CN114574188A - Mn-doped PEA (polyethylene terephthalate) synthesized by assistance of HBr (hydrogen bromide) solution2PbBr4Method for two-dimensional perovskite - Google Patents
Mn-doped PEA (polyethylene terephthalate) synthesized by assistance of HBr (hydrogen bromide) solution2PbBr4Method for two-dimensional perovskite Download PDFInfo
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- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 title claims description 149
- 229910000042 hydrogen bromide Inorganic materials 0.000 title claims description 74
- -1 polyethylene terephthalate Polymers 0.000 title claims description 7
- 229920000139 polyethylene terephthalate Polymers 0.000 title claims description 7
- 239000005020 polyethylene terephthalate Substances 0.000 title claims description 7
- 239000002243 precursor Substances 0.000 claims abstract description 77
- 238000000034 method Methods 0.000 claims abstract description 59
- 239000007787 solid Substances 0.000 claims abstract description 32
- 238000002156 mixing Methods 0.000 claims abstract description 24
- 229910021568 Manganese(II) bromide Inorganic materials 0.000 claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 13
- 239000013078 crystal Substances 0.000 claims description 9
- 238000000861 blow drying Methods 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 6
- 230000002194 synthesizing effect Effects 0.000 abstract description 4
- 238000005424 photoluminescence Methods 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 99
- 239000011572 manganese Substances 0.000 description 55
- 235000010582 Pisum sativum Nutrition 0.000 description 40
- 229920000120 polyethyl acrylate Polymers 0.000 description 40
- 241000219843 Pisum Species 0.000 description 26
- 240000004713 Pisum sativum Species 0.000 description 14
- 238000006862 quantum yield reaction Methods 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 238000004020 luminiscence type Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 239000011550 stock solution Substances 0.000 description 8
- 238000000103 photoluminescence spectrum Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- RJYMRRJVDRJMJW-UHFFFAOYSA-L dibromomanganese Chemical compound Br[Mn]Br RJYMRRJVDRJMJW-UHFFFAOYSA-L 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 4
- 238000001748 luminescence spectrum Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000013081 microcrystal Substances 0.000 description 4
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002159 nanocrystal Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- IRHSMHDWGTWASK-UHFFFAOYSA-N calcium barium(2+) oxygen(2-) Chemical compound [O--].[O--].[Ca++].[Ba++] IRHSMHDWGTWASK-UHFFFAOYSA-N 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent 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
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Abstract
The invention belongs to the technical field of preparation of two-dimensional perovskite materials, and particularly relates to Mn-doped PEA synthesized by assistance of HBr solution2PbBr4A method of two-dimensional perovskite comprising the steps of: mixing solid PbBr2Mixing with HBr solution to obtain PbBr2Precursor solution; adding solid MnBr2Mixing with HBr solution to obtain MnBr2Precursor solution; subjecting the MnBr to2Precursor solution and the PbBr2Mixing the precursor solutions, and adding the solid PEABr powder to obtain Mn-doped PEA2PbBr4And (4) platelets. The method can be used for inductively synthesizing Mn-doped PEA by a single HBr solvent at room temperature2PbBr4Two-dimensional perovskite, and its photoluminescence efficiency and stability.
Description
Technical Field
The invention belongs to the technical field of preparation of two-dimensional perovskite materials, and particularly relates to Mn-doped PEA (barium calcium oxide) synthesized by assistance of HBr (hydrogen bromide) solution2PbBr4A method of two-dimensional perovskite.
Background
Mn-doped two-dimensional perovskites have received much attention in recent years due to their excellent optical properties and thermal stability. PEA with Mn doped with phenethyl as A site2PbBr4Show excellentAnd (4) the optical magnetic property. Mn doped PEA2PbBr4Two-dimensional perovskite (Mn: PEA)2PbBr4) Can radiate exciton luminescence with edge to 415 nm and orange luminescence of Mn to 600 nm4T1To6A1The radiation originates from the energy transfer of band-edge excitons to the Mn d-d level. The relative proportion of two luminescence peaks can be effectively regulated and controlled by adjusting the doping concentration of Mn, which is beneficial to the application of the material in photoelectric sensor devices. High temperature thermal Injection methods are currently commonly used, such as the literature "Parobek, David, Dong, et al, direct Hot-Injection Synthesis of Mn-Doped CsPbBr3 Nanocrystals [ J]Chemistry of materials APublic of American Chemistry Society,2018,30(9):2939-2944. "and" Dutta S K, DuttaA, Das Adhikari S, et al. Doping Mn2+in Single Crystalline Layered Perovskite Microcrystals[J]ACS Energy Letters,2018 "mentions the preparation of nanocrystals using a high temperature thermal injection method, with a preparation temperature of 200 degrees celsius. However, the quantum yield of the Mn-doped two-dimensional perovskite nanocrystal prepared by the mainstream method is not high, the quantum yield is only 41%, the synthesis step is complicated, the required reaction temperature is high, and the required hardware conditions are harsh, which all limit the further development of the material.
Disclosure of Invention
The present invention solves at least one of the above problems.
The invention aims to solve the technical problem of at least providing a method for synthesizing Mn-doped PEA by using HBr solution for assistance2PbBr4A process for the two-dimensional synthesis of Mn-doped PEA by induction synthesis in a single HBr solvent and at room temperature2PbBr4Two-dimensional perovskite, and its photoluminescence efficiency and stability.
In order to solve the problems, the invention discloses a method for synthesizing Mn-doped PEA by using HBr solution for assistance2PbBr4A method of two-dimensional perovskite comprising the steps of:
the method comprises the following steps: mixing solid PbBr2Mixed with HBr solution and shaken to clear at room temperature to obtain PbBr2Precursor solution;
step two: adding solid MnBr2Mixing with HBr solution, and shaking at room temperature to clear to obtain MnBr2Precursor solution;
step three: subjecting the MnBr to2Precursor solution and the PbBr2Mixing the precursor solutions, stirring to clarify to obtain a mixed precursor solution, and adding solid PEABr powder into the mixed precursor solution to obtain Mn-doped PEA2PbBr4A crystal plate;
step four: doping the obtained Mn with PEA2PbBr4And grinding and blow-drying the platelets to remove unreacted HBr solution.
Preferably, PbBr is used in step one2The volume ratio of the substance(s) to the HBr solution is 0.08mmol (50-75) mu L; MnBr in the second step2The volume ratio of the substance(s) to the HBr solution is (0.32-0.64) mmol, (50-75) mu L; in the mixed precursor solution obtained in the third step, MnBr is added2/PbBr2The molar feed ratio of (A) is 2/1-6/1.
Preferably, PbBr in step one2The ratio of the amount of substance(s) to the volume of HBr solution is 0.08mmol: 50. mu.L; MnBr in the second step2The ratio of the amount of substance(s) in HBr solution is 0.32mmol: 50. mu.L; in the mixed precursor solution obtained in the third step, MnBr is contained in the mixed precursor solution2/PbBr2Is 4/1.
Preferably, PbBr in step one2The ratio of the amount of substance(s) to the volume of HBr solution is 0.08mmol: 50. mu.L; MnBr in the second step2The ratio of the amount of substance(s) in HBr solution is 0.64mmol: 50. mu.L; in the mixed precursor solution obtained in the third step, MnBr is contained in the mixed precursor solution2/PbBr2Is 6/1.
Preferably, the volume ratio of the mass of the solid PEABr powder to the mixed precursor solution is (0.3-0.35) g (100-150) mu L.
Preferably, the ratio of the mass of the solid PEABr powder to the volume of the mixed precursor solution is 0.35g: 100. mu.L.
Preferably, the solid PEABr powder is added into the mixed precursor solution and then stirred to react for 3-10 minutes.
Preferably, the concentration of the HBr solution is 30-50%.
The invention has the advantages of
1. The application firstly provides a method for synthesizing Mn-doped PEA at room temperature by HBr-assisted solid-liquid mixing2PbBr4The two-dimensional perovskite has the advantages of energy conservation, simple operation, simple and easy used equipment, controllable process and low cost, and is very favorable for production and manufacturing.
2. Mn-doped PEA synthesized in the present application2PbBr4The two-dimensional perovskite has excellent luminescence property and long service life. Experiments show that the orange (605nm) photoluminescence quantum yield of Mn is as high as 98%. In the method, due to the auxiliary action of HBr, the defect state of the surface covering the microchip is effectively passivated, and the Mn lifetime attenuation is proved to be in single exponential attenuation through a fluorescence attenuation curve.
Drawings
FIG. 1 shows Mn doped PEA prepared in comparative examples 1, 2 and 3 and example 12PbBr4The PL spectrum of (1).
FIG. 2 shows Mn doped PEA prepared in comparative examples 1, 2 and 3 and example 12PbBr4PL spectrum Mn of2+The attenuation curve of (c).
FIG. 3 shows Mn doped PEA prepared in comparative examples 1, 2 and 3 and example 12PbBr4PLQYs luminous efficiency and Mn PL lifetime plots.
FIG. 4 shows Mn doped PEAs prepared in examples 2, 4, 5, 6, 7, 8 and 92PbBr4PL spectrum of the platelet.
FIG. 5 shows Mn-doped PEAs prepared in examples 2, 4, 5, 6, 7, 8 and 92PbBr4PL QYs luminescence efficiency plot of platelets.
FIG. 6 shows Mn doped PEAs prepared in examples 2, 4, 5, 6, 7, 8 and 92PbBr4Exciton decay curve for platelets.
FIG. 7 shows Mn doped PEAs prepared in examples 2, 4, 5, 6, 7, 8 and 92PbBr4Mn of platelets2+The decay curve.
Fig. 8 shows examples 2 and 4. 2. 4, 5, 7,8. 9 Mn doped PEA2PbBr4SEM image and XRD pattern.
FIG. 9 shows Mn-doped PEAs prepared in examples 2, 9, 10, 11, 12 and 132PbBr4The luminescence spectrum of (2).
FIG. 10 shows Mn doped PEAs prepared in examples 2, 9, 10, 11, 12 and 132PbBr4Quantum yield curve of (a).
FIG. 11 shows Mn-doped PEAs prepared in examples 3, 14, 15, 16 and 172PbBr4The luminescence spectrum of (1).
FIG. 12 shows Mn doped PEAs prepared in examples 3, 14, 15, 16 and 172PbBr4Quantum yield curve of (a).
Detailed Description
The inventive concepts of the present disclosure will be described hereinafter using terms commonly employed by those skilled in the art to convey the substance of their work to others skilled in the art. These inventive concepts may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. These embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of their inclusion to those skilled in the art. It should also be noted that these embodiments are not mutually exclusive. A component, step, or element from one embodiment may be assumed to be present or used in another embodiment. The particular embodiments shown and described may be substituted for a wide variety of alternate and/or equivalent implementations without departing from the scope of the embodiments of the present disclosure. This application is intended to cover any adaptations or variations of the embodiments discussed herein. It will be apparent to those skilled in the art that alternative embodiments may be practiced using only some of the described aspects. Specific numbers, materials, and configurations are set forth in the examples for the purpose of illustration, however, alternative examples may be practiced by those skilled in the art without these specific details. In other instances, well-known features may be omitted or simplified in order not to obscure the illustrative embodiments.
Mn doping synthesized by HBr solutionHeteroPEA2PbBr4A method of two-dimensional perovskite comprising the steps of:
the method comprises the following steps: mixing solid PbBr2Mixed with HBr solution and shaken to clear at room temperature to obtain PbBr2Precursor solution;
step two: adding solid MnBr2Mixing with HBr solution, and shaking at room temperature to clear to obtain MnBr2Precursor solution;
step three: subjecting the MnBr to2Precursor solution and the PbBr2Mixing the precursor solutions, stirring to clarify to obtain a mixed precursor solution, and adding solid PEABr powder into the mixed precursor solution to obtain Mn-doped PEA2PbBr4A crystal plate;
step four: doping the obtained Mn with PEA2PbBr4And grinding and blow-drying the platelets to remove unreacted HBr solution.
PbBr in the first step2The volume ratio of the substance(s) to the HBr solution is 0.08mmol (50-75) mu L; MnBr in the second step2The volume ratio of the substance(s) to the HBr solution is (0.32-0.64) mmol, (50-75) mu L; in the mixed precursor solution obtained in the third step, MnBr is contained in the mixed precursor solution2/PbBr2The molar feed ratio of (A) is 2/1-6/1.
The volume ratio of the mass of the solid PEABr powder to the mixed precursor solution is (0.3-0.35) g (100-150) mu L.
And adding the solid PEABr powder into the mixed precursor solution, and then stirring and reacting for 3-10 minutes.
The concentration of the HBr solution is 30-50%.
The present invention is described in further detail below with reference to the attached drawing figures and more specific examples, wherein the starting materials are all commercially available. The HBr solution in the following examples was 43% in concentration.
Comparative example 1
The method comprises the following steps: 0.2mmol of PbBr2、0.6mmol MnBr2Mixing in 3mL of dimethylformamide to obtain a precursor stock solution;
step two: adding toluene into the precursor stock solution obtained in the step one, and stirring vigorously to obtain a reaction solution which is quickly turbid and generates white precipitates to obtain a flocculent product;
step three: centrifuging the obtained flocculent product to obtain two-dimensional perovskite solution precipitate to obtain Mn-doped PEA2PbBr4。
Comparative example 2
The method comprises the following steps: 0.2mmol of PbBr2、0.6mmol MnBr2Mixing in 3mL of dimethylformamide to obtain a precursor stock solution;
step two: adding 20 mu LHBr solution into the precursor stock solution, and stirring until the solution is clear;
step three: then adding toluene into the stock solution obtained in the first two steps, and violently stirring, wherein the reaction solution is quickly turbid in the process, and white precipitate is generated to obtain a flocculent product;
step four: centrifuging the obtained flocculent product to obtain two-dimensional perovskite solution precipitate to obtain Mn-doped PEA2PbBr4。
Comparative example 3
The method comprises the following steps: 0.2mmol of PbBr2、0.6mmol MnBr2Mixing in 3mL of dimethylformamide to obtain a precursor stock solution;
step two: adding 20 mu LHBr solution into the precursor stock solution, and stirring until the solution is clear;
step three: then adding toluene into the stock solution obtained in the first two steps, and violently stirring, wherein the reaction solution is quickly turbid in the process, and white precipitate is generated to obtain a flocculent product;
step four: centrifuging the obtained flocculent product to obtain two-dimensional perovskite solution precipitate to obtain Mn-doped PEA2PbBr4。
Step five: doping the obtained Mn with PEA2PbBr4Annealing at 100 ℃ for ten minutes to obtain Mn-doped PEA with improved performance2PbBr4。
Example 1
Mn-doped PEA (polyethylene terephthalate) synthesized by assistance of HBr (hydrogen bromide) solution2PbBr4A process for the preparation of a two-dimensional perovskite comprising the steps of:
the method comprises the following steps: 0.08mmol of solid PbBr was added2Mixed with 50 μ l HBr solution and shaken to clear at room temperature to give PbBr2Precursor solution;
step two: adding 0.24mmol of solid MnBr2Mixed with 50. mu.l HBr solution and shaken to clear at room temperature to give MnBr2Precursor solution;
step three: subjecting the MnBr to2Precursor solution and the PbBr2Mixing all the precursor solutions, stirring until the precursor solutions are clear to obtain a mixed precursor solution, and then adding 0.35g of solid PEABr powder into the mixed precursor solution to obtain Mn-doped PEA2PbBr4A crystal plate;
step four: the obtained Mn is doped with PEA2PbBr4And grinding and blow-drying the platelets to remove unreacted HBr solution.
FIGS. 1, 2, 3 are Mn-doped PEAs prepared in comparative examples 1, 2, 3 and example 12PbBr4PL spectrum and PL spectrum Mn of2+And Mn PL life graph, wherein comparative examples 1, 2, 3 and example 1 are respectively designated as S1, S2, S3 and S4. As can be seen from FIG. 3, the Mn-doped PEA obtained in comparative example one2PbBr4The luminous efficiency is lower than 30%. Mn-doped PEA obtained in comparative example one with addition of HBr2PbBr4The quantum yield of (A) is enhanced, but only reaches about 40% of the common level. And Mn is doped with PEA after annealing2PbBr4The quantum yield of the method is effectively improved to 70%, but solvents such as DMF, toluene and the like are still used in the experiment, so that the synthesis steps are not simplified. In example one, Mn-doped PEA was synthesized by a solid-liquid mixing single HBr-assisted synthesis strategy2PbBr4The performance is greatly improved, and the unified quantum yield also reaches 98%. Mn-doped PEA obtained in example 1, in comparison with comparative examples 1, 2 and 32PbBr4The unified quantum yield is greatly improved.
From fig. 2, it can be seen that the Mn emission band of S4 has a slow single exponential decay compared to S1, S2, S3. The Mn fluorescence lifetimes calculated for S1, S2, S3, and S4 were 0.55, 0.57, 0.61, and 0.68ms, respectively.The single exponential decay and longer fluorescence lifetime of S4 indicate that the Mn-doped PEA synthesized in example 12PbBr4Has the most excellent optical performance.
Example 2
Mn-doped PEA (polyethylene terephthalate) synthesized by assistance of HBr (hydrogen bromide) solution2PbBr4A method of two-dimensional perovskite comprising the steps of:
the method comprises the following steps: 0.08mmol of solid PbBr was added2Mixed with 50 μ l HBr solution and shaken to clear at room temperature to give PbBr2Precursor solution;
step two: adding 0.08mmol of solid MnBr2Mixed with 50. mu.l HBr solution and shaken to clear at room temperature to give MnBr2Precursor solution;
step three: subjecting the MnBr to2Precursor solution and the PbBr2Mixing all the precursor solutions, stirring until the precursor solutions are clear to obtain a mixed precursor solution, and then adding 0.35g of solid PEABr powder into the mixed precursor solution to obtain Mn-doped PEA2PbBr4A crystal plate;
step four: the obtained Mn is doped with PEA2PbBr4And grinding and blow-drying the platelets to remove unreacted HBr solution.
Example 3
Mn-doped PEA (polyethylene terephthalate) synthesized by assistance of HBr (hydrogen bromide) solution2PbBr4A method of two-dimensional perovskite comprising the steps of:
the method comprises the following steps: 0.08mmol of solid PbBr was added2Mixed with 50 μ l HBr solution and shaken to clear at room temperature to give PbBr2Precursor solution;
step two: adding 0.32mmol of solid MnBr2Mixed with 50. mu.l HBr solution and shaken to clear at room temperature to give MnBr2Precursor solution;
step three: subjecting the MnBr to2Precursor solution and the PbBr2Mixing all the precursor solutions, stirring until the precursor solutions are clear to obtain a mixed precursor solution, and then adding 0.35g of solid PEABr powder into the mixed precursor solution to obtain Mn-doped PEA2PbBr4A crystal plate;
step four: doping the obtained Mn with PEA2PbBr4And grinding and blow-drying the platelets to remove unreacted HBr solution.
Example 4
Mn-doped PEA (polyethylene terephthalate) synthesized by assistance of HBr (hydrogen bromide) solution2PbBr4A process for the preparation of a two-dimensional perovskite comprising the steps of:
the method comprises the following steps: 0.08mmol of solid PbBr was added2Mixed with 50 μ l HBr solution and shaken to clear at room temperature to give PbBr2Precursor solution;
step two: adding 0.48mmol of solid MnBr2Mixed with 50. mu.l HBr solution and shaken to clear at room temperature to give MnBr2Precursor solution;
step three: mixing the MnBr2Precursor solution and the PbBr2Mixing all the precursor solutions, stirring until the precursor solutions are clear to obtain a mixed precursor solution, and then adding 0.35g of solid PEABr powder into the mixed precursor solution to obtain Mn-doped PEA2PbBr4A crystal plate;
step four: doping the obtained Mn with PEA2PbBr4And grinding and blow-drying the platelets to remove unreacted HBr solution.
Example 5
The reaction conditions and procedure were the same as in example 1, except that the amount of manganese bromide in the procedure was 0 mmol.
Example 6
The reaction conditions and procedure were the same as in example 1, except that the amount of manganese bromide used in the procedure was 0.016 mmol.
Example 7
The reaction conditions and procedure were the same as in example 1, except that the amount of manganese bromide in the procedure was 0.04 mmol.
Example 8
The reaction conditions and procedure were the same as in example 1, except that the amount of manganese bromide in the procedure was 0.16 mmol.
Example 9
The reaction conditions and procedure were the same as in example 1, except that the amount of manganese bromide in the procedure was 0.64 mmol.
FIGS. 4 to 7 are Mn doped PEAs prepared in examples 2, 4, 5, 6, 7, 8 and 92PbBr4PL spectrum, PL QYs, exciton and Mn of2+The decay curve. In the examples, the molar charge ratio of manganese bromide to lead bromide was increased from 0:1 to 8:1, and it can be seen from the PL spectrum in fig. 4 that as the Mn/Pb addition ratio was increased, the exciton fluorescence intensity gradually decreased, while the Mn fluorescence intensity significantly increased, and the exciton lifetime sharply decreased, while the Mn lifetime slightly increased. As can be seen from the PL QYs graph in FIG. 5, the maximum luminescence quantum yield reached 98% when the Mn/Pb ratios were 6/1, respectively.
The improvement of the luminescence performance can be realized by regulating and controlling the doping concentration of Mn ions, different Mn ions are doped into crystal lattices, and the dual-photon emission component of two-dimensional perovskite microcrystal can also be regulated and controlled, under the condition of low-concentration doping, the perovskite presents dual-photon emission, when the Mn doping concentration in the microcrystal is increased, the energy transfer from excitons to Mn energy level is enhanced, and Mn is doped with PEA2PbBr4The two-dimensional perovskite microcrystal presents a single Mn emission band, and the quantum yield of the single Mn emission band is nearly uniform.
FIG. 8(a) (b) (c) shows Mn doped PEA prepared in examples 2 and 42PbBr4SEM image of wafer. FIG. 8(d) shows Mn doped PEAs prepared in examples 2, 4, 5, 7, 8, 92PbBr4XRD pattern of (a).
As can be seen from FIG. 8, the sample is flat and has a size of 1-10 μm, and the morphology and size of the microchip are not changed with the increase of the Mn doping concentration, and from the XRD spectrogram, the sample is a two-dimensional layered structure, and the diffraction peak moves to the high-angle direction with the increase of Mn content, and the surface Mn ions are effectively doped.
Example 10
The reaction conditions and procedure were the same as in example 2 except that 12.5. mu.L of hydrogen bromide was used in the first and second steps.
Example 11
The reaction conditions and procedure were the same as in example 2 except that 25. mu.L of hydrogen bromide was used in the first and second steps.
Example 12
The reaction conditions and procedure were the same as in example 2 except that 37.5. mu.L of hydrogen bromide was used in the first and second steps.
Example 13
The reaction conditions and procedure were the same as in example 2 except that 62.5. mu.L of hydrogen bromide was used in the first and second steps.
Example 14
The reaction conditions and procedure were the same as in example 3 except that 25. mu.L of hydrogen bromide was used in the first and second steps.
Example 15
The reaction conditions and procedure were the same as in example 3 except that 37.5. mu.L of hydrogen bromide was used in the first and second steps.
Example 16
The reaction conditions and procedure were the same as in example 3 except that 62.5. mu.L of hydrogen bromide was used in the first and second steps.
Example 17
The reaction conditions and procedure were the same as in example 3 except that 75. mu.L of hydrogen bromide was used in the first and second steps.
Referring to the data analysis of FIGS. 9-12, FIG. 9 is a Mn doped PEA prepared in examples 2, 9, 10, 11, 12, 132PbBr4The luminescence spectrum of (1). FIG. 10 shows Mn-doped PEAs prepared in examples 2, 9, 10, 11, 12 and 132PbBr4Quantum yield curve of (a). FIG. 11 shows Mn doped PEAs prepared in examples 3, 14, 15, 16 and 172PbBr4The luminescence spectrum of (1). FIG. 12 shows Mn doped PEAs prepared in examples 3, 14, 15, 16 and 172PbBr4Quantum yield curve of (a). The total amount of hydrogen bromide used in step two of examples 2, 9, 10, 11, 12, 13, 3, 14, 15, 16, 17 increased from 25 μ L to 150 μ L, and the luminescence quantum yield was effectively controlled up to 98% with increasing HBr volume. It can be seen that the total amount of hydrogen bromide used in step one and step two ranges from 100 μ L to 150 μ L, and the doping effect of Mn ions in the crystal lattice is better.
As can be seen from the above examples and analysis of test data, the present applicationPlease suggest that unlike the conventional process, the present application first proposes that Mn-doped PEA can be synthesized at room temperature by HBr-assisted solid-liquid mixing2PbBr4The two-dimensional perovskite greatly saves energy, is simple to operate, simple and easy to use equipment, controllable in process and low in cost, and is very favorable for production and manufacturing.
The above description is only a preferred embodiment of the present invention, and it should not be understood that the scope of the present invention is limited thereby, and it should be understood by those skilled in the art that various other modifications and equivalent arrangements can be made by applying the technical solutions and concepts of the present invention within the scope of the present invention as defined in the appended claims.
Claims (8)
1. Mn-doped PEA (polyethylene terephthalate) synthesized by assistance of HBr (hydrogen bromide) solution2PbBr4A method of two-dimensional perovskite, characterized in that it comprises the steps of:
the method comprises the following steps: mixing solid PbBr2Mixed with HBr solution and shaken to clear at room temperature to obtain PbBr2Precursor solution;
step two: adding solid MnBr2Mixing with HBr solution, and shaking at room temperature to clear to obtain MnBr2Precursor solution;
step three: subjecting the MnBr to2Precursor solution and the PbBr2Mixing the precursor solutions, stirring to clarify to obtain a mixed precursor solution, and adding solid PEABr powder into the mixed precursor solution to obtain Mn-doped PEA2PbBr4A crystal plate;
step four: doping the obtained Mn with PEA2PbBr4And grinding and blow-drying the platelets to remove unreacted HBr solution.
2. The method of claim 1, wherein PbBr in step one2The volume ratio of the substance(s) to the HBr solution is 0.08mmol (50-75) mu L; MnBr in the second step2The volume ratio of the substance(s) to the HBr solution is (0.32-0.64) mmol, (50-75) mu L; in the mixed precursor solution obtained in the third step, MnBr is contained in the mixed precursor solution2/PbBr2The molar feed ratio of (A) is 2/1-6/1.
3. The method of claim 2, wherein PbBr in step one2The ratio of the amount of substance(s) to the volume of HBr solution is 0.08mmol: 50. mu.L; MnBr in the second step2The ratio of the amount of substance(s) in HBr solution is 0.32mmol: 50. mu.L; in the mixed precursor solution obtained in the third step, MnBr is contained in the mixed precursor solution2/PbBr2Is 4/1.
4. The method of claim 2, wherein PbBr in step one2The volume ratio of the substance(s) to the HBr solution is 0.08mmol: 50. mu.L; MnBr in the second step2The ratio of the amount of substance(s) in HBr solution is 0.64mmol: 50. mu.L; in the mixed precursor solution obtained in the third step, MnBr is contained in the mixed precursor solution2/PbBr2Is 6/1.
5. The method of claim 2 wherein the mass of the solid PEABr powder to volume ratio of the mixed precursor solution is (0.3-0.35) g (100-150) μ L.
6. The method of claim 5 wherein the ratio of the mass of the solid PEABr powder to the volume of the mixed precursor solution is 0.35g:100 μ L.
7. The method of claim 1, wherein in step three, the solid PEABr powder is added into the mixed precursor solution and then stirred for reaction for 3-10 minutes.
8. The method of claim 1, wherein the HBr solution has a concentration of 30-50%.
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| US20180037813A1 (en) * | 2016-08-04 | 2018-02-08 | Florida State University Research Foundation, Inc. | Organic-Inorganic Hybrid Perovskites, Devices, and Methods |
| CN109920924A (en) * | 2019-03-11 | 2019-06-21 | 香港中文大学（深圳） | A kind of two dimension perovskite material, luminescent layer, LED component and preparation method thereof |
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| US20210230011A1 (en) * | 2018-07-13 | 2021-07-29 | Oxford University Innovation Limited | Tunable blue emitting lead halide perovskites |
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| US20180037813A1 (en) * | 2016-08-04 | 2018-02-08 | Florida State University Research Foundation, Inc. | Organic-Inorganic Hybrid Perovskites, Devices, and Methods |
| US20210230011A1 (en) * | 2018-07-13 | 2021-07-29 | Oxford University Innovation Limited | Tunable blue emitting lead halide perovskites |
| CN109920924A (en) * | 2019-03-11 | 2019-06-21 | 香港中文大学（深圳） | A kind of two dimension perovskite material, luminescent layer, LED component and preparation method thereof |
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