CN115181565A - Mixed cation chiral perovskite nanosheet and preparation method thereof - Google Patents
Mixed cation chiral perovskite nanosheet and preparation method thereof Download PDFInfo
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- 239000002135 nanosheet Substances 0.000 title claims abstract description 57
- 150000001768 cations Chemical class 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002243 precursor Substances 0.000 claims abstract description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 17
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003446 ligand Substances 0.000 claims abstract description 15
- 150000004820 halides Chemical class 0.000 claims abstract description 10
- 239000012296 anti-solvent Substances 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 18
- IRAGENYJMTVCCV-UHFFFAOYSA-N 2-phenylethanamine;hydrobromide Chemical compound [Br-].[NH3+]CCC1=CC=CC=C1 IRAGENYJMTVCCV-UHFFFAOYSA-N 0.000 claims description 10
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 6
- UPHCENSIMPJEIS-UHFFFAOYSA-N 2-phenylethylazanium;iodide Chemical compound [I-].[NH3+]CCC1=CC=CC=C1 UPHCENSIMPJEIS-UHFFFAOYSA-N 0.000 claims description 5
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims description 4
- 239000002055 nanoplate Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000002983 circular dichroism Methods 0.000 abstract description 22
- 238000001308 synthesis method Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 29
- 239000000523 sample Substances 0.000 description 22
- 238000000295 emission spectrum Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- 230000003287 optical effect Effects 0.000 description 12
- 238000000862 absorption spectrum Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000001142 circular dichroism spectrum Methods 0.000 description 8
- 238000002189 fluorescence spectrum Methods 0.000 description 8
- 230000005284 excitation Effects 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- -1 ammonium cations Chemical class 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
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- 238000013461 design Methods 0.000 description 3
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- 238000005406 washing Methods 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- HBAQYPYDRFILMT-UHFFFAOYSA-N 8-[3-(1-cyclopropylpyrazol-4-yl)-1H-pyrazolo[4,3-d]pyrimidin-5-yl]-3-methyl-3,8-diazabicyclo[3.2.1]octan-2-one Chemical class C1(CC1)N1N=CC(=C1)C1=NNC2=C1N=C(N=C2)N1C2C(N(CC1CC2)C)=O HBAQYPYDRFILMT-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
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- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
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- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000015654 memory Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- 238000004626 scanning electron microscopy Methods 0.000 description 1
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Abstract
The invention discloses a mixed cation chiral perovskite nanosheet and a preparation method thereof, wherein the preparation method comprises the following steps: s1: chiral organic ammonium, achiral organic ammonium and lead halide are used as perovskite precursors, organic micromolecules are used as surface ligands, and N, N' -dimethylformamide is used as a solvent to form a precursor solution; and S2, taking toluene as an anti-solvent, adding the precursor solution prepared in the step S1 into the anti-solvent, and synthesizing to obtain the mixed cation chiral perovskite nanosheet. The synthesis method is simple and rapid, and the obtained chiral perovskite nanosheet has strong circular dichroism signals.
Description
Technical Field
The invention relates to the field of organic-inorganic hybrid perovskite materials, in particular to a mixed cation chiral perovskite nanosheet and a preparation method thereof.
Background
Chirality, i.e., the inability of an object to coincide with its mirror image, is a fundamental property that exists not only in nature, but also in art, chemistry, construction and life where chiral materials and their mirror images are called enantiomers or enantiomers because of their non-centrosymmetric structure, and these materials exhibit interesting physical properties such as Circular Dichroism (CD), circularly polarized photoluminescence (CPL), nonlinear optical (NLO) effects, ferroelectrics, spintronics and photovoltaic effects.
Halide perovskites have proven to be a promising class of optoelectronic materials suitable for use in a variety of applications, including Light Emitting Diodes (LEDs), photonic lasers, photodetectors, and solar cells. Metal halide perovskite materials have valuable properties including flexible crystal structure, long charge carrier diffusion length, high dielectric constant, high tunable band gap, high optical absorption coefficient and strong spin-orbit coupling, and are extremely promising materials. However, their chemical structure is always centrosymmetric. Thus, chirality cannot be naturally generated in metal halide perovskites, nor can chiral molecules be directly applied to relevant optical applications. Research in recent years shows that chirality can be transferred from chiral organic molecules to halide perovskites, a new concept of chiral perovskite materials is generated, and the obtained chiral perovskites combine the advantages of the chiral materials and the halide perovskites and take a great step for the development of intelligent photoelectron and spintronic materials and devices.
Chiral perovskites absorb different amounts of right-handed and left-handed CPL and are therefore potential materials for CPL detection. CPL detection has been widely used in various fields such as optical communication, quantum computing, medical diagnosis, and image processing. And the circular polarization fluorescence spectrum of the chiral perovskite can capture the excitation state information of the chiral structure, and the chiral perovskite chiral fluorescence spectrum has wide application in the aspects of 3D display, optical safety, information storage, biological probes, photocatalytic asymmetric synthesis and the like. In addition, the chiral perovskite is also widely applied to applications such as circularly polarized photoelectric detectors, ferroelectrics, nonlinear optical effects, white light LEDs and the like. To better achieve these applications, the chiral optical properties (such as CD value and anisotropy factor g) are improved abs ) Is very gradual.
Various documents (J.Phys.chem.Lett.2021, 12,2676, adv.Mater.2021, 2008785) have reported that the circular dichroism signal of chiral perovskite formed by using chiral ligand R-/S-MBABr as A-site ion is very slight by using ligand-assisted co-precipitation (LARP) methodWeak and its anisotropy factor g abs And is also approximately zero, probably because the CD signal is nearly 0 due to too poor crystallinity, so it is significant to improve the crystallinity and CD signal to make them better applied to circularly polarized photoelectric detectors, circularly polarized light emitting diodes, three-dimensional displays, biological imaging, quantum computing, quantum communication, memories and spin transistors.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a high CD value and an anisotropy factor g abs The mixed cation chiral perovskite nano-sheet and the preparation method thereof. The method provides a new strategy for the design of the chiral optical characteristics of the chiral perovskite.
The first aspect of the invention provides a preparation method of mixed cation chiral perovskite nanosheets, which comprises the following steps:
s1: chiral organic ammonium, achiral organic ammonium and lead halide are used as perovskite precursors, organic micromolecules are used as surface ligands, and N, N' -dimethylformamide is used as a solvent to form a precursor solution;
and S2, taking toluene as an anti-solvent, adding the precursor solution prepared in the step S1 into the anti-solvent, and synthesizing to obtain the mixed cation chiral perovskite nanosheet.
The chiral organic ammonium is any one of R-/S-methylbenzyl ammonium bromide, R-/S-methylethyl ammonium bromide, R-/S-N-methylethyl ammonium bromide and R-/S-methylbenzyl ammonium iodide.
The further setting is that the non-chiral organic ammonium in the step S1 is any one of phenethyl ammonium bromide or phenethyl ammonium iodide.
Further setting that the lead halide in the step S1 is PbBr 2 Or PbI 2 。
It is further provided that the total amount of material of the respective mixed ammonium salts in step S1 should be kept constant, for example 0.08mmol.
It is further provided that the total amount of material of each mixed lead salt in step S1 should be kept constant, such as 0.04mmol.
Further setting the molar ratio of the mixed organic ammonium cation and the lead halide in the precursor liquid in the step S1 to be 2:1.
it is further set that the small organic molecule in step S1 is oleylamine.
It is further set that the volume of the precursor liquid taken in step S2 does not exceed 80 μ L.
In addition, the invention also provides the mixed cation chiral perovskite nanosheet prepared by the preparation method.
The method researches the relationship between chiral activity and chiral molecular structure of chiral perovskite and the crystalline state of the perovskite surface, and can obtain the perovskite nanosheet with adjustable light emission, narrow emission line width, high quantum yield and good environmental stability by changing the halogen atom at the X position of the two-dimensional perovskite.
The innovative mechanism of the invention is to improve the common chiral molecules (R-MBA) + ) The method adopts a dual-ligand strategy and applies a ligand-assisted co-sedimentation method to synthesize the mixed cation perovskite nanosheet, the method is simple and rapid, the synthesized nanosheet has a high circular dichroism signal at a fixed ratio, and the anisotropic factor g of the synthesized nanosheet is high abs ＝-3.8×10 -3 Aiming at the phenomenon, the chiral perovskite nanosheet is synthesized by applying a double-ligand assisted co-sedimentation method to three chiral ammonium cations with different structures, and the reason is verified through a circular dichroism test result. The invention can design high CD value and anisotropy factor g abs Provide a new approach and facilitate the development of chiral optical devices.
The invention has the following beneficial effects:
1. the synthetic method is simple and rapid, the obtained chiral perovskite nanosheet has strong circular dichroism signals, and in one embodiment of the invention, the anisotropy factor is g abs ＝3.8×10 -3 And the wavelength can be tuned, the emission from blue to green can be achieved, the stability is good, and the good fluorescence intensity can be still maintained after 21 days.
2. According to the invention, the surface crystallization condition and morphology are explored by researching the ratio of different chiral molecules and achiral molecules, the relationship between the crystallinity of the perovskite nanosheets and the circular dichroism signal can be explained through specific experimental results, and due to the addition of achiral ammonium cations, the surface crystallinity of the pure chiral perovskite nanosheets is improved, and further the circular dichroism of the pure chiral perovskite nanosheets is improved.
3. The invention is researched aiming at the chiral molecular structure and can design the high CD value and the anisotropy factor g abs Provide a new approach and facilitate the development of chiral optical devices.
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 introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is within the scope of the present invention for those skilled in the art to obtain other drawings based on the drawings without inventive exercise.
FIG. 1 shows chiral perovskite nanosheets ((R-MBA) in example 1 of the present invention x PEA 1-x ) 2 PbBr 4 NSs);
FIG. 2 shows chiral perovskite nanosheets ((R-MBA) in example 1 of the present invention x PEA 1-x ) 2 PbBr 4 NSs) XRD spectrum;
FIG. 3 shows chiral perovskite nanosheets ((R-MBA) in example 1 of the present invention x PEA 1-x ) 2 PbBr 4 NSs) ultraviolet absorption spectrum (solid line) and fluorescence emission spectrum (dashed line);
FIG. 4 shows chiral perovskite nanosheets ((R-/S-MBA) in example 1 of the present invention x PEA 1-x ) 2 PbBr 4 NSs) of (a) a circular dichroism spectrum and (b) of a corresponding g-value trend line plot;
FIG. 5 shows chiral perovskite nanoplates ((R-MPEA) in examples 2 and 3 of the present invention x PEA 1-x ) 2 PbBr 4 NSs、(R-N-DMBA x PEA 1-x ) 2 PbBr 4 NSs) ultraviolet absorption spectrum and fluorescence emission spectrum, a, b is (R-MPEA) x PEA 1-x ) 2 PbBr 4 NSs (a) ultraviolet absorption spectrum and (b) fluorescence emission spectrum, c, d is (R-N-DMBA) x PEA 1-x ) 2 PbBr 4 (c) ultraviolet absorption spectra and (d) fluorescence emission spectra of NSs;
FIG. 6 shows chiral perovskite nanoplate (a) ((R-MPEA) in examples 2 and 3 of the present invention x PEA 1-x ) 2 PbBr 4 NSs、(b)(R-N-DMBA x PEA 1-x ) 2 PbBr 4 NSs) and (c) a g-value trend line graph of a chiral perovskite nanosheet formed by chiral ammonium molecules with three different structures;
FIG. 7 shows chiral perovskite nanosheets ((R-MBA) in example 4 0.75 PEA 0.25 ) 2 PbBr 4(1-y) I 4y NSs) (a) fluorescence emission spectra, (b) ultraviolet absorption spectra, and (c) circular dichroism spectra;
FIG. 8 shows chiral perovskite nanosheets ((R-MBA) in example 1 of the present invention 0.75 PEA 0.25 ) 2 PbBr 4 NSs) fluorescence spectrum.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings.
Chiral organic ammonium and achiral organic ammonium are replaced by short names in the following embodiments, specifically:
R-/S-methylbenzylammonium bromide (R-/S-MBABr), R-/S-methylphenylammonium bromide (R-/S-MPEABr), R-/S-N-methylphenylammonium bromide (R-/S-N-DMBABr), R-/S-methylbenzylammonium iodide (R-/S-MBAI).
Phenethyl ammonium bromide (PEABr), phenethyl ammonium iodide (PEAI).
Example 1:
chiral double-ligand perovskite nanosheet ((R-/S-MBA) x PEA 1-x ) 2 PbBr 4 NSs) was prepared by the following steps: the raw materials for preparing the nano-sheet comprise: R-/S-MBABr and PEABrAmount of dry matter (see Table 1), pbBr 2 Dissolving (0.04 mmol) and oleylamine (1.25 μ L) in N, N-dimethylformamide (1 mL) to obtain precursor solution 1, adding 20 μ L of precursor solution 1 into vigorously stirred toluene (5 mL), stirring for 2min to obtain uniformly dispersed colloidal solution, and collecting the final solution (R-/S-MBA) x PEA 1-x ) 2 PbBr 4 NSs。
Specific ratios are as follows, for example, table 1:
| x | R-/S-MBABr | PEABr | |
| 0 | 0 | 0.08mmol | 0.04mmol |
| 0.25 | 0.02mmol | 0.06mmol | 0.04mmol |
| 0.50 | 0.04mmol | 0.04mmol | 0.04mmol |
| 0.75 | 0.06mmol | 0.02mmol | 0.04mmol |
| 1.00 | 0.08 |
0 | 0.04mmol |
FIG. 1 and FIG. 2 show (R-MBA) x PEA 1-x ) 2 PbBr 4 The scanning electron microscopy and XRD spectrogram corresponding to NSs show that the prepared product shows perovskite nanosheet characteristics from figures 1 and 2.
Example 2:
chiral double-ligand perovskite nanosheet ((R-MPEA) x PEA 1-x ) 2 PbBr 4 NSs) was prepared by the following steps: amounts of R-MPEABr and PEABr (see Table 2), pbBr 2 (0.04 mmol) and oleylamine (1.25. Mu.L) were dissolved in N, N-dimethylformamide (1 mL) to prepare a precursor solution 2, 20. Mu.L of the precursor solution 2 was added to toluene (5 mL) which was vigorously stirred for 2min to obtain a uniformly dispersed colloidal solution, and the final solution was (R-MPEA) x PEA 1-x ) 2 PbBr 4 NSs。
Specific ratios are as follows, for example, in table 2:
| x | R- | PEABr | PbBr | 2 |
| 0 | 0 | 0.08mmol | 0.04mmol | |
| 0.25 | 0.02mmol | 0.06mmol | 0.04mmol | |
| 0.50 | 0.04mmol | 0.04mmol | 0.04mmol | |
| 0.75 | 0.06mmol | 0.02mmol | 0.04mmol | |
| 1.00 | 0.08mmol | 0 | 0.04mmol |
example 3:
chiral double-ligand perovskite nanosheet ((R-N-DMBA) x PEA 1-x ) 2 PbBr 4 NSs) was prepared by the following steps: dissolving the amounts of R-N-DMBABr and PEABr (shown in Table 3), lead bromide (0.04 mmol) and oleylamine (1.25 μ L) in N, N-dimethylformamide (1 mL) to obtain precursor solution 3, adding 20 μ L of precursor solution 3 into vigorously stirred toluene (5 mL) for 2min to obtain uniformly dispersed colloidal solution, and collecting the final solution (R-N-DMBA) x PEA 1-x ) 2 PbBr 4 NSs。
Specific ratios are, for example, in table 3 below:
| x | R-N- | PEABr | PbBr | 2 |
| 0 | 0 | 0.08mmol | 0.04mmol | |
| 0.25 | 0.02mmol | 0.06mmol | 0.04mmol | |
| 0.50 | 0.04mmol | 0.04mmol | 0.04mmol | |
| 0.75 | 0.06mmol | 0.02mmol | 0.04mmol | |
| 1.00 | 0.08mmol | 0 | 0.04mmol |
example 4:
a series of chiral ammonium with different wavelength emission adopts double-ligand strategy double-ligand perovskite nanosheets ((R-MBA) 0.75 PEA 0.25 ) 2 PbBr 4(1-y) I 4y NSs) was prepared by the following steps: R-MBABr, PEABr, R-MBAI, PEAI, pbBr 2 、PbI 2 Dissolving the amount of each substance (see Table 4) and oleylamine (1.25 μ L) in N, N-dimethylformamide (1 mL) to obtain precursor solution 4, adding 20 μ L of precursor solution 4 into toluene (5 mL) under vigorous stirring for 2min to obtain uniformly dispersed colloidal solution, which is (R-MBA) as the final solution 0.75 PEA 0.25 ) 2 PbBr 4(1-y) I 4y NSs。
Specific ratios are as follows, for example, table 4:
in order to further verify the optical properties of the prepared chiral perovskite nanosheets, emission spectrum tests and circular dichroism spectrum tests are respectively carried out on the products obtained in typical examples 1,2 and 3. The method comprises the following specific steps:
(I): testing emission spectrum of prepared chiral perovskite nanosheet
1. And (3) testing the emission spectra of the chiral molecule perovskite nanosheets with different structures:
the samples used were: exemplary example 1, example 2 and example 3 preparation of (R-/S-MBA) x PEA 1-x ) 2 PbBr 4 NSs、(R-MPEA x PEA 1-x ) 2 PbBr 4 NSs、(R-N-DMBA x PEA 1-x ) 2 PbBr 4 NSs。
The apparatus used was: hitachi fluorescence detectors 5J1-0004.
The testing steps are as follows: putting a sample into a quartz cuvette with light transmission on four sides, opening a cover of an instrument, putting the cuvette into a support, covering the cover, then opening spectrum testing software on a computer, selecting a xenon lamp as a light source, setting the wavelength of excitation light to 365nm, finally selecting a proper slit by adjusting the size of the slit, selecting the wavelength range of emission spectrum 380 600nm on a testing interface, and starting clicking; storing data after one sample is tested; the samples after testing were again tested as above. And finally, adjusting the slit to be minimum, taking out the cuvette, pouring out the sample, washing the sample with ethanol, and putting the sample into a box.
And (3) testing results: the emission spectrum of the chiral perovskite nanosheets prepared in example 1, example 2 and example 3 under 365nm excitation light is 405-415nm, is a purple emission spectrum, and is shown in fig. 3 and fig. 5.
2. Emission spectrum test of chiral perovskite nanosheets emitting at different wavelengths
The samples used were: exemplary preparation of example 4 (R-MBA) 0.75 PEA 0.25 ) 2 PbBr 4(1-y) I 4y NSs。
The apparatus used was: the apparatus used was: hitachi fluorescence detectors 5J1-0004.
The testing steps are as follows: putting a sample into a quartz cuvette with light transmission on four sides, opening a cover of an instrument, putting the cuvette into a support, covering the cover, then opening spectrum testing software on a computer, selecting a xenon lamp as a light source, setting the wavelength of excitation light to be 365nm, finally selecting a proper slit by adjusting the size of the slit, selecting the wavelength range of emission spectrum 380 700nm on a testing interface, and starting clicking; storing data after one sample is tested; the samples after testing were again tested as above. And finally, adjusting the slit to be minimum, taking out the cuvette, pouring out the sample, washing the sample with ethanol, and putting the sample into a box.
And (3) testing results: under 365nm exciting light, the light-emitting spectrum of the chiral perovskite nanosheet prepared in example 4 is 400-530nm, is a purple-green emission spectrum, and the emission spectrum is shown in fig. 7.
3. Test for placing stability of emission spectrum of chiral perovskite nanosheet
The samples used were: (R-MBA) prepared in representative example 1 0.75 PEA 0.25 ) 2 PbBr 4 NSs。
The apparatus used was: the apparatus used was: hitachi fluorescence detectors 5J1-0004.
The testing steps are as follows: putting a sample into a quartz cuvette with light transmission on four sides, opening a cover of an instrument, putting the cuvette into a support, covering the cover, then opening spectrum testing software on a computer, selecting a xenon lamp as a light source, setting the wavelength of excitation light to 365nm, finally selecting a proper slit by adjusting the size of the slit, selecting the wavelength range of emission spectrum 380 700nm on a testing interface, and starting clicking; storing data after one sample is tested; at intervals, the sample was tested again as above until after 21 days the test was stopped. After the last test, the slit is adjusted to be minimum, then the cuvette is taken out, the sample is poured out, washed by ethanol and then placed in a box.
And (3) testing results: (R-MBA) prepared in example 1 under 365nm excitation light 0.75 PEA 0.25 ) 2 PbBr 4 NSs stability is good, fluorescence intensity is reduced by about 10% after 21 days, and a standing stability test is shown in figure 8.
(II): testing circular dichroism spectrum and ultraviolet absorption spectrum of prepared chiral perovskite nanosheet
The samples used were: a series of chiral perovskite nanoplates prepared in representative examples 1,2, 3 and 4
The apparatus used was: chirascan applied to Physics
And (3) testing: the apparatus was opened and preheated for 15 minutes by introducing nitrogen. Firstly, sweeping an air sample once, then deducting the background, putting a solvent toluene into a micro quartz cuvette with two light-transmitting surfaces, opening a cover of an instrument, respectively aligning the two light-transmitting surfaces of the cuvette with an incident light and a detector, then putting the cuvette into a bracket, covering the cover of the instrument on a computer operation page, setting, selecting a test range of 200 800nm, a scanning speed of 0.6nm/s, clicking a start button, taking out after the end, and storing data; then the test sample is put in, the instrument cover is covered, the test is started by clicking on a computer page, and the CD spectrum and the ultraviolet absorption spectrum are simultaneously scanned out. After the test, the data is saved, and the background is manually deducted. And then taking out the cuvette, pouring out the sample, washing the sample with ethanol, rinsing the sample with toluene, filling the sample into the cuvette, and continuing the test operation. After the last sample is tested and the instrument is closed, nitrogen is continuously introduced for 10 minutes, and then the gas is closed.
And (3) testing results: the test result shows that the absorption spectrum and the corresponding emission spectrum of a series of chiral perovskite nanosheets prepared by the method have the same evolution law and also have chiral signals. Moreover, circular dichroism spectrums of the perovskite nano sheets respectively prepared by using the R MBABr and the S MBABr are in a symmetrical form, which shows that chirality of the perovskite nano sheets is transferred to perovskite materials, and g value can reach 3.8 multiplied by 10 to the maximum -3 . And the relation between the chiral ammonium cation structure and the circular dichroism signal can be obviously found by changing the structure of the chiral molecules, and the corresponding shift of the peak position of the circular dichroism spectrum can be found by adjusting the halogen. The ultraviolet absorption spectrum is shown in fig. 3, 5 and 7, and the circular dichroism spectrum is shown in fig. 4, 6 and 7.
The method is simple and feasible by adopting a ligand-assisted co-precipitation method, the synthesized nano-sheet has excellent circular dichroism signals, the influence of the surface crystallization condition on the circular dichroism signals can be obtained by analyzing the proportion of chirality to achiral cations, and the relation between the circular dichroism signals and the structure of the nano-sheet is clearly found by comparing the circular dichroism signals of the double-ligand perovskite nano-sheet formed by three different chiral ammonium cations, so that the influence of the surface crystallization condition on the circular dichroism signals is further verified. By the method, a series of chiral perovskite nanosheets with circular dichroism response and tunable wavelength can be conveniently obtained. Due to its obvious chiral signal, the chiral compound, can be widely applied to the fields of photoelectric detectors, polarization optical devices and the like.
The above disclosure is only for the purpose of illustrating the preferred embodiments of the present invention, and it is therefore to be understood that the invention is not limited by the scope of the appended claims.
Claims (10)
1. A preparation method of a mixed cation chiral perovskite nanosheet is characterized by comprising the following steps:
s1: chiral organic ammonium, achiral organic ammonium and lead halide are used as perovskite precursors, organic micromolecules are used as surface ligands, and N, N' -dimethylformamide is used as a solvent to form a precursor solution;
and S2, taking toluene as an anti-solvent, adding the precursor solution prepared in the step S1 into the anti-solvent, and synthesizing to obtain the mixed cation chiral perovskite nanosheet.
2. The preparation method of the mixed cation chiral perovskite nanosheet according to claim 1, wherein: the chiral organic ammonium is any one of R-/S-methylbenzyl ammonium bromide, R-/S-methylethyl ammonium bromide, R-/S-N-methylethyl ammonium bromide and R-/S-methylbenzyl ammonium iodide.
3. The method for preparing mixed cation chiral perovskite nanosheets of claim 1, wherein: the non-chiral organic ammonium in the step S1 is any one of phenethyl ammonium bromide or phenethyl ammonium iodide.
4. The method for preparing mixed cation chiral perovskite nanosheets of claim 1, wherein: in the step S1, the lead halide is PbBr 2 Or PbI 2 。
5. The method for preparing mixed cation chiral perovskite nanosheets of claim 1, wherein: the total amount of the respective mixed ammonium salts in step S1 remains unchanged.
6. The method for preparing mixed cation chiral perovskite nanosheets of claim 1, wherein: the total amount of the substances of each mixed lead salt in step S1 is kept constant.
7. The method for preparing mixed cation chiral perovskite nanosheets of claim 1, wherein: in the step S1, the molar ratio of the mixed organic ammonium cation and the lead halide in the precursor solution is 2:1.
8. the method for preparing mixed cation chiral perovskite nanosheets of claim 1, wherein: in the step S1, the organic micromolecules are oleylamine.
9. The method for preparing mixed cation chiral perovskite nanosheets of claim 1, wherein: the volume of the precursor liquid taken in the step S2 is not more than 80 mu L.
10. A mixed cation chiral perovskite nanoplate prepared by the preparation method as claimed in any one of claims 1 to 9.
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| CN111362809A (en) * | 2020-03-24 | 2020-07-03 | 国家纳米科学中心 | Chiral perovskite nanosheet, and preparation method and application thereof |
| CN112840473A (en) * | 2018-09-24 | 2021-05-25 | 牛津光伏有限公司 | Method for forming crystalline or polycrystalline layers of organic-inorganic metal halide perovskites |
| US20210343948A1 (en) * | 2019-09-12 | 2021-11-04 | Purdue Research Foundation | Two-Dimensional Halide Perovskite Materials |
| CN113881431A (en) * | 2021-10-11 | 2022-01-04 | 南京工业大学 | Chiral perovskite Cs4PbBr6Nano-rod and preparation method thereof |
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| CN112840473A (en) * | 2018-09-24 | 2021-05-25 | 牛津光伏有限公司 | Method for forming crystalline or polycrystalline layers of organic-inorganic metal halide perovskites |
| US20210343948A1 (en) * | 2019-09-12 | 2021-11-04 | Purdue Research Foundation | Two-Dimensional Halide Perovskite Materials |
| CN111362809A (en) * | 2020-03-24 | 2020-07-03 | 国家纳米科学中心 | Chiral perovskite nanosheet, and preparation method and application thereof |
| CN113881431A (en) * | 2021-10-11 | 2022-01-04 | 南京工业大学 | Chiral perovskite Cs4PbBr6Nano-rod and preparation method thereof |
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| 周明浩;姜爽;张天永;史永宏;金雪;段鹏飞;: "手性钙钛矿纳米材料的构筑及光电性能", 化学进展, no. 04, 24 April 2020 (2020-04-24), pages 361 * |
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