CN111575001A - Organic-inorganic hybrid perovskite emitting room-temperature phosphorescence and preparation method and application thereof - Google Patents
Organic-inorganic hybrid perovskite emitting room-temperature phosphorescence and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an organic-inorganic hybrid perovskite emitting room temperature phosphorescence, and a preparation method and application thereof, wherein the preparation method of the organic-inorganic hybrid perovskite comprises the following steps: mixing 2-phenylethylamine and methanol, and dropwise adding an HBr solution to prepare bromophenylethylamine; dissolving bromonaphthylmethylamine, bromophenylethylamine and lead bromide in an N, N-dimethylformamide solvent to obtain a mixed solution, and then dropping the mixed solution into a poor solvent to precipitate the organic-inorganic hybrid perovskite. In the invention, the triplet state energy level is lower than that of the inorganic layer [ PbBr ]4]2‑The typical organic fluorescent molecule of excited state energy level is doped with naphthalene methyl ammonium (NEA) in two dimensionsIn the inorganic-inorganic hybrid perovskite, the RTP is generated by energy transfer from inorganic components to organic triplet states, and the problem of realizing the RTP in the two-dimensional organic-inorganic hybrid perovskite is solved.
Description
Technical Field
The invention relates to the field of photoelectric materials, in particular to an organic-inorganic hybrid perovskite emitting room-temperature phosphorescence, and a preparation method and application thereof.
Background
Room Temperature Phosphorescence (RTP) is a photophysical process that is generated in triplet excitons of organic molecules and radiated to a ground state, and is widely applied in the fields of organic luminescence, bio-optical imaging, optical anti-counterfeiting and the like due to its unique advantages of slow exciton decay rate, high luminous efficiency and the like. Commonly used methods for producing room temperature phosphorescence are: by introducing heavy metals such as Pt and Ir into the organic ligand, intersystem crossing between the organic and the intermetallic is promoted, so that phosphorescence at room temperature is observed; by enabling organic molecules to form crystals, the molecular vibration is reduced, so that the non-radiative transition is reduced, and room-temperature phosphorescence is generated; or the guest molecules are doped into the host molecules, so that the doped material has stronger phosphorescence emission and generates room temperature phosphorescence.
At present, some organic molecules such as carbazole, phenylphosphine, etc. have been widely studied in the field of room temperature phosphorescence, among which organic-inorganic hybrid perovskites (ABX)3,A=CH3NH3 +,HC(NH2)2+;B=Pb2+,Sn2+;X=Cl-,Br-,I-) The advantages of adjustable band gap, high light absorption coefficient, strong photoelectric conversion efficiency and the like are widely concerned in the photoelectric field. The organic-inorganic hybrid perovskite can be divided into three-dimensional organic-inorganic hybrid perovskite and two-dimensional organic-inorganic hybrid perovskite, and compared with the three-dimensional organic-inorganic hybrid perovskite, the two-dimensional organic-inorganic hybrid perovskite can increase the hydrophobicity of the material due to the introduction of larger organic molecules, so that the stability of the material in the air is obviously improved, but the two-dimensional organic-inorganic hybrid perovskite is carried outRTP is rarely studied and is difficult to implement. In the invention, large pi conjugated organic functional group is introduced and is connected with an inorganic semiconductor layer [ PbBr ]4]2-The combination is beneficial to generating room temperature phosphorescence, and the prepared room temperature phosphorescence-emitting organic-inorganic hybrid perovskite can expand the research of the perovskite in the optical field.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a preparation method and application of an organic-inorganic hybrid perovskite emitting room-temperature phosphorescence, and aims to solve the problem that RTP is difficult to realize in the conventional two-dimensional organic-inorganic hybrid perovskite.
The technical scheme of the invention is as follows:
a preparation method of organic-inorganic hybrid perovskite emitting room temperature phosphorescence comprises the following steps:
uniformly mixing 2-phenylethylamine and methanol, and dropwise adding an HBr solution to prepare bromophenylethylamine;
uniformly mixing naphthylmethylamine and methanol, and dropwise adding an HBr solution to prepare bromonaphthylmethylamine;
dissolving bromonaphthylmethylamine, bromophenylethylamine and lead bromide in an N, N-dimethylformamide solvent to obtain a mixed solution, and then dropping the mixed solution into a poor solvent to precipitate the organic-inorganic hybrid perovskite.
The preparation method of the organic-inorganic hybrid perovskite emitting room temperature phosphorescence comprises the following steps of uniformly mixing 2-phenylethylamine and methanol, and dropwise adding an HBr solution to prepare bromophenylethylamine:
mixing and stirring 2-phenylethylamine and methanol at 0 ℃, and then slowly dripping an HBr solution to obtain a first mixed solution;
evaporating the solvent in the first mixed solution at 60-70 ℃ to obtain a white precipitate, washing the white precipitate with diethyl ether, then placing the white precipitate in a rotary evaporator to remove excessive diethyl ether, and drying the white precipitate in a vacuum drying oven at 60-70 ℃ to obtain bromophenylethylamine.
The preparation method of the organic-inorganic hybrid perovskite emitting room temperature phosphorescence comprises the following steps of uniformly mixing naphthylmethylamine and methanol, and dripping HBr solution to obtain bromonaphthylmethylamine:
mixing and stirring naphthylmethylamine and methanol at 0 ℃, and then slowly dripping an HBr solution to obtain a second mixed solution;
and (3) carrying out rotary evaporation on the solvent in the second mixed solution at the temperature of 60-70 ℃ to obtain a brown yellow precipitate, washing the brown yellow precipitate with diethyl ether for multiple times, then placing the brown yellow precipitate in a rotary evaporator to remove excessive diethyl ether, and drying the brown yellow precipitate in a vacuum drying oven at the temperature of 60-70 ℃ to obtain bromonaphthylmethylamine.
The preparation method of the organic-inorganic hybrid perovskite emitting room temperature phosphorescence comprises the following steps of dropping the mixed solution into a toluene solution to precipitate the organic-inorganic hybrid perovskite:
dripping the mixed solution into a toluene solution at the rotation speed of 400r/s for stirring for 30min to prepare organic-inorganic hybrid perovskite powder;
and carrying out vacuum filtration on the organic-inorganic hybrid perovskite powder, then placing the powder in a vacuum drying oven, and drying the powder for 2h at the temperature of 50 ℃ to obtain white organic-inorganic hybrid perovskite powder.
The preparation method of the organic-inorganic hybrid perovskite emitting room temperature phosphorescence comprises the step of dropping the mixed solution into a toluene solution in a glove box to precipitate the organic-inorganic hybrid perovskite.
The preparation method of the organic-inorganic hybrid perovskite emitting room temperature phosphorescence is characterized in that the poor solvent is a toluene solution.
An organic-inorganic hybrid perovskite emitting room temperature phosphorescence, which is prepared by any one of the preparation methods.
Use of an organic-inorganic hybrid perovskite emitting room temperature phosphorescence, wherein the organic-inorganic hybrid perovskite emitting room temperature phosphorescence is used for preparing a white light emitting diode based on an ultraviolet lamp.
Has the advantages that: the invention provides organic-inorganic hybrid perovskite powder capable of emitting room temperature phosphorescence, and a preparation method and application thereof4]2-Typical organic fluorescent molecules of naphthylmethyl ammonium (NEA) with excited state energy levels are doped into the two-dimensional organic-inorganic hybrid perovskite, so that the energy transfer from inorganic components to organic triplet states is realized, the RTP is generated, and the problem of realizing the RTP in the two-dimensional organic-inorganic hybrid perovskite is solved.
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FIG. 1 is a schematic flow chart of a preparation method of an organic-inorganic hybrid perovskite emitting room temperature phosphorescence according to the present invention.
FIG. 2 is a schematic operation diagram of a preferred embodiment of the preparation method of the room temperature phosphorescent organic-inorganic hybrid perovskite of the invention.
Fig. 3 is an XRD pattern of the room temperature phosphorescent organic-inorganic hybrid perovskite prepared in the examples of the present invention.
FIG. 4 is a scanning electron microscope image of the room temperature phosphorescent organic-inorganic hybrid perovskite prepared in the examples of the present invention.
FIG. 5 is an infrared spectrum of a room temperature phosphorescent organic-inorganic hybrid perovskite prepared in an example of the present invention.
FIG. 6 is a UV and PL plots of room temperature phosphorescent organic-inorganic hybrid perovskites prepared in examples of the present invention.
FIG. 7 is a graph of phosphorescence lifetime of room temperature phosphorescent organic-inorganic hybrid perovskites prepared in the examples of the present invention.
FIG. 8 shows a two-dimensional room temperature phosphorescent Perovskite (PEA) prepared in example 3 according to the present invention0.8(NEA)1.2PbBr4Schematic flow diagram for preparing WLED.
FIG. 9 is a two-dimensional room temperature phosphorescent Perovskite (PEA) prepared in example 3 of the present invention0.8(NEA)1.2PbBr4The WLED luminescence spectrum and the CIE chromaticity diagram and the color temperature diagram of (a).
Detailed Description
The invention provides an organic-inorganic hybrid perovskite emitting phosphorescence at room temperature, a preparation method and application thereof, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Referring to fig. 1, fig. 1 is a flow chart of a preferred embodiment of a method for preparing room temperature phosphorescent organic-inorganic hybrid perovskite according to the present invention, and as shown in the figure, the method comprises the steps of:
s10, uniformly mixing 2-phenylethylamine and methanol, and dropwise adding an HBr solution to prepare bromophenylethylamine;
s20, uniformly mixing the naphthylmethylamine and the methanol, and dropwise adding an HBr solution to prepare bromonaphthylmethylamine;
s30, dissolving bromonaphthylmethylamine, bromophenethylamine and lead bromide in an N, N-dimethylformamide solvent to obtain a mixed solution, and then dropping the mixed solution into a toluene solution to precipitate the organic-inorganic hybrid perovskite.
Based on the problem that the conventional room temperature phosphorescence research in two-dimensional organic-inorganic hybrid perovskites (OIHPs) is very rare and difficult to realize, in the embodiment, the organic fluorescent molecule naphthylmethyl ammonium (NEA) with low triplet state energy level is introduced into the two-dimensional organic-inorganic hybrid Perovskites (PEA) as an organic ligand2PbBr4Obtaining two-dimensional organic-inorganic hybrid Perovskite (PEA)x(NEA)2–xPbBr4Wherein the excited state energy of organic molecule Phenylethylamine (PEA) is 3.60eV, and inorganic layer [ PbBr ] in perovskite4]2-In a two-dimensional Perovskite (PEA) at an excited state energy of 3.08eV2PbBr4In (b), the triplet energy of the organic molecule PEA is higher than that of the inorganic moiety [ PbBr ]4]2–The energy of (a) results in the exciton being confined to the inorganic layer portion, while the organic molecule NEA is a simple aromatic carbon with triplet energy (T1) at-2.60 eV lower than the energy of the inorganic portion, which will transfer the exciton energy of the inorganic portion to the triplet state of the organic molecule NEA to generate phosphorescence. Therefore, organic fluorescent molecule naphthylmethyl ammonium (NEA) is introduced into two-dimensional organic-inorganic hybrid perovskite as organic ligand(PEA)2PbBr4In (b), excitons can be made to be excited from the inorganic component [ PbBr ]4]2-Transfer to the triplet energy of the organic molecule NEA and generate RTP.
In this embodiment, the step S10 of uniformly mixing 2-phenylethylamine and methanol, and dropping an HBr solution to prepare bromophenylethylamine specifically includes:
s11, mixing and stirring 2-phenylethylamine and methanol at 0 ℃, and then slowly dropping an HBr solution to obtain a first mixed solution;
and S12, evaporating the solvent in the first mixed solution at the temperature of 60-70 ℃ to obtain a white precipitate, washing the white precipitate with diethyl ether, then placing the white precipitate in a rotary evaporator to remove excessive diethyl ether, and drying the white precipitate in a vacuum drying oven at the temperature of 60-70 ℃ to obtain the bromophenylethylamine.
In this embodiment, 2-phenylethylamine and methanol are mixed and stirred for 30-60min under an ice bath condition at 0 ℃, then an HBr solution is slowly dropped in, the ice bath is removed after the dropping is completed, the solution is stirred at room temperature of 25 ℃ until the solution is clarified to obtain a first mixed solution, a solvent in the first mixed solution is evaporated and removed at 60-70 ℃ through a rotary evaporator to obtain a white precipitate, the white precipitate is washed with diethyl ether for multiple times, the rotary evaporator is used to remove excess diethyl ether, and then a vacuum drying oven is used for drying at 60-70 ℃ overnight to obtain bromophenylethylamine.
Further, in this embodiment, the step S20 of uniformly mixing the naphthylmethylamine and the methanol, and dropping the mixture into the HBr solution to obtain the bromonaphthylmethylamine specifically includes:
s21, mixing and stirring the naphthylmethylamine and the methanol at 0 ℃, and then slowly dropping an HBr solution to obtain a second mixed solution;
s22, carrying out rotary evaporation on the solvent in the second mixed solution at the temperature of 60-70 ℃ to obtain a brown yellow precipitate, washing the brown yellow precipitate with diethyl ether for multiple times, then placing the precipitate in a rotary evaporator to remove excessive diethyl ether, and carrying out drying treatment in a vacuum drying oven at the temperature of 60-70 ℃ to obtain bromonaphthylmethylamine.
In the embodiment, firstly, under the condition of an ice bath at 0 ℃, naphthylmethylamine and methanol are mixed and stirred for 30-60min, then, an HBr solution is slowly dropped in, the ice bath is removed after the dropping is finished, the solution is stirred at room temperature of 25 ℃ until the solution is clarified to obtain a second mixed solution, a rotary evaporator is used for evaporating and removing a solvent in the second mixed solution at 60-70 ℃ to obtain a brownish yellow precipitate, the brownish yellow precipitate is washed with diethyl ether for multiple times, the washed precipitate is placed in the rotary evaporator to remove excess diethyl ether, and then, a vacuum drying oven is used for drying at 60-70 ℃ overnight to obtain the bromonaphthylmethylamine.
Further, in this embodiment, the dropping of the mixed solution into a toluene solution to precipitate the organic-inorganic hybrid perovskite includes:
s31, dripping the mixed solution into a toluene solution at the rotation speed of 400r/S, and stirring for 30min to prepare organic-inorganic hybrid perovskite powder;
s32, carrying out vacuum filtration on the organic-inorganic hybrid perovskite powder, then placing the powder in a vacuum drying oven, and drying the powder for 2 hours at the temperature of 50 ℃ to obtain white organic-inorganic hybrid perovskite powder.
The preparation method of the organic-inorganic hybrid perovskite emitting room temperature phosphorescence comprises the step of dropping the mixed solution into a toluene solution in a glove box to precipitate the organic-inorganic hybrid perovskite.
An organic-inorganic hybrid perovskite emitting room temperature phosphorescence, which is prepared by any one of the preparation methods.
Use of an organic-inorganic hybrid perovskite emitting room temperature phosphorescence for the preparation of a white light emitting diode based on ultraviolet lamps.
The scheme of the invention is further explained by the following specific examples:
example 1
(1) Preparation of bromonaphthylmethylamine (NEABr)
5mL of naphthylmethylamine and 15mL of methanol were added to a round-bottom flask, and stirred in an ice bath at 0 ℃ for 30 min. Thereafter, 5.5mL of HBr solution was slowly added dropwise, the ice bath was removed, and stirring was continued at room temperature until the mixture was clear. Further, the methanol solvent in the mixture was evaporated by a rotary evaporator at 70 ℃ to obtain a brown-yellow precipitate. The brown-yellow precipitate was washed 3 times with ether and the washing solvent ether was removed by rotary evaporation. Finally, the mixture is placed in a vacuum drying oven at 70 ℃ for drying overnight to obtain bromonaphthylmethylamine.
(2) Preparation of organic-inorganic perovskite (NEA) emitting phosphorescence at room temperature2PbBr4
In a glove box, 95.2mg of NEABr and 73.4mg of PbBr2Dissolved in 168.76mg of DMF solvent and the solution was left clear. Dropwise adding the mixed solution into a reaction bottle of a toluene solution, and rotating at the rotating speed of 400r/s for 30min to obtain white organic-inorganic hybrid perovskite powder; placing the organic-inorganic hybrid perovskite powder into a filter flask for vacuum filtration, and carrying out vacuum filtration at room temperature for 10min to obtain white organic-inorganic hybrid perovskite (NEA) emitting room-temperature phosphorescence2PbBr4And finally, placing the powder into a vacuum drying oven to be dried for 2 hours at the temperature of 50 ℃.
Example 2
(1) Preparation of bromophenethylamine (PEABr)
5mL of 2-phenylethylamine and 15mL of methanol were added to a round bottom flask and stirred in an ice bath at 0 ℃ for 30min, after which 5.5mL of HBr solution was slowly added dropwise, the ice bath was removed and stirring continued at room temperature until the mixture was clear. Further evaporating the methanol solvent in the mixed solution at 70 ℃ by a rotary evaporator to obtain a white precipitate, washing the white precipitate with diethyl ether for 3 times, evaporating to remove the diethyl ether, and placing the white precipitate in a vacuum drying oven at 70 ℃ for drying overnight to obtain the bromophenylethylamine.
(2) Preparation of organic-inorganic Perovskite (PEA) emitting phosphorescence at room temperature2PbBr4
In a glove box, 80.8mg of PEABr and 73.4mg of PbBr were charged2Is dissolved in154.1mg of DMF solvent, standing the solution until the solution is clear, dropwise adding the mixed solution into a reaction bottle of toluene solution, and rotating at the rotating speed of 400r/s for 30min to obtain white organic-inorganic hybrid perovskite powder; placing the organic-inorganic hybrid perovskite powder into a filter flask for vacuum filtration, and carrying out vacuum filtration at room temperature for 10min to obtain white organic-inorganic hybrid Perovskite (PEA) emitting room-temperature phosphorescence2PbBr4And finally, placing the powder into a vacuum drying oven to be dried for 2 hours at the temperature of 50 ℃.
Example 3
(1) Preparation of bromophenethylamine (PEABr)
5mL of 2-phenylethylamine and 15mL of methanol were added to a round-bottom flask, and stirred in an ice bath at 0 ℃ for 30 min. Thereafter, 5.5mL of HBr solution was slowly added dropwise, the ice bath was removed, and stirring was continued at room temperature until the mixture was clear. Further evaporating the methanol solvent in the mixed solution at 70 ℃ by a rotary evaporator to obtain a white precipitate, washing the white precipitate with diethyl ether for 3 times, evaporating to remove the diethyl ether, and placing the white precipitate in a vacuum drying oven at 70 ℃ for drying overnight to obtain the bromophenylethylamine.
(2) Preparation of bromonaphthylmethylamine (NEABr)
5mL of naphthylmethylamine and 15mL of methanol were added to a round bottom flask and stirred in an ice bath at 0 ℃ for 30min, after which 5.5mL of HBr solution was slowly added dropwise, the ice bath was removed and stirring continued at room temperature until the mixture was clear. Further, evaporating the methanol solvent in the mixed solution at 70 ℃ by a rotary evaporator to obtain a brown yellow precipitate, washing the brown yellow precipitate with diethyl ether for 3 times, evaporating to remove the diethyl ether, and placing the precipitate in a vacuum drying oven at 70 ℃ for drying overnight to obtain bromonaphthylmethylamine.
(3) Preparation of organic-inorganic Perovskite (PEA) emitting phosphorescence at room temperature0.8(NEA)1.2PbBr4
In a glove box, 32.32mg of PEABr, 57.12mg of NEABr and 73.4mg of PbBr were placed2Dissolving in 168.74mg DMF solvent, standing the solution until it is clear, dripping the mixed solution into a toluene solution reaction bottle dropwise, and rotating at 400r/s for 30min, obtaining white organic-inorganic hybrid perovskite powder; placing the organic-inorganic hybrid perovskite powder into a filter flask for vacuum filtration, and carrying out vacuum filtration at room temperature for 10min to obtain white organic-inorganic hybrid Perovskite (PEA) emitting room-temperature phosphorescence0.8(NEA)1.2PbBr4And finally, placing the powder into a vacuum drying oven to be dried for 2 hours at the temperature of 50 ℃.
In the present invention, organic-inorganic Perovskite (PEA) emitting phosphorescence at room temperature was prepared in example 30.8(NEA)1.2PbBr4Furthermore, different organic-inorganic Perovskites (PEAs) emitting phosphorescence at room temperature can be obtained according to the ratio of the added PEABr and NEABrx(NEA)2–xPbBr4Wherein 0. ltoreq. x.ltoreq.2, e.g. in the present invention, with reference to the preparation process in example 3, gives (PEA)0.4(NEA)1.6PbBr4、(PEA)1(NEA)1PbBr4、(PEA)1.2(NEA)0.8PbBr4、(PEA)1.6(NEA)0.4PbBr4And for the organic-inorganic Perovskite (PEA) emitting phosphorescence at room temperature prepared as abovex(NEA)2–xPbBr4The analysis results are shown in FIGS. 3 to 7, and it is apparent from the analysis results that the Perovskite (PEA) prepared in this examplex(NEA)2–xPbBr4Capable of effecting energy transfer from inorganic components to organic triplet states and generating RTP, and with increasing NEA incorporation, (PEA)x(NEA)2–xPbBr4The longer the phosphorescence lifetime at 473nm, wherein (PEA)0.8(NEA)1.2PbBr4The phosphorescence lifetime of the perovskite can reach 2.95ms at 473nm, and various perovskites emitting room temperature phosphorescence can be synthesized by adjusting the proportion of different organic fluorescent molecules.
Further, the prepared organic-inorganic hybrid perovskite emitting room temperature phosphorescence can be used in a white light emitting diode driven by ultraviolet light. As shown in FIG. 8, FIG. 8 is a room temperature phosphorescent organic-inorganic hybrid Perovskite (PEA) prepared in example 30.8(NEA)1.2PbBr4Schematic diagram of the preparation process of WLED (1). In the inventionThe performance of the prepared WLED was analyzed, and the results are shown in FIG. 9, where FIG. 9 is based on room temperature phosphorescence-emitting organic-inorganic hybrid Perovskite (PEA)0.8(NEA)1.2PbBr4The WLED prepared by the invention has better luminescence property as seen from the luminescence spectrum, the CIE chromaticity diagram and the color temperature diagram.
In summary, the invention provides an organic-inorganic hybrid perovskite emitting room temperature phosphorescence, and a preparation method and application thereof, wherein the triplet state energy level is lower than the inorganic layer [ PbBr ]4]2-The typical organic fluorescent molecule, Naphthylmethylammonium (NEA), at the excited state level, is incorporated into a two-dimensional organic-inorganic hybrid perovskite. Realizes the energy transfer from inorganic components to organic triplet states and generates RTP, and solves the problem of RTP generated in two-dimensional organic-inorganic hybrid perovskite.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (8)
1. A preparation method of organic-inorganic hybrid perovskite emitting room temperature phosphorescence is characterized by comprising the following steps:
mixing 2-phenylethylamine and methanol, and dropwise adding an HBr solution to prepare bromophenylethylamine;
mixing naphthylmethylamine with methanol, and dropwise adding an HBr solution to prepare bromonaphthylmethylamine;
dissolving bromonaphthylmethylamine, bromophenylethylamine and lead bromide in an N, N-dimethylformamide solvent to obtain a mixed solution, and then dropping the mixed solution into a poor solvent to precipitate the organic-inorganic hybrid perovskite.
2. The method for preparing the room temperature phosphorescent organic-inorganic hybrid perovskite as claimed in claim 1, wherein the step of mixing 2-phenylethylamine with methanol and adding HBr solution dropwise to obtain bromophenylethylamine comprises the following steps:
mixing and stirring 2-phenylethylamine and methanol at 0 ℃, and then slowly dripping an HBr solution to obtain a first mixed solution;
evaporating the solvent in the first mixed solution at 60-70 ℃ to obtain a white precipitate, washing the white precipitate with diethyl ether, then placing the white precipitate in a rotary evaporator to remove excessive diethyl ether, and drying the white precipitate in a vacuum drying oven at 60-70 ℃ to obtain bromophenylethylamine.
3. The method for preparing the room temperature phosphorescent organic-inorganic hybrid perovskite as claimed in claim 1, wherein the step of mixing the naphthylmethylamine with methanol and adding HBr solution dropwise to obtain the bromonaphthylmethylamine comprises:
mixing and stirring naphthylmethylamine and methanol at 0 ℃, and then slowly dripping an HBr solution to obtain a second mixed solution;
and (3) carrying out rotary evaporation on the solvent in the second mixed solution at the temperature of 60-70 ℃ to obtain a brown yellow precipitate, washing the brown yellow precipitate with diethyl ether for multiple times, then placing the brown yellow precipitate in a rotary evaporator to remove excessive diethyl ether, and drying the brown yellow precipitate in a vacuum drying oven at the temperature of 60-70 ℃ to obtain bromonaphthylmethylamine.
4. The method according to claim 1, wherein the step of dropping the mixed solution into a toluene solution to precipitate the organic-inorganic hybrid perovskite comprises:
dripping the mixed solution into a poor solvent at the rotation speed of 400r/s, and stirring for 30min to prepare organic-inorganic hybrid perovskite powder;
and carrying out vacuum filtration on the organic-inorganic hybrid perovskite powder, then placing the powder in a vacuum drying oven, and drying the powder for 2h at the temperature of 50 ℃ to obtain white organic-inorganic hybrid perovskite powder.
5. The method according to claim 4, wherein the mixed solution is dropped into a toluene solution in a glove box to precipitate the organic-inorganic hybrid perovskite.
6. The method according to claim 1, wherein the poor solvent is toluene.
7. An organic-inorganic hybrid perovskite emitting phosphorescence at room temperature, characterized by being prepared by the preparation method as claimed in claims 1 to 6.
8. Use of a room temperature phosphorescent organic-inorganic hybrid perovskite for the preparation of a light-emitting diode, wherein the room temperature phosphorescent organic-inorganic hybrid perovskite of claim 7 is used for the preparation of a light-emitting diode.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112980438A (en) * | 2021-02-22 | 2021-06-18 | 南京邮电大学 | Organic-inorganic two-dimensional perovskite room temperature phosphorescent material and preparation method and application thereof |
CN114023885A (en) * | 2021-11-05 | 2022-02-08 | 中国科学院福建物质结构研究所 | Self-driven polarized light detector based on ferroelectric photovoltaic effect and preparation method thereof |
CN114574188A (en) * | 2022-01-29 | 2022-06-03 | 吉林师范大学 | Mn-doped PEA (polyethylene terephthalate) synthesized by assistance of HBr (hydrogen bromide) solution2PbBr4Method for two-dimensional perovskite |
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---|---|---|---|---|
CN114959867B (en) * | 2022-05-30 | 2023-10-27 | 陕西师范大学 | Two-dimensional structure (PEA) 2 PbBr 4 Single crystal scintillator and method for producing the same |
CN116675608B (en) * | 2023-05-31 | 2024-03-08 | 天津大学 | Method for preparing blue perovskite quantum dots in situ by single crystal powder |
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104019922A (en) * | 2014-04-29 | 2014-09-03 | 北京理工大学 | Organic-inorganic hybrid perovskite material for temperature detection |
CN108276989A (en) * | 2018-01-10 | 2018-07-13 | 天津大学 | A kind of preparation method of the 2D perovskite quantum well thin-films with high gain characteristics |
CN108690601A (en) * | 2018-05-03 | 2018-10-23 | 内蒙古师范大学 | A kind of preparation method of hybrid inorganic-organic perovskite quantum dot and film |
CN108865116A (en) * | 2018-07-16 | 2018-11-23 | 福建师范大学 | A kind of film and preparation method thereof with room temperature phosphorimetry |
CN109134265A (en) * | 2018-09-07 | 2019-01-04 | 南京邮电大学 | A kind of preparation method of hybrid inorganic-organic perovskite nano wire |
-
2020
- 2020-05-21 CN CN202010434392.8A patent/CN111575001A/en active Pending
- 2020-07-22 WO PCT/CN2020/103536 patent/WO2021232578A1/en active Application Filing
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104019922A (en) * | 2014-04-29 | 2014-09-03 | 北京理工大学 | Organic-inorganic hybrid perovskite material for temperature detection |
CN108276989A (en) * | 2018-01-10 | 2018-07-13 | 天津大学 | A kind of preparation method of the 2D perovskite quantum well thin-films with high gain characteristics |
CN108690601A (en) * | 2018-05-03 | 2018-10-23 | 内蒙古师范大学 | A kind of preparation method of hybrid inorganic-organic perovskite quantum dot and film |
CN108865116A (en) * | 2018-07-16 | 2018-11-23 | 福建师范大学 | A kind of film and preparation method thereof with room temperature phosphorimetry |
CN109134265A (en) * | 2018-09-07 | 2019-01-04 | 南京邮电大学 | A kind of preparation method of hybrid inorganic-organic perovskite nano wire |
Non-Patent Citations (2)
Title |
---|
SHUMING YANG 等: "Highly Efficient Organic Afterglow from a 2D Layered Lead-Free Metal Halide in Both Crystals and Thin Films under an Air Atmosphere", 《ACS APPL. MATER. INTERFACES》 * |
YANG,SHUMING 等: "Highly Efficient Room-Temperature Phosphorescence and Afterglow Luminescence from Common Organic Fluorophores in 2D Hybrid Perovskites", 《CHEMICAL SCIENCE》 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112980438A (en) * | 2021-02-22 | 2021-06-18 | 南京邮电大学 | Organic-inorganic two-dimensional perovskite room temperature phosphorescent material and preparation method and application thereof |
CN114023885A (en) * | 2021-11-05 | 2022-02-08 | 中国科学院福建物质结构研究所 | Self-driven polarized light detector based on ferroelectric photovoltaic effect and preparation method thereof |
CN114574188A (en) * | 2022-01-29 | 2022-06-03 | 吉林师范大学 | Mn-doped PEA (polyethylene terephthalate) synthesized by assistance of HBr (hydrogen bromide) solution2PbBr4Method for two-dimensional perovskite |
CN114574188B (en) * | 2022-01-29 | 2024-01-23 | 吉林师范大学 | Mn-doped PEA (polyethylene terephthalate) synthesized with assistance of HBr solution 2 PbBr 4 Method for two-dimensional perovskite |
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