CN114464739A - Method for preparing high-performance near-infrared perovskite film in air - Google Patents
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- 239000000463 material Substances 0.000 claims abstract description 9
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- 238000002425 crystallisation Methods 0.000 claims description 23
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 22
- 230000008025 crystallization Effects 0.000 claims description 22
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 20
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000010408 film Substances 0.000 claims description 9
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- 229910052710 silicon Inorganic materials 0.000 claims description 8
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- MJFXORGVTOGORM-UHFFFAOYSA-L lead(2+) methanamine dibromide Chemical compound [Pb+2].[Br-].CN.[Br-] MJFXORGVTOGORM-UHFFFAOYSA-L 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
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- LLWRXQXPJMPHLR-UHFFFAOYSA-N methylazanium;iodide Chemical compound [I-].[NH3+]C LLWRXQXPJMPHLR-UHFFFAOYSA-N 0.000 description 2
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- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 description 1
- FZHSXDYFFIMBIB-UHFFFAOYSA-L diiodolead;methanamine Chemical compound NC.I[Pb]I FZHSXDYFFIMBIB-UHFFFAOYSA-L 0.000 description 1
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- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- ISWNAMNOYHCTSB-UHFFFAOYSA-N methanamine;hydrobromide Chemical compound [Br-].[NH3+]C ISWNAMNOYHCTSB-UHFFFAOYSA-N 0.000 description 1
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- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
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Abstract
The invention discloses a method for preparing a high-performance near-infrared perovskite thin film in air, which comprises the following four steps: (1) preparing a perovskite precursor solution, (2) doping and preparing an anti-solvent, (3) spin-coating perovskite on a substrate by using a spin-coating method, and (4) transferring the substrate onto a heat platform, and annealing and crystallizing to form a perovskite thin film; the general formula of the perovskite material is ABX3Wherein A is a monovalent cation, B is a divalent metal cation, and X is a halide anion; the anti-solvent is mixed with and doped with tetrabutylammonium hexafluorophosphate (TBAPF-6) and polymethyl methacrylate (PMMA), the two materials are doped together, and the fluorescence intensity of the perovskite thin film can be improved to 15 times that of the untreated perovskite thin film under the condition that the air humidity is 40%.
Description
Technical Field
The invention relates to the technical field of photoluminescence, in particular to a method for preparing a high-performance near-infrared perovskite film in air.
Background
Perovskite is a high-efficiency luminescent material, has excellent properties of high color purity, adjustable emission wavelength covering the whole visible light region, ultrahigh photoluminescence quantum yield and the like, is widely applied to the field of photoelectric devices by researchers, and has the advantages of high performance, easiness in preparation and the like.
However, the perovskite active layer currently used as the core of perovskite optoelectronic devices has the following problems:
(1) the perovskite active layer is very sensitive to water vapor and oxygen and can be degraded after being exposed to a humid air environment for a long time. Almost all perovskite thin films are therefore produced in a glove box under nitrogen atmosphere, which undoubtedly increases the production cost of the device.
(2) The working environment of the perovskite photoelectric device is mostly air. Due to the poor stability of perovskite in air, the working time of the device is far shorter than that of the like products, such as silicon-based solar cells, OLEDs and the like.
(3) The large-scale semiconductor process is mostly carried out in an air environment, if perovskite is introduced into commercial large-scale production, the whole production line needs to be arranged in a nitrogen environment under the current condition to obtain high-quality perovskite photoelectric devices, which undoubtedly raises the commercial cost, that is, the preparation of efficient and stable perovskite thin films in the air is imperative. However, when the perovskite thin film without any treatment is directly prepared in the air, compared with the thin film prepared in the glove box, the luminous efficiency and the stability are greatly reduced, and in a high-humidity environment, the luminous intensity of the perovskite thin film prepared in the air is even only one tenth of that of the perovskite thin film prepared in the glove box.
Disclosure of Invention
Aiming at the problems, the invention provides a method for preparing a perovskite thin film in air, which realizes the preparation of the perovskite thin film with high fluorescence intensity and good stability in the air by doping an anti-solvent required in the preparation of the perovskite thin film.
In order to solve the technical problems, the invention provides the following technical scheme:
a method for preparing a perovskite thin film in air comprises four steps: (1) preparing a substrate and preparing a perovskite precursor solution; (2) doping and preparing an anti-solvent; (3) spin coating the perovskite on the substrate by using a spin coating method; (4) annealing and crystallizing to form a perovskite thin film; the doping materials in the anti-solvent are tetrabutylammonium hexafluorophosphate and polymethyl methacrylate.
Preferably, the preparation of the substrate is in particular: cutting the substrate into square substrates, cleaning the square substrates by using an RCA cleaning method, and drying the square substrates;
preparing a perovskite precursor solution: dissolving monovalent cation halide and lead halide and/or tin halide powder into a mixed solution of N, N-dimethylformamide and dimethyl sulfoxide, and rapidly dissolving the monovalent cation halide and the lead halide and/or the tin halide powder by magnetic stirring or ultrasound, wherein the concentration of the monovalent cation lead halide and/or tin in the obtained perovskite precursor solution is 0.2-1M;
doping and preparing the anti-solvent: adding tetrabutyl ammonium hexafluorophosphate and 2% PMMA chlorobenzene solution into an anti-solvent, and uniformly mixing by magnetic stirring or ultrasound, wherein the doping concentrations of the obtained solutions are respectively as follows: 0.1-0.7 mg/ml of tetrabutylammonium hexafluorophosphate and 0.1-0.4% of PMMA;
the perovskite thin film is spin-coated by a two-step spin-coating method, and a doped anti-solvent is dripped 9-11 s before the second step is finished;
the annealing crystallization specifically comprises the following steps: and transferring the substrate after the spin coating to a hot stage for annealing and crystallization to form the perovskite thin film.
Preferably, the anti-solvent is one or more of toluene, chlorobenzene, dichloromethane or ethyl acetate.
Preferably, the volume ratio of the N, N-dimethylformamide to the dimethyl sulfoxide is 9: 1.
preferably, the substrate is one of an ITO or FTO conductive glass substrate, p-type silicon, n-type silicon, silicon dioxide, a flexible substrate, or graphene.
Preferably, the two-step spin coating method comprises the following specific steps: dropwise adding the perovskite precursor solution on the substrate, wherein the spin coating time of the first step is 9-11 s, the spin coating speed is 950-1100 rpm, the spin coating time of the second step is 19-21 s, and the spin coating speed is 4900-5100 rpm.
Preferably, the annealing crystallization temperature is 95-105 ℃, the annealing time is 9-11 min, and the perovskite thin film which is good in crystallization and can be stably stored in an air environment for a long time is obtained after the annealing crystallization is completed.
The perovskite crystalline material is formed by annealing and crystallizing the method for preparing the perovskite thin film in the air, and the general formula of the perovskite crystalline material is ABX3Wherein A is a monovalent cation, B is a divalent metal cation, and X is a halide anion.
Preferably, the monovalent cation is Rb+、Na+、K+、Cs+、(NH2)2CH+Or CH3NH3 +One or more of; wherein the divalent metal cation is Pb2+And/or Sn2+(ii) a The halide anion is Cl-、Br-And I-One or more of (a).
The invention has the following beneficial effects:
(1) it can be prepared in a humid air environment instead of in a glove box: through the doping of PMMA in an anti-solvent, the perovskite can be normally crystallized and formed into a film in an air environment with the humidity of less than 70%;
(2) the prepared perovskite thin film has high fluorescence intensity: through the doping of PMMA, the surface defects of perovskite can be passivated, the fluorescence luminous intensity of perovskite is improved to 3.5 times that of the untreated perovskite thin film, the defect of PMMA in carrier transmission can be made up through the further doping of tetrabutylammonium hexafluorophosphate, the surface defects of perovskite can also be passivated, the fluorescence intensity is improved, the effects of the two materials are superposed, the effect that 1+1 is far greater than 2 can be exerted, and the fluorescence intensity of the perovskite thin film after the anti-solvent doping can be improved to 15 times that of the untreated perovskite thin film under the condition that the air humidity is 40%;
(3) the stability in air environment is good: the prepared perovskite thin film can be stored in an air environment of about 40% for one month and still keeps the fluorescence intensity close to the initial fluorescence intensity.
Drawings
FIG. 1 shows MAPbI before and after anti-solvent doping in the present invention3Comparative plot of photoluminescence intensity of perovskite thin films.
FIG. 2 shows MAPbI before and after anti-solvent doping in the present invention3The change curve of the fluorescence intensity of the perovskite thin film is placed in an air environment for 28 days.
FIG. 3 shows MAPbI after anti-solvent doping in accordance with the present invention3Scanning electron microscope image of surface morphology of perovskite thin film.
FIG. 4 shows MAPbI before anti-solvent doping in the present invention3Scanning electron microscope image of surface morphology of perovskite thin film.
FIG. 5 shows MAPbBr before and after antisolvent doping in the present invention3Comparative plot of photoluminescence intensity of perovskite thin films.
FIG. 6 shows MAPbBr before and after antisolvent doping in accordance with the present invention3The change curve of the fluorescence intensity of the perovskite thin film is placed in an air environment for 28 days.
FIG. 7 shows MAPbBr after antisolvent doping in accordance with the present invention3Scanning electron microscope image of surface morphology of perovskite thin film.
FIG. 8 shows MAPbBr before anti-solvent doping in accordance with the present invention3Scanning electron microscope image of surface morphology of perovskite thin film.
FIG. 9 shows MAPbI grown on different substrates in accordance with the present invention3Scanning electron microscope image of surface morphology of perovskite thin film.
FIG. 10 shows MApB after anti-solvent doping in accordance with the invention0.9Sn0.1I3Scanning electron microscope image of surface morphology of perovskite thin film.
FIG. 11 shows MApB before and after anti-solvent doping in accordance with the invention0.9Sn0.1I3Comparative plot of photoluminescence intensity of perovskite thin films.
FIG. 12 shows MApB before and after anti-solvent doping in accordance with the invention0.9Sn0.1I3The change curve of the fluorescence intensity of the perovskite thin film is placed in an air environment for 28 days.
FIG. 13 shows Cs after antisolvent doping in the present invention0.05FA0.9MA0.05PbI2.85Br0.15Perovskite thin filmScanning electron microscopy of surface topography.
FIG. 14 shows Cs before and after antisolvent doping in the present invention0.05FA0.9MA0.05PbI2.85Br0.15Comparative plot of photoluminescence intensity of perovskite thin films.
FIG. 15 shows Cs before and after antisolvent doping in the present invention0.05FA0.9MA0.05PbI2.85Br0.15The change curve of the fluorescence intensity of the perovskite thin film is placed in an air environment for 28 days.
FIG. 16 shows MA after anti-solvent doping in accordance with the present invention0.9K0.1PbI2.8Cl0.2Scanning electron microscope image of surface morphology of perovskite thin film.
FIG. 17 shows MA before and after anti-solvent doping in accordance with the invention0.9K0.1PbI2.8Cl0.2Comparative plot of photoluminescence intensity of perovskite thin films.
FIG. 18 shows MA before and after anti-solvent doping in accordance with the invention0.9K0.1PbI2.8Cl0.2The change curve of the fluorescence intensity of the perovskite thin film is placed in an air environment for 28 days.
Detailed Description
The following examples are included to provide further detailed description of the present invention and to provide those skilled in the art with a more complete, concise, and exact understanding of the principles and spirit of the invention.
Example 1: under the condition of 40% of air humidity, the perovskite thin film is prepared by the following method:
the first step is as follows: a square p-type silicon substrate of 1cm × 1cm in size was prepared, cleaned by RCA cleaning method, and then baked.
The second step is that: 48mg of methylamine iodide (CH)3NH3I, MAI) and 138mg of PbI2Dissolving the powder in a solvent with the volume ratio of 9:1 in a mixed solution of N, N-Dimethylformamide (DMF) and dimethyl sulfoxide (DMSO), wherein the DMF is 635 μ l and the DMSO is 72 μ l, and rapidly dissolving the mixture by ultrasonic treatment to obtain methylamine lead iodide (CH)3NH3PbI3,MAPbI3) PerovskiteThe concentration of the precursor solution was 0.3M.
The third step: 0.5mg of tetrabutylammonium hexafluorophosphate (TBAPF-6) and 100. mu.l of a 2% polymethyl methacrylate (PMMA) chlorobenzene solution were added together to 1ml of ethyl acetate and mixed uniformly by magnetic stirring or ultrasonic, and the doping concentrations of the obtained solutions were respectively: tetrabutylammonium hexafluorophosphate 0.5mg/mL and PMMA 0.2%.
The fourth step: and (3) dropwise adding 20 mu l of precursor solution on the substrate by using a two-step spin coating method, wherein the time length of the first step is 10s, the rotating speed is 1000rpm, the time length of the second step is 20s, the rotating speed is 5000rpm, and 150 mu l of anti-solvent is dropwise added 10s before the second step is completed.
The fifth step: transferring the spin-coated substrate to a hot stage, setting the temperature to be 100 ℃, annealing for 10 minutes, and obtaining MAPbI with good crystallization and long-time stable storage in air environment3A perovskite thin film.
The thickness of the finally prepared film is about 90nm, the luminescence peak is positioned at 760nm, and figure 1 shows MAPbI before and after anti-solvent doping3Comparison of the photoluminescence intensity spectra of perovskite thin films by doping with tetrabutylammonium hexafluorophosphate and PMMA, MAPbI3The fluorescence intensity of the perovskite thin film is improved by 15 times; FIG. 2 is a graph comparing the fluorescence intensity after long-term storage in air, MAPbI, by doping with tetrabutylammonium hexafluorophosphate and PMMA, after 28 days of storage in air3The fluorescence intensity of the perovskite thin film is attenuated to 98 percent of the initial fluorescence intensity and is far better than that of undoped MAPbI3A perovskite thin film. FIG. 3 and FIG. 4 are MAPbI, respectively3SEM images of the surface appearance of the perovskite after anti-solvent doping and before doping.
The doping of PMMA can ensure MAPbI3The perovskite is normally crystallized to form a film in a humid air environment, and both PMMA and tetrabutylammonium hexafluorophosphate can passivate MAPbI3Perovskite surface defects to promote MAPbI3The perovskite fluorescence intensity and the doping of the tetrabutyl ammonium hexafluorophosphate can make up the deficiency of PMMA in carrier transmission, and the effect of the two materials is superposed, so that the effect that 1+1 is far greater than 2 can be exerted.
Example 2: under the condition of air humidity of 70%, perovskite thin film is prepared according to the following method:
the first step is as follows: a square ITO conductive glass substrate of 1cm × 1cm in size is prepared, cleaned by an RCA cleaning method, and dried.
The second step is that: 112mg of MABr methyl ammonium bromide and 367mg of PbBr2Dissolving the powder in a solvent with the volume ratio of 9:1 in a mixed solution of N, N-Dimethylformamide (DMF) and dimethyl sulfoxide (DMSO), wherein the DMF is 635 μ l and the DMSO is 72 μ l, and rapidly dissolving the DMF and the DMSO by ultrasonic to obtain methylamine lead bromide (CH)3NH3PbBr3,MAPbBr3) The concentration of the perovskite precursor solution is 1M.
The third step: 0.5mg of tetrabutylammonium hexafluorophosphate and 100. mu.l of 2% PMMA chlorobenzene solution were added together to 1ml of ethyl acetate and mixed uniformly by magnetic stirring or ultrasound, the doping concentrations of the obtained solutions were respectively: tetrabutylammonium hexafluorophosphate 0.5mg/mL and PMMA 0.2%.
The fourth step: and (3) dropwise adding 50 mu l of precursor solution on the substrate by using a two-step spin coating method, wherein the time length of the first step is 10s, the rotating speed is 1000rpm, the time length of the second step is 20s, the rotating speed is 5000rpm, and 1ml of anti-solvent is dropwise added when the first 10s of the second step is completed.
The fifth step: transferring the spin-coated substrate to a hot stage, setting the temperature to 100 ℃, annealing for 10 minutes, and obtaining MAPbBr with good crystallization and long-time stable storage in air environment3A perovskite thin film.
The final film thickness was about 300nm, the luminescence peak was 520nm, FIG. 5 shows MAPbBr before and after anti-solvent doping3Comparison of the photoluminescence intensity spectra of perovskite thin films by doping with tetrabutylammonium hexafluorophosphate and PMMA, MAPbBr3The fluorescence intensity of the perovskite thin film is improved by 13 times; FIG. 6 is a graph comparing fluorescence intensity after long-term storage in air, MAPbBr after storage in air for 30 days by doping with tetrabutylammonium hexafluorophosphate and PMMA3The fluorescence intensity of the perovskite thin film is attenuated to 98 percent of the initial fluorescence intensity and is far better than that of undoped MAPbBr3A perovskite thin film. FIG. 7 and FIG. 8 are MAPbBr, respectively3After counter-solvent doping of the perovskiteSurface topography SEM images before doping.
The doping of PMMA can ensure MAPbBr3The perovskite is normally crystallized to form a film in a humid air environment, and both PMMA and tetrabutylammonium hexafluorophosphate can passivate MAPbBr3Perovskite surface defects, promote MAPbBr3The perovskite fluorescence intensity and the doping of the tetrabutyl ammonium hexafluorophosphate can make up the deficiency of PMMA in carrier transmission, and the effect of the two materials is superposed, so that the effect that 1+1 is far greater than 2 can be exerted.
Example 3: the rest is the same as example 1 except that: the perovskite thin film is prepared under the condition that the air humidity is 60%, the p-type silicon substrate can be optionally replaced by one of FTO conductive glass, n-type silicon, silicon dioxide, flexible substrates (such as PET or PEN materials) or graphene according to the requirement, and the final perovskite crystal formation is not influenced by the replacement. FIG. 9 shows undoped MAPbI deposited on different substrates3A perovskite thin film.
Example 4: the rest is the same as example 2, except that:
0.1mg of tetrabutylammonium hexafluorophosphate and 50. mu.l of a 2% PMMA chlorobenzene solution were added together to 1ml of toluene and mixed uniformly by magnetic stirring or sonication.
Methylamine halide raw material MABr is replaced by methylamine iodide MAI, PbBr2Replacement is PbI2And SnI2A mixture of (a). PbI2And SnI2The molar ratio of the mixture of (a) to (b) is 9: 1. The resulting MAPb0.9Sn0.1I3The concentration in the perovskite precursor solution was 0.2M.
The two-step spin coating method comprises the following specific steps: and dropwise adding the perovskite precursor solution on the substrate, wherein the spin coating time of the first step is 9s, the spin coating speed is 1100rpm, the spin coating time of the second step is 19s, and the spin coating speed is 5100 rpm. Dripping the doped anti-solvent when the first 9s of the second step is finished;
the annealing crystallization temperature is 95 ℃, the annealing time is 11min, and MApB which has good crystallization and can be stably stored in air environment for a long time is obtained after the annealing crystallization is finished0.9Sn0.1I3A perovskite thin film. FIG. 10 is a crystallized film after dopingFig. 11 is a photoluminescence intensity comparison graph of the perovskite thin film before and after doping, and fig. 12 is a photoluminescence intensity comparison graph of the doped and undoped thin films after long-term placement in air.
Example 5: the rest is the same as example 2, except that:
0.7mg of tetrabutylammonium hexafluorophosphate and 200. mu.l of a 2% PMMA chlorobenzene solution were added together to 1ml of chlorobenzene and mixed homogeneously by magnetic stirring or ultrasound.
Methylamine halide raw material MABr is doped with formamidine halide (CH (NH)2)2I, FAI) and metal halides CsI, PbBr2Middle doped PbI2. Wherein PbI2/PbBr2The molar ratio of FAI/MABr was fixed at 0.95:0.05, and the molar ratio of CsI/(FAI + MABr) was 0.05:0.95, (FAI + MABr + CsI)/(PbI)2+PbBr2) The molar ratio of (a) to (b) was fixed at 1: 1. The obtained Cs0.05FA0.9MA0.05PbI2.85Br0.15The concentration in the perovskite precursor solution was 0.6M.
The specific method of the two-step spin coating method comprises the following steps: and dropwise adding the perovskite precursor solution on the substrate, wherein the spin coating time of the first step is 11s, the spin coating speed is 950rpm, the spin coating time of the second step is 21s, and the spin coating speed is 4900 rpm. Dropping the doped anti-solvent 11s before the second step;
the annealing crystallization temperature is 105 ℃, the annealing time is 9min, and the Cs with good crystallization and long-term stable storage in the air environment is obtained after the annealing crystallization0.05FA0.9MA0.05PbI2.85Br0.15A perovskite thin film. FIG. 13 is a graph showing a comparison of photoluminescence intensity of perovskite thin films after doping and crystallization, FIG. 14 is a graph showing a comparison of photoluminescence intensity of perovskite thin films before and after doping, and FIG. 15 is a graph showing a comparison of photoluminescence intensity of doped and undoped thin films after long-term standing in air.
Example 6: the rest is the same as example 2, except that:
0.4mg of tetrabutylammonium hexafluorophosphate and 150. mu.l of a 2% PMMA chlorobenzene solution are added together to 1ml of diethyl ether and mixed homogeneously by magnetic stirring or ultrasound.
Replacement of methylamine halide feedstock MABr with a mixture of MAI and KCl, PbBr2Replacement by PbCl2And PbI2A mixture of (a). Obtained MA0.9K0.1PbI2.8Cl0.2The concentration in the perovskite precursor solution was 0.5M. Wherein the molar ratio of MAI to KCl is 9:1, PbI2And PbCl2In a molar ratio of 1.9:0.1 while maintaining (MAI + KCl)/(PbI)2+SnI2) The molar ratio of (a) to (b) was fixed at 1: 1.
The annealing crystallization temperature is 100 ℃, the annealing time is 9min, and the MA which has good crystallization and can be stably stored for a long time in the air environment is obtained after the annealing crystallization is finished0.9K0.1PbI2.8Cl0.2A perovskite thin film. FIG. 16 is a graph showing the comparison of photoluminescence intensity of perovskite thin films after doping and crystallization, FIG. 17 is a graph showing the comparison of photoluminescence intensity of perovskite thin films before and after doping, and FIG. 18 is a graph showing the comparison of photoluminescence intensity of doped and undoped thin films after long-term standing in the air.
The above embodiments are only for illustrating the technical idea of the present invention, and the protection scope of the present invention cannot be limited thereby, and any modification made on the basis of the technical scheme according to the technical idea proposed by the present invention falls within the protection scope of the present invention; the technology not related to the invention can be realized by the prior art.
Claims (9)
1. A method for preparing a perovskite thin film in air is characterized by comprising the following steps: the preparation method of the perovskite thin film comprises four steps: (1) preparing a substrate and preparing a perovskite precursor solution; (2) doping and preparing an anti-solvent; (3) spin coating the perovskite on the substrate by using a spin coating method; (4) annealing and crystallizing to form a perovskite film; the doping materials in the anti-solvent are tetrabutylammonium hexafluorophosphate and polymethyl methacrylate.
2. The method for preparing perovskite thin film in air as claimed in claim 1, wherein:
the preparation of the substrate specifically comprises: cutting the substrate into square substrates, cleaning the square substrates by using an RCA cleaning method, and drying the square substrates;
preparing a perovskite precursor solution: dissolving monovalent cation halide and lead halide and/or tin halide powder into a mixed solution of N, N-dimethylformamide and dimethyl sulfoxide, and rapidly dissolving the monovalent cation halide and the lead halide and/or the tin halide powder by magnetic stirring or ultrasound, wherein the concentration of the monovalent cation lead halide and/or tin in the obtained perovskite precursor solution is 0.2-1M;
doping and preparing the anti-solvent: adding tetrabutyl ammonium hexafluorophosphate and 2% PMMA chlorobenzene solution into an anti-solvent, and uniformly mixing by magnetic stirring or ultrasound, wherein the doping concentrations of the obtained solutions are respectively as follows: 0.1-0.7 mg/ml of tetrabutylammonium hexafluorophosphate and 0.1-0.4% of PMMA;
the perovskite thin film is spin-coated by a two-step spin-coating method, and a doped anti-solvent is dripped 9-11 s before the second step is finished;
the annealing crystallization specifically comprises the following steps: and transferring the substrate after the spin coating to a hot stage for annealing and crystallization to form the perovskite thin film.
3. The method for preparing perovskite thin film in air as claimed in claim 2, wherein: the antisolvent is one or more of toluene, chlorobenzene, dichloromethane, ethyl acetate or diethyl ether.
4. The method for preparing perovskite thin film in air as claimed in claim 2, wherein: the volume ratio of the N, N-dimethylformamide to the dimethyl sulfoxide is 9: 1.
5. the method for preparing perovskite thin film in air as claimed in claim 2, wherein: the substrate is one of an ITO or FTO conductive glass substrate, p-type silicon, n-type silicon, silicon dioxide, a flexible substrate or graphene.
6. The method for preparing perovskite thin film in air as claimed in claim 2, wherein: the two-step spin coating method comprises the following specific steps: and dropwise adding the perovskite precursor solution on the substrate, wherein the first step of spin coating lasts for 9-11 s, the spin coating speed is 950-1100 rpm, the second step of spin coating lasts for 19-21 s, and the spin coating speed is 4900-5100 rpm.
7. The method for preparing perovskite thin film in air as claimed in claim 2, wherein: and the annealing crystallization temperature is 95-105 ℃, the annealing time is 9-11 min, and the perovskite thin film which has good crystallization and can be stably stored for a long time in an air environment is obtained after the annealing crystallization.
8. A perovskite crystalline material formed by annealing and crystallizing by the method for preparing a perovskite thin film in air as claimed in any one of claims 1 to 7, wherein the perovskite crystalline material has a general formula of ABX3Wherein A is a monovalent cation, B is a divalent metal cation, and X is a halide anion.
9. The perovskite crystalline material as claimed in claim 8, wherein the monovalent cation is Rb+、Na+、K+、Cs+、(NH2)2CH+Or CH3NH3 +One or more of; wherein the divalent metal cation is Pb2+And/or Sn2+(ii) a The halide anion is Cl-、Br-And I-One or more of (a).
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115124747A (en) * | 2022-07-27 | 2022-09-30 | 暨南大学 | Anti-solvent for preparing perovskite solar cell and preparation method of perovskite-PMMA composite film |
| CN116004229A (en) * | 2023-01-04 | 2023-04-25 | 吉林大学 | Chlorophyll-modified CsPbCl3: yb3+ perovskite film and preparation method and application thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115124747A (en) * | 2022-07-27 | 2022-09-30 | 暨南大学 | Anti-solvent for preparing perovskite solar cell and preparation method of perovskite-PMMA composite film |
| CN115124747B (en) * | 2022-07-27 | 2023-10-10 | 暨南大学 | Anti-solvent for preparing perovskite solar cell and preparation method of perovskite-PMMA composite film |
| CN116004229A (en) * | 2023-01-04 | 2023-04-25 | 吉林大学 | Chlorophyll-modified CsPbCl3: yb3+ perovskite film and preparation method and application thereof |
| CN116004229B (en) * | 2023-01-04 | 2023-12-05 | 吉林大学 | Chlorophyll-modified CsPbCl3: yb3+ perovskite film and preparation method and application thereof |
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