chloroform, dichloromethane, diethyl ether, acetone and acetonitrile.
2. The method for producing a chiral perovskite nanowire crystal according to claim 1, characterized in that: the chiral alicyclic amine comprises compounds shown in the following formulas IA1-IA4, the chiral aromatic amine comprises compounds shown in the following formulas IB1 and IB2, and the chiral naphthylamine comprises compounds shown in the following formulas IC1-IC 2:
3. the method for producing a chiral perovskite nanowire crystal according to claim 1 or 2, characterized in that: the hydrohalic acid comprises one or more of hydroiodic acid, hydrobromic acid, and hydrochloric acid.
4. The method for producing a chiral perovskite nanowire crystal according to claim 3, characterized in that: the first solvent is a mixed solvent of N, N-dimethylformamide and dimethyl sulfoxide, and the volume ratio of the N, N-dimethylformamide to the dimethyl sulfoxide is 2: 3.
5. The method for producing a chiral perovskite nanowire crystal according to claim 1, characterized in that: after the chiral ammonium salt is dissolved in the first solvent, the solution is filtered to remove impurities therein.
6. The method for producing a chiral perovskite nanowire crystal according to claim 5, characterized in that: filtering the solution with a filter membrane having a pore size of 200nm or less.
7. A chiral perovskite nanowire crystal produced by the method for producing a chiral perovskite nanowire crystal according to any one of claims 1 to 6.
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| CN111362809B (en) * | 2020-03-24 | 2023-03-31 | 国家纳米科学中心 | Chiral perovskite nanosheet, and preparation method and application thereof |
| CN115362563A (en) * | 2020-05-28 | 2022-11-18 | 国立研究开发法人科学技术振兴机构 | Film and method for manufacturing the same, circularly polarized light detecting element, circularly polarized light detecting device, and circularly polarized light detecting method |
| CN114369104A (en) * | 2021-12-20 | 2022-04-19 | 深圳市林上科技有限公司 | Frequency doubling chiral material and preparation method thereof |
| CN114875472B (en) * | 2022-04-25 | 2023-11-03 | 河南大学 | Organic-inorganic hybrid chiral perovskite helical structure micron sheet and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105366652A (en) * | 2015-11-23 | 2016-03-02 | 温州生物材料与工程研究所 | Chiral one-dimensional semiconductor nano-material self-assembly preparation method |
| WO2016151535A1 (en) * | 2015-03-24 | 2016-09-29 | King Abdullah University Of Science And Technology | Methods of preparation of organometallic halide structures |
| CN106629834A (en) * | 2016-12-14 | 2017-05-10 | 南京理工大学 | Method for using recrystallization method to prepare lead-halide perovskite nanowire |
| CN108129326A (en) * | 2017-12-21 | 2018-06-08 | 深圳大学 | A kind of chirality perovskite is nanocrystalline and preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2016151535A1 (en) * | 2015-03-24 | 2016-09-29 | King Abdullah University Of Science And Technology | Methods of preparation of organometallic halide structures |
| CN105366652A (en) * | 2015-11-23 | 2016-03-02 | 温州生物材料与工程研究所 | Chiral one-dimensional semiconductor nano-material self-assembly preparation method |
| CN106629834A (en) * | 2016-12-14 | 2017-05-10 | 南京理工大学 | Method for using recrystallization method to prepare lead-halide perovskite nanowire |
| CN108129326A (en) * | 2017-12-21 | 2018-06-08 | 深圳大学 | A kind of chirality perovskite is nanocrystalline and preparation method and application |
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