CN107170896B - Perovskite flexible photodetector and preparation method thereof - Google Patents

Perovskite flexible photodetector and preparation method thereof Download PDF

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CN107170896B
CN107170896B CN201710295145.2A CN201710295145A CN107170896B CN 107170896 B CN107170896 B CN 107170896B CN 201710295145 A CN201710295145 A CN 201710295145A CN 107170896 B CN107170896 B CN 107170896B
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perovskite
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scraper
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CN107170896A (en
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赵奎
李剑波
刘渝城
刘生忠
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Shaanxi Normal University
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    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
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Abstract

The invention relates to a perovskite flexible photodetector and a preparation method thereof, comprising the following steps of 1, preparing perovskite solution; step 2, preparing a perovskite thin film on the cleaned and dried flexible substrate through a one-way scraper method to obtain the perovskite flexible thin film; step 3, annealing the prepared perovskite flexible film; and 4, evaporating a gold electrode on the annealed perovskite flexible film to obtain the perovskite flexible optical detector. Compared with the perovskite film prepared by the traditional spin-coating method, the film has the advantages of high crystalline quality, few crystal boundaries, wide absorption wave band, long service life of current carriers, good air stability and the like in performance, and has low cost, simple production process, low energy consumption and large-scale production in the aspect of preparation technology. The perovskite flexible light detector based on the invention has excellent light detectivity, light responsivity, bending stability and device life.

Description

Perovskite flexible photodetector and preparation method thereof
Technical Field
The invention relates to a flexible photodetector, in particular to a perovskite flexible photodetector and a preparation method thereof.
Background
Organic-inorganic perovskites have caused a tremendous surge of research in the field of photovoltaics due to their wide light absorption and carrier transport distances. The optical detector based on perovskite large-size single crystals obtains excellent performance. However, large-sized perovskite single crystals cannot be prepared by continuous roll-to-roll technology and flexible device preparation. Although the perovskite thin film-based photodetector has advantages of light weight, large-scale fabrication, and flexible fabrication; however, the perovskite nano-particle thin film prepared at present has a large number of crystal boundaries and defects, so that the recombination of photon-generated carriers is serious, the quantum efficiency and the service life of the carriers are limited, and the perovskite nano-particle thin film becomes a bottleneck for further development of a perovskite flexible photodetector.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a perovskite flexible photodetector and a preparation method thereof, and the quality of the prepared perovskite thin film is close to that of a single crystal, so that the flexible photodetector based on the perovskite thin film has very excellent optical detectivity, responsivity, bending stability and device life.
The invention is realized by the following technical scheme:
a preparation method of a perovskite flexible photodetector comprises the following steps,
step 1, preparing a perovskite solution;
step 2, preparing a perovskite thin film on the cleaned and dried flexible substrate by a scraper method to obtain the perovskite flexible thin film;
firstly, fixing a cleaned and dried flexible substrate on a working plane of a hot table, and preheating for 5 minutes at 80-140 ℃;
secondly, fixing the scraper, adjusting the included angle between the scraper and the horizontal substrate to be 30-90 degrees, and adjusting the slit distance between the scraper and the flexible substrate to be fixed; filling a slit between the flexible substrate and the scraper by dripping perovskite solution;
finally, under the air or nitrogen environment with the humidity lower than 80%, the temperature of a hot table is controlled to be 80-140 ℃, a scraper is horizontally moved in a single direction at the speed of 10-50mm/min, and the perovskite solution is dragged to form a film on the flexible substrate, so that the perovskite oriented single crystal fiber flexible film with the fiber crystal having the single crystal property, namely the perovskite flexible film, is obtained;
step 3, annealing the prepared perovskite flexible film;
and 4, evaporating a gold electrode on the annealed perovskite flexible film to obtain the perovskite flexible optical detector.
Preferably, in step 2, the slit distance between the doctor blade and the flexible substrate is 50 to 200 μm.
Preferably, in the step 2, the relation between the volume of the dropwise added perovskite solution and the area of the perovskite thin film is 3-5 mu L/cm2。
Preferably, in step 1, when preparing the perovskite solution;
adding an organic-inorganic halogen perovskite precursor into an organic solvent, wherein the concentration is between 0.5M and 1.2M; placing the uniformly mixed solution at 60 ℃ and stirring for 2 hours, then cooling to room temperature and stirring for more than four hours; filtering with a polytetrafluoroethylene filter membrane with the aperture of 0.45 mu m to obtain a perovskite solution for later use;
wherein the organic-inorganic halogen perovskite is MAPbI respectively3Or MAPbBr3(ii) a The corresponding precursors are MAI and PbI respectively2And MABr and PbBr2(ii) a The molar ratio of the corresponding precursor is MAI to PbI2=1:（0.5-1.5），MABr:PbBr2=1:（0.5-1.5）；
The organic solvent is dimethylformamide, dimethyl sulfoxide or gamma-butyrolactone respectively.
Further, according to different perovskite solutions, the temperature of the hot stage is respectively 80-120 ℃ when a dimethyl formamide solution is adopted, 110-140 ℃ when a dimethyl sulfoxide solution is adopted, and 120-150 ℃ when a gamma-butyrolactone solution is adopted.
Preferably, when annealing is performed in the step 3, the prepared perovskite flexible thin film is placed on a hot stage at the temperature of 80-150 ℃ for thermal annealing for 8-10 minutes.
Preferably, in step 2, the flexible substrate is a flexible PET film.
A perovskite flexible photodetector is prepared by the preparation method.
Compared with the prior art, the invention has the following beneficial technical effects:
the perovskite film in the perovskite optical detector is single crystal perovskite orientation fiber crystal prepared by a one-way doctor blade method. Compared with the perovskite film prepared by the traditional spin-coating method, the film has the advantages of high crystalline quality, few crystal boundaries, wide absorption wave band, long service life of current carriers, good air stability and the like in performance, and has low cost, simple production process, low energy consumption and large-scale production in the aspect of preparation technology. The perovskite flexible light detector based on the invention has excellent light detectivity, light responsivity, bending stability and device life.
Drawings
FIG. 1 is a scanning electron microscope image of a flexible thin film of perovskite oriented single crystal fibers prepared by the method in the embodiment of the invention.
FIG. 2a is a transmission electron microscopy electron diffraction pattern of a flexible thin film of perovskite oriented single crystal fibers prepared by the method in the embodiment of the invention.
FIG. 2b is a wide angle grazing incidence X-ray diffraction pattern of a flexible thin film of perovskite oriented single crystal fibers prepared by the method described in the examples of the present invention.
FIG. 3a is a graph of the UV absorption spectrum of a flexible thin film of perovskite oriented single crystal fibers prepared by the method of the embodiment of the invention; perovskite nano-particle thin films prepared by a common spin coating method are used as reference substances.
FIG. 3b is a time resolved photoluminescence spectrum of a flexible thin film of perovskite-oriented single crystal fibers prepared by the method of the embodiment of the invention; perovskite nano-particle thin films prepared by a common spin coating method are used as reference substances.
FIG. 4a is the optical response of a flexible photodetector of perovskite oriented single crystal fibers prepared by the method in the example of the invention at a wavelength of 560 nm; perovskite nano-particle thin films prepared by a common spin coating method are used as reference substances.
FIG. 4b is the optical detectivity of a flexible optical detector of perovskite oriented single crystal fibers prepared by the method in the example of the invention at a wavelength of 560 nm; perovskite nano-particle thin films prepared by a common spin coating method are used as reference substances.
FIG. 5a is a bending test of a perovskite-oriented single crystal fiber flexible photodetector prepared by the method described in the examples of the present invention.
FIG. 5b is an in-air lifetime test of a perovskite-oriented single crystal fiber flexible photodetector prepared as described in the examples of the present invention.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
The invention discloses a preparation method of a perovskite broadband flexible photodetector, which comprises the following steps:
step 1, selecting a regular flexible substrate of high-quality polyethylene terephthalate (PET), ultrasonically cleaning the regular flexible substrate in acetone, ethanol and isopropanol for 15 minutes respectively, blow-drying the regular flexible substrate by using nitrogen, and treating the regular flexible substrate by using oxygen plasma for 5 minutes for later use;
and 2, adding the organic-inorganic halogen perovskite precursor into an organic solvent, wherein the concentration is between 0.5M and 1.2M. The solution was stirred at 60 ℃ for 2 hours, then cooled to room temperature and stirred overnight. The solution was filtered through a Polytetrafluoroethylene (PTFE) filter membrane with a pore size of 0.45 μm before use. Wherein the organic-inorganic halogen perovskite is MAPbI respectively3And MAPbBr3. The precursors are MAI and PbI respectively2And MABr and PbBr2. The molar ratio of the precursor is MAI to PbI2=1:（0.5-1.5），MABr:PbBr2And (1) = 0.5-1.5. The organic solvent of the perovskite is a good solvent thereof, and is Dimethylformamide (DMF), gamma-butyrolactone (GBL) and dimethyl sulfoxide (DMSO), respectively.
And 3, fixing the cleaned PET substrate on a flat hot table, and preheating for 5 minutes at the temperature of 80-140 ℃. The scraper is fixed and the included angle between the scraper and the horizontal substrate is adjusted to be 30-90 degrees. The slit distance between the doctor blade and the substrate is adjusted to 50-200 μm. A quantity of perovskite solution is taken to fill the slit between the substrate and the doctor blade. And (3) moving a scraper horizontally in a single direction at the speed of 1-50 mm/min, and dragging the perovskite solution to form a film on the PET substrate. Wherein the blade coating environment is an air or nitrogen environment with the humidity lower than 80%; according to different properties of the solution, the temperature of the hot stage is respectively 80-100 ℃ when the DMF solution is adopted, 110-130 ℃ when the DMSO solution is adopted and 120-140 ℃ when the GBL solution is adopted; the relationship between the volume of the dropwise added perovskite solution and the area of the perovskite film is as follows: 3 to 5 μ L/cm2And dropwise adding a corresponding volume of perovskite solution according to the size of the perovskite flexible film to be prepared.
And 4, after blade coating is stopped, transferring the perovskite flexible film to a hot bench at 100 ℃ for thermal annealing for 8-10 minutes. The prepared perovskite thin film can observe highly oriented fiber crystals through shape tests of scanning electron microscopes at 200 mu m and 100 mu m, as shown in figure 1; the fiber crystal can be determined to have single crystal property through a transmission electron microscope and a wide-angle grazing incidence X-ray diffraction crystal structure test, as shown in figures 2a and 2 b; through the ultraviolet absorption spectrum film light absorption property test, the oriented single crystal fiber film can be observed to have wider light absorption than the traditional nanoparticle film, as shown in fig. 3 a; through a lifetime test of the photo-generated carriers of the time-resolved photoluminescence spectrum, it can be observed that the lifetime of the carriers in the oriented single crystal fiber film is longer than that of the conventional nanoparticle film, as shown in fig. 3 b. Wherein the thermal annealing environment is an air or nitrogen environment with humidity lower than 80%.
And 5, transferring the thermally annealed perovskite flexible film into an evaporation chamber, and performing evaporation on the gold electrode with the aid of a mask. The perovskite thin film between the gold electrodes has an effective size of 40 μm width and 1 mm length. The gold electrode was 300 nm thick. The effective area of illumination is 2.7 multiplied by 10-7m2。
Step 6, configuring laser sources with visible light in different wave bands between 480 nm and 750 nm on a Keithley2400 Source Meter instrument platform, and respectively adjusting the output wave bands and the output power of the lasers (0.08-0.5 mw/cm)2) And testing the detection rate and the responsiveness of the perovskite flexible photodetector, as shown in fig. 4a and 4 b.
Step 7, the stability of the freshly prepared perovskite flexible photodetector is tested by 1000 times of bending as shown in fig. 5a, and the device lifetime after 48 hours of exposure to an air environment with 50-70% humidity as shown in fig. 5b, respectively.
The flexible optical detector of the perovskite orientation fiber crystal is prepared by adopting a doctor blade method. The preparation method of the perovskite photodetector fully utilizes the blade coating printing technology with low cost, has simple production process and low energy consumption, and can grow on a large scale. The prepared perovskite film has high crystal quality, few crystal boundaries, wide absorption wave band, long service life of current carriers and good air stability. The perovskite flexible light detector based on the invention has excellent light detectivity, light responsivity, bending stability and device life.
Example 1
The best mode of the invention is to mix 1.0M MAPbI3Precursors MAI and PbI of (2)2Added to Dimethylformamide (DMF) solvent at a 1:1 molar ratio, the solution was stirred at 60 ℃ for 2 hours, then cooled to room temperature and stirred overnight. The solution was filtered through Polytetrafluoroethylene (PTFE) with a pore size of 0.45 μm before useAnd (5) membrane filtration.
Cleaning the PET substrate (3X 3 cm)2) Fixed on a flat hot bench and preheated at 100 ℃ for 5 minutes. The scraper is fixed and the included angle between the scraper and the horizontal plane is adjusted to be 50 degrees. The slit distance between the doctor blade and the substrate was adjusted to 100 μm. Taking 40 mu L MAI to PbI2The DMF solution fills the gap between the substrate and the doctor blade. And (3) dragging the perovskite solution to form a film on the substrate by a scraper which is horizontally moved in a single direction at the speed of 10 mm/min.
And after blade coating is stopped, transferring the perovskite flexible film to a hot bench at 100 ℃ for thermal annealing for 10 minutes. The prepared perovskite film passes the morphology and crystal structure test, and the test of photoresponse, detectivity, bending stability and service life in air.
Example 2
0.5M MAPbI3Precursors MAI and PbI of (2)2Added to Dimethylformamide (DMF) solvent at a 1:1 molar ratio, the solution was stirred at 60 ℃ for 2 hours, then cooled to room temperature and stirred overnight. The solution was filtered through a Polytetrafluoroethylene (PTFE) filter membrane with a pore size of 0.45 μm before use.
Cleaning the PET substrate (3X 3 cm)2) Fixed on a flat hot bench and preheated at 80 ℃ for 5 minutes. The scraper is fixed and the included angle between the scraper and the horizontal plane is adjusted to be 50 degrees. The slit distance between the doctor blade and the substrate was adjusted to 50 μm. Taking 40 mu L MAI to PbI2The DMF solution fills the gap between the substrate and the doctor blade. And (3) dragging the perovskite solution to form a film on the substrate by a scraper which is horizontally moved in a single direction at the speed of 10 mm/min.
And after blade coating is stopped, transferring the perovskite flexible film to a hot bench at 100 ℃ for thermal annealing for 10 minutes. The other steps are the same as in example 1.
Example 3
1.2M MAPbI3Precursors MAI and PbI of (2)2Added to Dimethylformamide (DMF) solvent at a 1:1 molar ratio, the solution was stirred at 60 ℃ for 2 hours, then cooled to room temperature and stirred overnight. The solution was filtered through a Polytetrafluoroethylene (PTFE) filter membrane with a pore size of 0.45 μm before use.
Cleaning the PET substrate (3X 3 cm)2) Fixed on a flat hot bench and preheated at 90 ℃ for 5 minutes. The scraper is fixed and the included angle between the scraper and the horizontal plane is adjusted to be 50 degrees. The slit distance between the doctor blade and the substrate was adjusted to 100 μm. Taking 40 mu L MAI to PbI2The DMF solution fills the gap between the substrate and the doctor blade. And (3) dragging the perovskite solution to form a film on the substrate by a scraper which is horizontally moved in a single direction at the speed of 1 mm/min.
And after blade coating is stopped, transferring the perovskite flexible film to a hot bench at the temperature of 80 ℃ for thermal annealing for 10 minutes. The other steps are the same as in example 1.
Example 4
1.0M MAPbI3Precursors MAI and PbI of (2)2Added to Dimethylformamide (DMF) solvent at a 1:0.8 molar ratio, and the solution was stirred at 60 ℃ for 2 hours, then cooled to room temperature and stirred overnight. The solution was filtered through a Polytetrafluoroethylene (PTFE) filter membrane with a pore size of 0.45 μm before use.
Cleaning the PET substrate (3X 3 cm)2) Fixed on a flat hot bench and preheated at 100 ℃ for 5 minutes. The scraper is fixed and the included angle between the scraper and the horizontal plane is adjusted to be 60 degrees. The slit distance between the doctor blade and the substrate was adjusted to 100 μm. Taking 40 mu L MAI to PbI2The DMF solution fills the gap between the substrate and the doctor blade. And (3) dragging the perovskite solution to form a film on the substrate by a scraper which is horizontally moved in a single direction at the speed of 10 mm/min.
And after blade coating is stopped, transferring the perovskite flexible film to a hot bench at 100 ℃ for thermal annealing for 10 minutes. The other steps are the same as in example 1.
Example 5
1.0M MAPbI3Precursors MAI and PbI of (2)2Added to Dimethylformamide (DMF) solvent at a 1:1.2 molar ratio, and the solution was stirred at 60 ℃ for 2 hours, then cooled to room temperature and stirred overnight. The solution was filtered through a Polytetrafluoroethylene (PTFE) filter membrane with a pore size of 0.45 μm before use.
Cleaning the PET substrate (3X 3 cm)2) Fixed on a flat hot bench and preheated at 110 ℃ for 5 minutes. The scraper is fixed and the included angle between the scraper and the horizontal plane is adjusted to be 90 degrees. The slit distance between the doctor blade and the substrate was adjusted to 120 μm. Taking 40 μ L of MAI:PbI2The DMF solution fills the gap between the substrate and the doctor blade. And (3) dragging the perovskite solution to form a film on the substrate by a scraper which is horizontally moved in a single direction at the speed of 30 mm/min.
And after blade coating is stopped, transferring the perovskite flexible film to a hot bench at 100 ℃ for thermal annealing for 10 minutes. The other steps are the same as in example 1.
Example 6
1.2M MAPbI3Precursors MAI and PbI of (2)2Added into a dimethyl sulfoxide (DMSO) solvent in a molar ratio of 1:1, and the solution is stirred at 60 ℃ for 2 hours, then cooled to room temperature and stirred overnight. The solution was filtered through a Polytetrafluoroethylene (PTFE) filter membrane with a pore size of 0.45 μm before use.
Cleaning the PET substrate (3X 3 cm)2) Fixed on a flat hot bench and preheated at 110 ℃ for 5 minutes. The scraper is fixed and the included angle between the scraper and the horizontal plane is adjusted to be 50 degrees. The slit distance between the doctor blade and the substrate was adjusted to 50 μm. Taking 40 mu L MAI to PbI2The DMF solution fills the gap between the substrate and the doctor blade. And (3) dragging the perovskite solution to form a film on the substrate by a scraper which is horizontally moved in a single direction at the speed of 50 mm/min.
And after blade coating is stopped, transferring the perovskite flexible film to a hot bench at 100 ℃ for thermal annealing for 10 minutes. The other steps are the same as in example 1.
Example 7
1.0M MAPbI3Precursors MAI and PbI of (2)2Added into a dimethyl sulfoxide (DMSO) solvent in a molar ratio of 1:0.5, and the solution is stirred at 60 ℃ for 2 hours, then cooled to room temperature and stirred overnight. The solution was filtered through a Polytetrafluoroethylene (PTFE) filter membrane with a pore size of 0.45 μm before use.
Cleaning the PET substrate (3X 3 cm)2) Fixed on a flat hot bench and preheated at 120 ℃ for 5 minutes. The scraper is fixed and the included angle between the scraper and the horizontal plane is adjusted to be 50 degrees. The slit distance between the doctor blade and the substrate was adjusted to 100 μm. Taking 40 mu L MAI to PbI2The DMF solution fills the gap between the substrate and the doctor blade. And (3) dragging the perovskite solution to form a film on the substrate by a scraper which is horizontally moved in a single direction at the speed of 10 mm/min.
And after blade coating is stopped, transferring the perovskite flexible film to a hot bench at 100 ℃ for thermal annealing for 10 minutes. The other steps are the same as in example 1.
Example 8
1.0M MAPbI3Precursors MAI and PbI of (2)2Added into a dimethyl sulfoxide (DMSO) solvent in a molar ratio of 1:0.8, and the solution is stirred at 60 ℃ for 2 hours, then cooled to room temperature and stirred overnight. The solution was filtered through a Polytetrafluoroethylene (PTFE) filter membrane with a pore size of 0.45 μm before use.
Cleaning the PET substrate (3X 10 cm)2) Fixed on a flat hot bench and preheated at 130 ℃ for 5 minutes. The scraper is fixed and the included angle between the scraper and the horizontal plane is adjusted to be 50 degrees. The slit distance between the doctor blade and the substrate was adjusted to 200 μm. Taking 40 mu L MAI to PbI2The DMF solution fills the gap between the substrate and the doctor blade. And (3) dragging the perovskite solution to form a film on the substrate by a scraper which is horizontally moved in a single direction at the speed of 10 mm/min.
And after blade coating is stopped, transferring the perovskite flexible film to a hot bench at 100 ℃ for thermal annealing for 10 minutes. The other steps are the same as in example 1.
Example 9
1.0M MAPbI3Precursors MAI and PbI of (2)2Added into a dimethyl sulfoxide (DMSO) solvent in a molar ratio of 1:1.5, and the solution is stirred at 60 ℃ for 2 hours, then cooled to room temperature and stirred overnight. The solution was filtered through a Polytetrafluoroethylene (PTFE) filter membrane with a pore size of 0.45 μm before use.
Cleaning the PET substrate (3X 3 cm)2) Fixed on a flat hot bench and preheated at 140 ℃ for 5 minutes. The scraper is fixed and the included angle between the scraper and the horizontal plane is adjusted to be 30 degrees. The slit distance between the doctor blade and the substrate was adjusted to 150 μm. Taking 40 mu L MAI to PbI2The DMF solution fills the gap between the substrate and the doctor blade. And (3) dragging the perovskite solution to form a film on the substrate by a scraper which is horizontally moved in a single direction at the speed of 30 mm/min.
And after blade coating is stopped, transferring the perovskite flexible film to a hot bench at 100 ℃ for thermal annealing for 10 minutes. The other steps are the same as in example 1.
Example 10
1.5M MAPbI3Precursors MAI and PbI of (2)2Added to a gamma-butyrolactone (GBL) solvent in a 1:1 molar ratio, the solution was stirred at 60 ℃ for 2 hours, then cooled to room temperature and stirred overnight. The solution was filtered through a Polytetrafluoroethylene (PTFE) filter membrane with a pore size of 0.45 μm before use.
Cleaning the PET substrate (3X 3 cm)2) Fixed on a flat hot bench and preheated at 120 ℃ for 5 minutes. The scraper is fixed and the included angle between the scraper and the horizontal plane is adjusted to be 90 degrees. The slit distance between the doctor blade and the substrate was adjusted to 100 μm. Taking 40 mu L MAI to PbI2The DMF solution fills the gap between the substrate and the doctor blade. And (3) dragging the perovskite solution to form a film on the substrate by a scraper which is horizontally moved in a single direction at the speed of 30 mm/min.
And after blade coating is stopped, transferring the perovskite flexible film to a hot bench at the temperature of 80 ℃ for thermal annealing for 10 minutes. The other steps are the same as in example 1.
Example 11
1.0M MAPbI3Precursors MAI and PbI of (2)2Added to a gamma-butyrolactone (GBL) solvent in a 1:1 molar ratio, the solution was stirred at 60 ℃ for 2 hours, then cooled to room temperature and stirred overnight. The solution was filtered through a Polytetrafluoroethylene (PTFE) filter membrane with a pore size of 0.45 μm before use.
Cleaning the PET substrate (3X 3 cm)2) Fixed on a flat hot bench and preheated at 130 ℃ for 5 minutes. The scraper is fixed and the included angle between the scraper and the horizontal plane is adjusted to be 50 degrees. The slit distance between the doctor blade and the substrate was adjusted to 100 μm. Taking 40 mu L MAI to PbI2The DMF solution fills the gap between the substrate and the doctor blade. And (3) dragging the perovskite solution to form a film on the substrate by a scraper which is horizontally moved in a single direction at the speed of 1 mm/min.
And after blade coating is stopped, transferring the perovskite flexible film to a hot bench at 100 ℃ for thermal annealing for 10 minutes. The other steps are the same as in example 1.
Example 12
1.2M MAPbI3Precursors MAI and PbI of (2)2Added to a gamma-butyrolactone (GBL) solvent in a 1:1 molar ratio, the solution was stirred at 60 ℃ for 2 hours, then cooled to room temperature and stirred overnight. SolutionThe solution was filtered through a Polytetrafluoroethylene (PTFE) filter membrane having a pore size of 0.45 μm before use.
Cleaning the PET substrate (3X 3 cm)2) Fixed on a flat hot bench and preheated at 150 ℃ for 5 minutes. The scraper is fixed and the included angle between the scraper and the horizontal plane is adjusted to be 50 degrees. The slit distance between the doctor blade and the substrate was adjusted to 100 μm. Taking 40 mu L MAI to PbI2The DMF solution fills the gap between the substrate and the doctor blade. And (3) dragging the perovskite solution to form a film on the substrate by a scraper which is horizontally moved in a single direction at the speed of 30 mm/min.
And after blade coating is stopped, transferring the perovskite flexible film to a hot bench at 100 ℃ for thermal annealing for 10 minutes. The other steps are the same as in example 1.
Example 13
1.0M MAPbI3Precursors MAI and PbI of (2)2Added to Dimethylformamide (DMF) solvent at a 1:1 molar ratio, the solution was stirred at 60 ℃ for 2 hours, then cooled to room temperature and stirred overnight. The solution was filtered through a Polytetrafluoroethylene (PTFE) filter membrane with a pore size of 0.45 μm before use.
Cleaning the PET substrate (3X 3 cm)2) Fixed on a flat hot bench and preheated at 100 ℃ for 5 minutes. The scraper is fixed and the included angle between the scraper and the horizontal plane is adjusted to be 60 degrees. The slit distance between the doctor blade and the substrate was adjusted to 100 μm. Taking 40 mu L MAI to PbI2The DMF solution fills the gap between the substrate and the doctor blade. And (3) dragging the perovskite solution to form a film on the substrate by a scraper which is horizontally moved in a single direction at the speed of 5 mm/min.
And after blade coating is stopped, transferring the perovskite flexible film to a hot bench at the temperature of 80 ℃ for thermal annealing for 10 minutes. The other steps are the same as in example 1.
Example 14
1.0M MAPbI3Precursors MAI and PbI of (2)2Added to Dimethylformamide (DMF) solvent at a 1:1 molar ratio, the solution was stirred at 60 ℃ for 2 hours, then cooled to room temperature and stirred overnight. The solution was filtered through a Polytetrafluoroethylene (PTFE) filter membrane with a pore size of 0.45 μm before use.
Cleaning the PET substrate (3X 3 cm)2) Fixed on a flat hot table and arranged atPreheating for 5 minutes at the temperature of 100 ℃. The scraper is fixed and the included angle between the scraper and the horizontal plane is adjusted to be 50 degrees. The slit distance between the doctor blade and the substrate was adjusted to 100 μm. Taking 40 mu L MAI to PbI2The DMF solution fills the gap between the substrate and the doctor blade. And (3) dragging the perovskite solution to form a film on the substrate by a scraper which moves horizontally in a single direction at the speed of 20 mm/min.
And after blade coating is stopped, transferring the perovskite flexible film to a hot bench at the temperature of 150 ℃ for thermal annealing for 10 minutes. The other steps are the same as in example 1.
Example 15
1.0M MAPbI3Precursors MAI and PbI of (2)2Added to Dimethylformamide (DMF) solvent at a 1:1 molar ratio, the solution was stirred at 60 ℃ for 2 hours, then cooled to room temperature and stirred overnight. The solution was filtered through a Polytetrafluoroethylene (PTFE) filter membrane with a pore size of 0.45 μm before use.
Cleaning the PET substrate (3X 3 cm)2) Fixed on a flat hot bench and preheated at 100 ℃ for 5 minutes. The scraper is fixed and the included angle between the scraper and the horizontal plane is adjusted to be 50 degrees. The slit distance between the doctor blade and the substrate was adjusted to 100 μm. Taking 40 mu L MAI to PbI2The DMF solution fills the gap between the substrate and the doctor blade. And (3) dragging the perovskite solution to form a film on the substrate by a scraper which is horizontally moved in a single direction at the speed of 30 mm/min.
And after blade coating is stopped, transferring the perovskite flexible film to a hot bench at 100 ℃ for thermal annealing for 5 minutes. The other steps are the same as in example 1.
Example 16
Adding 1.0M MAPbBr3Precursors of (A) MABr and PbBr2Added to Dimethylformamide (DMF) solvent at a 1:1 molar ratio, the solution was stirred at 60 ℃ for 2 hours, then cooled to room temperature and stirred overnight. The solution was filtered through a Polytetrafluoroethylene (PTFE) filter membrane with a pore size of 0.45 μm before use.
Cleaning the PET substrate (3X 3 cm)2) Fixed on a flat hot bench and preheated at 80 ℃ for 5 minutes. The scraper is fixed and the included angle between the scraper and the horizontal plane is adjusted to be 50 degrees. The slit distance between the doctor blade and the substrate was adjusted to 150 μm. Taking 40 mu L MAI to PbI2DMF solution-filled substrateAnd a slit between the blades. And (3) dragging the perovskite solution to form a film on the substrate by a scraper which is horizontally moved in a single direction at the speed of 50 mm/min.
And after blade coating is stopped, transferring the perovskite flexible film to a hot bench at 100 ℃ for thermal annealing for 10 minutes. The other steps are the same as in example 1.
Example 17
Adding 1.0M MAPbBr3Precursors of (A) MABr and PbBr2Added to Dimethylformamide (DMF) solvent at a 1:1.2 molar ratio, and the solution was stirred at 60 ℃ for 2 hours, then cooled to room temperature and stirred overnight. The solution was filtered through a Polytetrafluoroethylene (PTFE) filter membrane with a pore size of 0.45 μm before use.
Cleaning the PET substrate (3X 3 cm)2) Fixed on a flat hot bench and preheated at 100 ℃ for 5 minutes. The scraper is fixed and the included angle between the scraper and the horizontal plane is adjusted to be 50 degrees. The slit distance between the doctor blade and the substrate was adjusted to 100 μm. Taking 40 mu L MAI to PbI2The DMF solution fills the gap between the substrate and the doctor blade. And (3) dragging the perovskite solution to form a film on the substrate by a scraper which is horizontally moved in a single direction at the speed of 5 mm/min.
And after blade coating is stopped, transferring the perovskite flexible film to a hot bench at the temperature of 150 ℃ for thermal annealing for 10 minutes. The other steps are the same as in example 1.
Example 18
Adding 1.0M MAPbBr3Precursors of (A) MABr and PbBr2Added to Dimethylformamide (DMF) solvent at a 1:0.8 molar ratio, and the solution was stirred at 60 ℃ for 2 hours, then cooled to room temperature and stirred overnight. The solution was filtered through a Polytetrafluoroethylene (PTFE) filter membrane with a pore size of 0.45 μm before use.
Cleaning the PET substrate (3X 3 cm)2) Fixed on a flat hot bench and preheated at 100 ℃ for 5 minutes. The scraper is fixed and the included angle between the scraper and the horizontal plane is adjusted to be 50 degrees. The slit distance between the doctor blade and the substrate was adjusted to 50 μm. Taking 40 mu L MAI to PbI2The DMF solution fills the gap between the substrate and the doctor blade. And (3) dragging the perovskite solution to form a film on the substrate by a scraper which is horizontally moved in a single direction at the speed of 5 mm/min.
And after blade coating is stopped, transferring the perovskite flexible film to a hot bench at the temperature of 150 ℃ for thermal annealing for 10 minutes. The other steps are the same as in example 1.
Example 19
Adding 1.0M MAPbBr3Precursors of (A) MABr and PbBr2Added into a dimethyl sulfoxide (DMSO) solvent in a molar ratio of 1:1, and the solution is stirred at 60 ℃ for 2 hours, then cooled to room temperature and stirred overnight. The solution was filtered through a Polytetrafluoroethylene (PTFE) filter membrane with a pore size of 0.45 μm before use.
Cleaning the PET substrate (3X 3 cm)2) Fixed on a flat hot bench and preheated at 110 ℃ for 5 minutes. The scraper is fixed and the included angle between the scraper and the horizontal plane is adjusted to be 50 degrees. The slit distance between the doctor blade and the substrate was adjusted to 100 μm. Taking 40 mu L MAI to PbI2The DMF solution fills the gap between the substrate and the doctor blade. And (3) dragging the perovskite solution to form a film on the substrate by a scraper which is horizontally moved in a single direction at the speed of 5 mm/min.
And after blade coating is stopped, transferring the perovskite flexible film to a hot bench at the temperature of 150 ℃ for thermal annealing for 10 minutes. The other steps are the same as in example 1.
Example 20
Adding 1.0M MAPbBr3Precursors of (A) MABr and PbBr2Added into a dimethyl sulfoxide (DMSO) solvent in a molar ratio of 1:1, and the solution is stirred at 60 ℃ for 2 hours, then cooled to room temperature and stirred overnight. The solution was filtered through a Polytetrafluoroethylene (PTFE) filter membrane with a pore size of 0.45 μm before use.
Cleaning the PET substrate (3X 3 cm)2) Fixed on a flat hot bench and preheated at 120 ℃ for 5 minutes. The scraper is fixed and the included angle between the scraper and the horizontal plane is adjusted to be 50 degrees. The slit distance between the doctor blade and the substrate was adjusted to 100 μm. Taking 40 mu L MAI to PbI2The DMF solution fills the gap between the substrate and the doctor blade. And (3) dragging the perovskite solution to form a film on the substrate by a scraper which is horizontally moved in a single direction at the speed of 5 mm/min.
And after blade coating is stopped, transferring the perovskite flexible film to a hot bench at 100 ℃ for thermal annealing for 10 minutes. The other steps are the same as in example 1.
Example 21
Adding 1.0M MAPbBr3Precursors of (A) MABr and PbBr2Added into a dimethyl sulfoxide (DMSO) solvent in a molar ratio of 1:1, and the solution is stirred at 60 ℃ for 2 hours, then cooled to room temperature and stirred overnight. The solution was filtered through a Polytetrafluoroethylene (PTFE) filter membrane with a pore size of 0.45 μm before use.
Cleaning the PET substrate (2X 10 cm)2) Fixed on a flat hot bench and preheated at 140 ℃ for 5 minutes. The scraper is fixed and the included angle between the scraper and the horizontal plane is adjusted to be 50 degrees. The slit distance between the doctor blade and the substrate was adjusted to 100 μm. Taking 40 mu L MAI to PbI2The DMF solution fills the gap between the substrate and the doctor blade. And (3) dragging the perovskite solution to form a film on the substrate by a scraper which is horizontally moved in a single direction at the speed of 5 mm/min.
And after blade coating is stopped, transferring the perovskite flexible film to a hot bench at the temperature of 80 ℃ for thermal annealing for 10 minutes. The other steps are the same as in example 1.
Example 22
Adding 0.8M MAPbBr3Precursors of (A) MABr and PbBr2Added to a gamma-butyrolactone (GBL) solvent in a 1:1 molar ratio, the solution was stirred at 60 ℃ for 2 hours, then cooled to room temperature and stirred overnight. The solution was filtered through a Polytetrafluoroethylene (PTFE) filter membrane with a pore size of 0.45 μm before use.
Cleaning the PET substrate (3X 3 cm)2) Fixed on a flat hot bench and preheated at 120 ℃ for 5 minutes. The scraper is fixed and the included angle between the scraper and the horizontal plane is adjusted to be 50 degrees. The slit distance between the doctor blade and the substrate was adjusted to 100 μm. Taking 40 mu L MAI to PbI2The DMF solution fills the gap between the substrate and the doctor blade. And (3) dragging the perovskite solution to form a film on the substrate by a scraper which is horizontally moved in a single direction at the speed of 5 mm/min.
And after blade coating is stopped, transferring the perovskite flexible film to a hot bench at the temperature of 150 ℃ for thermal annealing for 10 minutes. The other steps are the same as in example 1.
Example 23
Adding 1.2M MAPbBr3Precursors of (A) MABr and PbBr2Added to a gamma-butyrolactone (GBL) solvent in a 1:1 molar ratio, the solution was stirred at 60 ℃ for 2 hours, then cooled to room temperature and stirred overnight. Before the solution is usedFiltering with 0.45 μm pore size Polytetrafluoroethylene (PTFE) filter membrane.
Cleaning the PET substrate (3X 3 cm)2) Fixed on a flat hot bench and preheated at 130 ℃ for 5 minutes. The scraper is fixed and the included angle between the scraper and the horizontal plane is adjusted to be 90 degrees. The slit distance between the doctor blade and the substrate was adjusted to 200 μm. Taking 40 mu L MAI to PbI2The DMF solution fills the gap between the substrate and the doctor blade. And (3) dragging the perovskite solution to form a film on the substrate by a scraper which is horizontally moved in a single direction at the speed of 5 mm/min.
And after blade coating is stopped, transferring the perovskite flexible film to a hot bench at 100 ℃ for thermal annealing for 10 minutes. The other steps are the same as in example 1.
Example 24
Adding 0.8M MAPbBr3Precursors of (A) MABr and PbBr2Added to a gamma-butyrolactone (GBL) solvent in a 1:1 molar ratio, the solution was stirred at 60 ℃ for 2 hours, then cooled to room temperature and stirred overnight. The solution was filtered through a Polytetrafluoroethylene (PTFE) filter membrane with a pore size of 0.45 μm before use.
Cleaning the PET substrate (3X 3 cm)2) Fixed on a flat hot bench and preheated at 150 ℃ for 5 minutes. The scraper is fixed and the included angle between the scraper and the horizontal plane is adjusted to be 50 degrees. The slit distance between the doctor blade and the substrate was adjusted to 100 μm. Taking 40 mu L MAI to PbI2The DMF solution fills the gap between the substrate and the doctor blade. And (3) dragging the perovskite solution to form a film on the substrate by a scraper which is horizontally moved in a single direction at the speed of 50 mm/min.
And after blade coating is stopped, transferring the perovskite flexible film to a heating table at the temperature of 120 ℃ for thermal annealing for 10 minutes. The other steps are the same as in example 1.

Claims (2)

1. A preparation method of a perovskite flexible photodetector is characterized by comprising the following steps,
step 1, preparing a perovskite solution;
adding an organic-inorganic halogen perovskite precursor into an organic solvent, wherein the concentration is between 0.5M and 1.2M; placing the uniformly mixed solution at 60 ℃ and stirring for 2 hours, then cooling to room temperature and stirring for more than four hours; filtering with a polytetrafluoroethylene filter membrane with the aperture of 0.45 mu m to obtain a perovskite solution for later use;
wherein the organic-inorganic halogen perovskite is MAPbI respectively3Or MAPbBr3(ii) a The corresponding precursors are MAI and PbI respectively2And MABr and PbBr2(ii) a The molar ratio of the corresponding precursor is MAI to PbI2=1:（0.5-1.5），MABr:PbBr2=1 (0.5-1.5); the organic solvent is dimethylformamide, dimethyl sulfoxide or gamma-butyrolactone respectively;
step 2, preparing a perovskite film on the cleaned and dried flexible substrate through a scraper method, wherein the relation between the volume of the dropwise added perovskite solution and the area of the perovskite film is 3-5 mu L/cm2Obtaining a perovskite flexible film; the flexible substrate is a flexible PET film;
firstly, fixing a cleaned and dried flexible substrate on a working plane of a hot table, and preheating for 5 minutes at 80-140 ℃; according to different perovskite solutions, the temperature of the hot platform is respectively 80-120 ℃ when a dimethylformamide solution is adopted, 110-140 ℃ when a dimethyl sulfoxide solution is adopted, and 120-150 ℃ when a gamma-butyrolactone solution is adopted;
secondly, fixing the scraper and adjusting the included angle between the scraper and the horizontal substrate to be 30-60 degrees, wherein the slit distance between the scraper and the flexible substrate is 50-200 mu m, and the slit distance between the scraper and the flexible substrate is adjusted to be kept fixed; filling a slit between the flexible substrate and the scraper by dripping perovskite solution;
finally, under the air or nitrogen environment with the humidity lower than 80%, the temperature of a hot table is controlled to be 80-140 ℃, a scraper is horizontally moved in a single direction at the speed of 10-50mm/min, and the perovskite solution is dragged to form a film on the flexible substrate, so that the perovskite oriented single crystal fiber flexible film with the fiber crystal having the single crystal property, namely the perovskite flexible film, is obtained;
step 3, placing the prepared perovskite flexible film on a hot bench with the temperature of 80-150 ℃ for thermal annealing for 8-10 minutes;
and 4, evaporating a gold electrode on the annealed perovskite flexible film to obtain the perovskite flexible optical detector.
2. A perovskite flexible photodetector prepared by the preparation method of claim 1.
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