CN109166970B - Perovskite device and preparation method thereof - Google Patents

Perovskite device and preparation method thereof Download PDF

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CN109166970B
CN109166970B CN201810925014.2A CN201810925014A CN109166970B CN 109166970 B CN109166970 B CN 109166970B CN 201810925014 A CN201810925014 A CN 201810925014A CN 109166970 B CN109166970 B CN 109166970B
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perovskite
tin oxide
film
solution
preparing
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CN109166970A (en
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赵奎
樊园园
常晓明
李剑波
牛天启
刘生忠
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Shaanxi Normal University
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H10K71/13—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Abstract

The invention provides a perovskite device and a preparation method thereof, wherein the method comprises the following steps of 1, diluting a hydrogel tin oxide dispersion liquid, preparing a tin oxide film on a substrate by using the obtained solution, and carrying out heat treatment on the tin oxide film to obtain an electron transport layer; step 2, adding an organic-inorganic halogen perovskite precursor into DMI to obtain a perovskite solution, preparing a perovskite thin film on the electron transport layer by adopting the solution, and processing the perovskite thin film to obtain a perovskite absorption layer; step 3, preparing a Spiro-OMTeAD film on the electron transport layer by adopting the Spiro-OMTeAD solution to serve as a hole transport layer; and 4, preparing an electrode on the hole transport layer to obtain the perovskite device. The method completely adopts green solvents, is environment-friendly and efficient, can be directly operated in the air, has good air stability of devices, low cost, simple production process and low energy consumption, and is suitable for large-scale production.

Description

Perovskite device and preparation method thereof
Technical Field
The invention relates to a perovskite solar device and preparation thereof, in particular to a perovskite device and a preparation method thereof.
Background
The traditional silicon solar cell has certain limitation on large-scale application due to the problems of high cost, large environmental pollution caused by a silicon purification process and the like. Therefore, the search for new low-cost, environmentally friendly solar cells is a major concern. The perovskite solar cell can be prepared by a full-solution method at low temperature, is expected to realize large-area low-cost solar cell by adopting a cheap printing mode, and is considered as a solar technology with huge application prospect. However, a large amount of toxic solvents are used in the mainstream solution preparation process at present, and potential threats are brought to the environment and personal safety. Therefore, the realization of green and safe preparation of the perovskite solar cell has important significance for future large-area printing preparation and application.
From 2013 onwards, the efficiency of perovskite solar cells has increased. To date, the efficiency of perovskite solar cells has reached up to 23.3%, and the rate of efficiency increase is unprecedented. At present, Dimethylformamide (DMF), dimethyl sulfoxide (DMSO) and gamma-butyrolactone (GBL) are mostly used for preparing high-quality perovskite polycrystalline thin films in laboratories, the solvents are not suitable for large-scale production due to self toxicity, and common film forming methods such as a spin coating method cannot effectively prepare large-area thin film batteries. Therefore, a low-toxicity solvent system is found, and the preparation of high-quality perovskite thin films by a printing technology is crucial to realize the large-scale production of perovskite solar cells.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a perovskite device and a preparation method thereof, which are all made of green solvents, are environment-friendly and efficient, can be directly operated in the air, and have the advantages of good air stability of the device, low cost of the method, simple production process, low energy consumption and suitability for large-scale production.
The invention is realized by the following technical scheme:
a method for preparing a perovskite device comprises the following steps,
step 1, diluting a hydrogel tin oxide dispersion liquid to obtain a tin oxide solution, preparing a tin oxide film on a substrate by using the tin oxide solution, and performing heat treatment on the tin oxide film to obtain an electron transport layer;
step 2, adding an organic-inorganic halogen perovskite precursor into an organic solvent DMI, stirring and filtering to obtain a perovskite solution, preparing a perovskite thin film on an electron transport layer by adopting the perovskite solution, and treating the perovskite thin film to obtain a perovskite absorption layer;
step 3, preparing a Spiro-OMTeAD film on the electron transport layer by adopting the Spiro-OMTeAD solution to serve as a hole transport layer;
and 4, preparing an electrode on the hole transport layer to obtain the perovskite device.
Preferably, in the step 1, when preparing the tin oxide solution, 1mL of 15% mass fraction hydrogel tin oxide dispersion is diluted by 8-10 times and stirred at normal temperature for 5 hours to prepare the tin oxide solution; when the tin oxide film is prepared, the volume ratio of the tin oxide solution to the area of the film is 0.7-2 mu L/cm2。
Preferably, in the step 1, a blade coating method is adopted to print on the substrate to prepare the tin oxide film; fixing the scraper, adjusting the included angle between the scraper and the horizontal substrate to be 50-90 degrees, and unidirectionally and horizontally moving the scraper at the speed of 50-150mm/s at the temperature of 100 ℃ to drag the tin oxide solution to form a film on the substrate to obtain the tin oxide film.
Preferably, in the step 1, the tin oxide film is annealed to obtain the electron transport layer, wherein the annealing temperature is 110-180 ℃, and the annealing time is 20-30 minutes.
Preferably, in step 2, the organic-inorganic halogen perovskite precursor adopts MAI and Pb (Ac)2·3H2O, mixing the precursors MAI and Pb (Ac) in a molar ratio of 3:12·3H2Adding O into organic solvent DMI, mixing, stirring at 40 deg.C for more than 6 hr, and filtering with 0.45 μ M-pore polytetrafluoroethylene filter membrane to obtain 1.2M organic-inorganic halogen perovskite MAPbI3And (3) solution.
Preferably, in the step 2, a blade coating method is adopted to print the electron transmission layer to prepare the perovskite thin film; the specific steps are as follows,
step 2.1, preheating the electron transport layer for 3 minutes at the temperature of 190-;
step 2.2, fixing the scraper and adjusting the included angle between the scraper and the horizontal substrate to be 50-90 degrees;
and 2.3, in an air environment with humidity lower than 50%, and at the temperature of 190-.
Preferably, in step 2, the perovskite thin film is annealed to obtain the perovskite absorption layer, and the annealing condition is 100 ℃ for 6-12 minutes.
Preferably, in step 3, when preparing the Spiro-OMTeAD solution, 0.45mg of Spiro-OMTeAD is weighed and dissolved in 1mL of ultra-dry ethyl acetate solution with the purity of 99.9%, and stirred until the solution is completely dissolved, 22 muL of lithium salt solution with the mass concentration of 520mg/mL and 36 muL of TBP are added, and stirred for 10 minutes at normal temperature to obtain the Spiro-OMTeAD solution.
Preferably, in the step 3, a doctor blade method is adopted to print and prepare the Spiro-OMTeAD film on the perovskite absorption layer; and (3) at the temperature of 25-70 ℃, moving a scraper horizontally at the speed of 600-.
A perovskite device made by the method of any one of the above.
Compared with the prior art, the invention has the following beneficial technical effects:
in the preparation process of the perovskite device, toxic solvents N, N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), gamma-butyrolactone (GBL) and Chlorobenzene (CB) are replaced by green solvents DMI (1, 3-dimethyl-2-imidazolidinone) and ethyl acetate; therefore, the device can be prepared directly in the air without isolation or ventilation treatment, the safety of experimenters is guaranteed, and industrial mass production can be realized.
Furthermore, the electron transport layer, the perovskite absorption layer and the hole transport layer in the perovskite device can be prepared by adopting a blade coating method, so that the full printing of the perovskite device is realized; the film prepared by the high-temperature blade coating method has the advantages of large grain size, few defects, good photoelectric conversion efficiency, environment friendliness, capability of preparing a high-quality perovskite film by a printing technology, and hopeful realization of large-scale production of perovskite solar cells.
Drawings
FIG. 1a is a schematic representation of the process of example 9 of the present inventionSnO prepared by method2Scanning electron micrographs of the film at 100 μm.
FIG. 1b is a SnO prepared by the method described in example 9 of the present invention2Scanning electron micrograph of the film at 10 μm.
FIG. 1c is a scanning electron micrograph of a perovskite thin film prepared by the method described in example 9 of the present invention at 100 μm.
FIG. 1d is a scanning electron micrograph of a perovskite thin film prepared by the method described in example 9 of the present invention at 10 μm.
FIG. 1e is a scanning electron micrograph of a Spiro film of 100 μm prepared according to the method described in example 9 of the present invention.
FIG. 1f is a scanning electron micrograph at 10 μm of a Spiro film produced by the method described in example 9 of the present invention.
FIG. 2 is a Scanning Electron Microscope (SEM) cross-section at 1 μm of a device prepared by the method described in example 9 of the present invention.
FIG. 3 is a graph showing the UV absorption of a perovskite thin film prepared by the method described in example 9 of the present invention.
FIG. 4 is an X-ray diffraction (XRD) pattern of a perovskite thin film prepared by the method described in example 9 of the present invention.
Fig. 5 is a graph of the photoelectric conversion efficiency of the perovskite solar cell prepared by the method described in example 9 of the present invention.
Fig. 6 is a graph of the external quantum efficiency of the perovskite solar cell fabricated by the method described in example 9 of the present invention.
Fig. 7 is a dark state IV diagram of a perovskite solar cell fabricated as described in example 9 of the present invention.
FIG. 8 is a transient fluorescence plot of a perovskite thin film prepared as described in example 9 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.
According to the preparation method of the perovskite device, the green solvent is adopted in the whole process, the preparation method is environment-friendly and pollution-free, the perovskite device can be directly operated in the air, and further the perovskite device can be preferably prepared through full printing. The invention specifically comprises the following steps when the green solvent is adopted for full printing,
step 1, preparing a tin oxide solution; step 2, preparing a perovskite precursor solution; step 3, preparing a tin oxide film on the cleaned and dried substrate by a one-way scraper method, and annealing to obtain an electron transmission layer; step 4, preparing a perovskite thin film on the prepared electron transmission layer by a one-way scraper method; step 5, annealing the perovskite thin film; step 6, preparing a hole transport layer by blade coating; and 7, evaporating gold for 100 nm. After the preparation, the photoelectric conversion efficiency was tested by a solar simulator.
Wherein, the substrate adopts ITO conductive glass, FTO conductive glass, AZO conductive glass or ITO conductive film; the slit distance of the doctor blade was 50 to 150 μm when the doctor blade was applied.
Specifically, the invention relates to a method for preparing a perovskite device by printing green solvent completely, which comprises the following steps:
step 1: selecting a high-quality FTO conductive glass substrate, respectively ultrasonically cleaning the FTO conductive glass substrate in acetone, ethanol and isopropanol for 30min, then blow-drying the FTO conductive glass substrate by using a nitrogen gun, and placing the FTO conductive glass substrate into oxygen plasma for treatment for 5min for later use;
step 2: when preparing the tin oxide solution, 1mL of hydrogel tin oxide dispersion with the mass fraction of 15% is diluted by 8-10 times and stirred for 5 hours at normal temperature for later use.
And step 3: preparing a perovskite precursor solution; the organic-inorganic halogen perovskite precursor adopts MAI and Pb (Ac)2·3H2O, mixing the precursors MAI and Pb (Ac) in a molar ratio of 3:12·3H2Adding O into organic solvent DMI (1, 3-dimethyl-2-imidazolidinone), uniformly mixing, placing the uniformly mixed solution at 40 ℃ and stirring for more than 6 hours, and then carrying out thermal filtration by using a polytetrafluoroethylene filter membrane with the aperture of 0.45 mu M to obtain organic-inorganic halogen perovskite MAPbI with the concentration of 1.2M3And (3) solution.
And 4, step 4: preparing a hole transport layer solution, weighing 0.45mg of Spiro-OMTeAD, dissolving the Spiro-OMTeAD in 1mL of ultra-dry ethyl acetate solution with the purity of 99.9%, stirring the solution until the solution is completely dissolved, and then adding 22 mu L of lithium salt solution with the preset mass concentration of 520mg/mL and 36 mu L of TBP; stirring at normal temperature for 10min, and filtering with 0.45 μm-pore polytetrafluoroethylene filter membrane. The solution is ready for use.
And 5: cleaning FTO conductive glass substrate (2.8 x 2.8 cm)2) Fixed on a flat hot table and preheated at 100 ℃ for 5 min. The doctor blade was fixed and the slit distance between the doctor blade and the substrate was adjusted to 100 μm. The volume of the tin oxide solution and the area ratio of the thin film are 0.7-2 mu L/cm2In this example, 7. mu.L of the tin oxide solution was taken to fill the slit between the substrate and the doctor blade. Printing on a substrate by adopting a blade coating method to obtain a tin oxide film; fixing the scraper, adjusting the included angle between the scraper and the horizontal substrate to be 50-90 degrees, and unidirectionally and horizontally moving the scraper at the speed of 50-150mm/s at the temperature of 100 ℃ to drag the tin oxide solution to form a film on the substrate to obtain the tin oxide film. In this example, the tin oxide solution was drawn by a horizontal doctor blade at a speed of 100mm/s in one direction to form a film on the substrate.
And after the blade coating is stopped, annealing the tin oxide film to obtain the electron transport layer, wherein the annealing temperature is 110-180 ℃, and the annealing time is 20-30 minutes. In this example, the transfer film was thermally annealed on a 150 ℃ hot stage for 25 min. The prepared film is used for preparing perovskite film.
And step 6, fixing the prepared tin oxide film on a flat hot table, and preheating for 3min at the temperature of 190-210 ℃. The scraper is fixed and the included angle between the scraper and the horizontal plane is adjusted to be 50-90 degrees. The slit distance between the doctor blade and the substrate was adjusted to 100 μm. Fill the slit between the substrate and the doctor blade with 6 μ L of precursor solution. The scraper is moved horizontally in a single direction at the speed of 600 plus 1800mm/min, and the perovskite solution is dragged by the scraper to form a film on the substrate in the single direction at the speed of 1000mm/s in the example.
After the blade coating was stopped, the perovskite thin film was transferred to a 100 ℃ hot stage for thermal annealing for 6-12min, in this example for 10 min.
And 7: fixing the prepared perovskite film on a flat hot table, and preheating for 3min at the temperature of 25-70 ℃. The scraper is fixed and the included angle between the scraper and the horizontal plane is adjusted to be 50-90 degrees. The slit distance between the doctor blade and the substrate was adjusted to 100 μm. Fill the slit between the substrate and the doctor blade with 6 μ L of precursor solution. The scraper is moved horizontally in a single direction at the speed of 600 plus 1800mm/min, and the perovskite solution is dragged by the scraper to form a film on the substrate in the single direction at the speed of 1000mm/min in the example.
And 8, transferring the prepared film into an evaporation chamber, and performing evaporation plating on the gold electrode with the aid of a mask. The effective size of the perovskite thin film between the gold electrodes is 0.09cm2. The gold electrode is 100nm thick.
And 9, testing.
The invention adopts a blade coating method to prepare the perovskite solar device. 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 be prepared in a large area.
Example 1
A process for preparing the perovskite device features use of green solvent, and the operation in air environment at ordinary temp includes such steps as,
step 1, diluting a hydrogel tin oxide dispersion liquid to obtain a tin oxide solution, preparing a tin oxide film on an FTO (fluorine-doped tin oxide) conductive glass substrate by using the tin oxide solution, and performing heat treatment on the tin oxide film to obtain an electron transport layer;
when preparing the tin oxide solution, taking 1mL of 15% mass fraction hydrogel tin oxide dispersion, diluting by 9 times, and stirring at normal temperature for 5 hours to prepare the tin oxide solution; when preparing the tin oxide film, the volume of the tin oxide solution and the area ratio of the film are 1.0 mu L/cm2。
Step 2, adding an organic-inorganic halogen perovskite precursor into an organic solvent DMI (1, 3-dimethyl-2-imidazolidinone), stirring and filtering to obtain a perovskite solution, preparing a perovskite film on the electron transport layer by adopting the perovskite solution, and treating the perovskite film to obtain a perovskite absorption layer;
the organic-inorganic halogen perovskite precursor adopts MAI and Pb (Ac)2·3H2O, mixing the precursors MAI and Pb (Ac) in a molar ratio of 3:12·3H2Adding O into organic solvent DMI, mixing, stirring at 40 deg.C for more than 6 hr, and mixing with waterFiltering with 0.45 μ M-pore Polytetrafluoroethylene (PTFE) filter membrane to obtain MAPbI with concentration of 1.2M3And (3) solution.
Step 3, preparing a Spiro-OMTeAD film on the electron transport layer by adopting the Spiro-OMTeAD solution to serve as a hole transport layer;
when preparing the Spiro-OMTeAD solution, 0.45mg of Spiro-OMTeAD is weighed and dissolved in 1mL of ultra-dry ethyl acetate solution with the purity of 99.9 percent, the mixture is stirred until the solution is completely dissolved, 22 muL of lithium salt solution with the mass concentration of 520mg/mL and 36 muL of TBP are added, and the mixture is stirred at normal temperature for 10 minutes to obtain the Spiro-OMTeAD solution.
And 4, preparing an electrode on the hole transport layer to obtain the perovskite device.
Example 2
A process for preparing the perovskite device features use of green solvent, and the operation in air environment at ordinary temp includes such steps as,
step 1, diluting a hydrogel tin oxide dispersion liquid to obtain a tin oxide solution, preparing a tin oxide film on an ITO (indium tin oxide) conductive glass substrate by using the tin oxide solution, and performing heat treatment on the tin oxide film to obtain an electron transport layer;
when preparing the tin oxide solution, taking 1mL of 15% mass fraction hydrogel tin oxide dispersion, diluting by 8 times, and stirring at normal temperature for 5 hours to prepare the tin oxide solution; when preparing the tin oxide film, the volume of the tin oxide solution and the area ratio of the film are 0.7 mu L/cm2。
Step 2, adding an organic-inorganic halogen perovskite precursor into an organic solvent DMI, stirring and filtering to obtain a perovskite solution, preparing a perovskite thin film on an electron transport layer by adopting the perovskite solution, and treating the perovskite thin film to obtain a perovskite absorption layer;
the organic-inorganic halogen perovskite precursor adopts MAI and Pb (Ac)2·3H2O, mixing the precursors MAI and Pb (Ac) in a molar ratio of 3:12·3H2Adding O into organic solvent DMI, mixing, stirring at 40 deg.C for more than 6 hr, and polymerizing with 0.45 μm pore diameterThe tetrafluoroethylene is filtered by a filter membrane to obtain the organic-inorganic halogen perovskite MAPbI with the concentration of 1.2M3And (3) solution.
Step 3, preparing a Spiro-OMTeAD film on the electron transport layer by adopting the Spiro-OMTeAD solution to serve as a hole transport layer;
when preparing the Spiro-OMTeAD solution, 0.45mg of Spiro-OMTeAD is weighed and dissolved in 1mL of ultra-dry ethyl acetate solution with the purity of 99.9 percent, the mixture is stirred until the solution is completely dissolved, 22 muL of lithium salt solution with the mass concentration of 520mg/mL and 36 muL of TBP are added, and the mixture is stirred at normal temperature for 10 minutes to obtain the Spiro-OMTeAD solution.
And 4, preparing an electrode on the hole transport layer to obtain the perovskite device.
Example 3
On the basis of example 1, in step 1, the tin oxide solution is used on an AZO conductive glass substrate; when preparing the tin oxide solution, taking 1mL of 15% mass fraction hydrogel tin oxide dispersion, diluting by 10 times, and stirring at normal temperature for 5 hours to prepare the tin oxide solution; when preparing the tin oxide film, the volume of the tin oxide solution and the area ratio of the film are 1.2 mu L/cm2. The rest of the procedure was the same as in example 1.
Example 4
On the basis of example 1, in step 1, the tin oxide solution is applied to an ITO conductive film substrate; when preparing the tin oxide solution, taking 1mL of 15% mass fraction hydrogel tin oxide dispersion, diluting by 9 times, and stirring at normal temperature for 5 hours to prepare the tin oxide solution; when preparing the tin oxide film, the volume of the tin oxide solution and the area ratio of the film are 1.4 mu L/cm2. The rest of the procedure was the same as in example 1.
Example 5
On the basis of example 1, in step 1, the tin oxide solution is applied to an ITO conductive film substrate; when preparing the tin oxide solution, taking 1mL of 15% mass fraction hydrogel tin oxide dispersion, diluting by 8.5 times, and stirring at normal temperature for 5 hours to prepare the tin oxide solution; when preparing the tin oxide film, the volume of the tin oxide solution and the area ratio of the film are 1.6 mu L/cm2. The rest of the procedure was the same as in example 1.
Example 6
On the basis of the embodiment 1, in the step 1, the tin oxide solution is adopted on an FTO conductive glass substrate; when preparing the tin oxide solution, taking 1mL of 15% mass fraction hydrogel tin oxide dispersion, diluting by 9 times, and stirring at normal temperature for 5 hours to prepare the tin oxide solution; when preparing the tin oxide film, the volume of the tin oxide solution and the area ratio of the film are 1.8 mu L/cm2. The rest of the procedure was the same as in example 1.
Example 7
On the basis of example 1, in step 1, the tin oxide solution is used on an AZO conductive glass substrate; when preparing the tin oxide solution, taking 1mL of 15% mass fraction hydrogel tin oxide dispersion, diluting by 9.5 times, and stirring at normal temperature for 5 hours to prepare the tin oxide solution; when preparing the tin oxide film, the volume of the tin oxide solution and the area ratio of the film are 2.0 mu L/cm2. The rest of the procedure was the same as in example 1.
Example 8
On the basis of the embodiment 1, in the step 1, the tin oxide solution is adopted on an ITO conductive glass substrate; when preparing the tin oxide solution, taking 1mL of 15% mass fraction hydrogel tin oxide dispersion, diluting by 10 times, and stirring at normal temperature for 5 hours to prepare the tin oxide solution; when preparing the tin oxide film, the volume of the tin oxide solution and the area ratio of the film are 1.0 mu L/cm2. The rest of the procedure was the same as in example 1.
Example 9
The preparation method is characterized in that a full-green solvent is adopted in the embodiment 1, the operation can be carried out in the air environment at normal temperature, a blade coating method is matched, the green full-printing preparation of the perovskite device is realized, the specific blade coating process steps are adopted on the basis of the green solvent disclosed in the embodiment 1, and the slit distance of a scraper is 80 microns.
In the step 1, printing on a substrate by adopting a blade coating method to prepare a tin oxide film; fixing the scraper, adjusting the included angle between the scraper and the horizontal substrate to be 60 degrees, and moving the scraper horizontally in a single direction at the speed of 100mm/s at the temperature of 100 ℃ to drag the tin oxide solution to form a film on the substrate to obtain the tin oxide film.
And annealing the tin oxide film to obtain the electron transport layer, wherein the annealing temperature is 150 ℃, and the annealing time is 25 minutes.
Step 2, printing on the electron transmission layer by adopting a blade coating method to obtain a perovskite thin film; comprises the following steps of preparing a mixture of a plurality of raw materials,
step 2.1, preheating the electron transport layer at the temperature of 200 ℃ for 3 minutes;
step 2.2, fixing the scraper and adjusting the included angle between the scraper and the horizontal substrate to be 60 degrees;
and 2.3, in an air environment with humidity lower than 50%, at the temperature of 200 ℃, moving a scraper horizontally in a single direction at the speed of 1000mm/min, and dragging the perovskite solution to form a film on the electron transmission layer to obtain the perovskite film.
Annealing the perovskite thin film to obtain the perovskite absorption layer, wherein the annealing condition is 100 ℃ for 8 minutes.
Step 3, printing on the perovskite absorption layer by adopting a blade coating method to obtain a Spiro-OMTeAD film; and (3) at the temperature of 35 ℃, moving a scraper horizontally in a single direction at the speed of 1000mm/min, and dragging the Spiro-OMTeAD solution to form a film on the perovskite absorption layer to obtain the hole transport layer.
SnO finally obtained2Scanning Electron micrographs of the films at 100 μm and 10 μm are shown in FIGS. 1a and 1b, SnO2The film is uniformly covered, and a good electron transmission layer can be made; scanning electron micrographs of the perovskite thin film under 100 mu m and 10 mu m are shown in figure 1c and figure 1d, the perovskite thin film prepared by the blade coating method has large grain size, the thin film has small uniform defects and is a good light absorption layer; as shown in FIG. 3, the absorption edge of the perovskite thin film is about 760nm, and MAPbI is represented3Absorption edge of perovskite point; the X-ray diffraction (XRD) pattern of the perovskite thin film is shown in figure 4, and the perovskite thin film has characteristic peaks; scanning electron micrographs of the Spiro film at 100 μm and 10 μm are shown in FIGS. 1e and 1 f; the film is uniform and is a better hole transport layer; the cross section of the device prepared by the method is a scanning electron microscope image under 1 mu m, and is shown in FIG. 2; the perovskite solar cell photoelectric conversion efficiency is shown in fig. 5, and the perovskite solar cell can have better photoelectric conversion efficiency; external quantum efficiency of perovskite solar cellThe rates are shown in FIG. 6; the dark state IV diagram of the perovskite solar cell is shown in FIG. 7, and it can be seen that the perovskite device has the characteristics of few defects and good electron mobility; transient fluorescence patterns of the perovskite thin film are shown in fig. 8, and the perovskite thin film prepared by the doctor blade method has longer fluorescence lifetime compared with the thin film prepared by spin coating.
Example 10
On the basis that any one of the embodiments 1 to 8 adopts a full-green solvent and can be operated in an air environment at normal temperature, a blade coating method is matched to realize the green full-printing preparation of the perovskite device, and on the basis of the green solvent disclosed in the embodiment 1, the specific blade coating process is adopted as follows, and the slit distance of a scraper is 70 mu m.
In the step 1, printing on a substrate by adopting a blade coating method to prepare a tin oxide film; fixing the scraper, adjusting the included angle between the scraper and the horizontal substrate to be 60 degrees, and moving the scraper horizontally in a single direction at the speed of 120mm/s at the temperature of 100 ℃ to drag the tin oxide solution to form a film on the substrate to obtain the tin oxide film.
And annealing the tin oxide film to obtain the electron transport layer, wherein the annealing temperature is 150 ℃, and the annealing time is 25 minutes.
Step 2, printing on the electron transmission layer by adopting a blade coating method to obtain a perovskite thin film; comprises the following steps of preparing a mixture of a plurality of raw materials,
step 2.1, preheating the electron transport layer at 190 ℃ for 3 minutes;
step 2.2, fixing the scraper and adjusting the included angle between the scraper and the horizontal substrate to be 70 degrees;
and 2.3, under the air environment with the humidity lower than 50 percent and at the temperature of 190 ℃, moving a scraper horizontally in a single direction at the speed of 1300mm/min, and dragging the perovskite solution to form a film on the electron transmission layer to obtain the perovskite film.
Annealing the perovskite thin film to obtain the perovskite absorption layer, wherein the annealing condition is 100 ℃ for 10 minutes.
Step 3, printing on the perovskite absorption layer by adopting a blade coating method to obtain a Spiro-OMTeAD film; and (3) at the temperature of 50 ℃, moving a scraper horizontally in a single direction at the speed of 600mm/min, and dragging the Spiro-OMTeAD solution to form a film on the perovskite absorption layer to obtain the hole transport layer.
Example 11
On the basis that any one of the embodiments 1 to 8 adopts a full-green solvent and can be operated in an air environment at normal temperature, a blade coating method is matched to realize the green full-printing preparation of the perovskite device, and on the basis of the green solvent disclosed in the embodiment 1, the specific blade coating process is adopted as follows, and the slit distance of a scraper is 60 mu m.
In the step 1, printing on a substrate by adopting a blade coating method to prepare a tin oxide film; fixing the scraper, adjusting the included angle between the scraper and the horizontal substrate to be 80 degrees, and moving the scraper horizontally in a single direction at the speed of 150mm/s at the temperature of 100 ℃ to drag the tin oxide solution to form a film on the substrate to obtain the tin oxide film.
And annealing the tin oxide film to obtain the electron transport layer, wherein the annealing temperature is 155 ℃, and the annealing time is 25 minutes.
Step 2, printing on the electron transmission layer by adopting a blade coating method to obtain a perovskite thin film; comprises the following steps of preparing a mixture of a plurality of raw materials,
step 2.1, preheating the electron transport layer at 210 ℃ for 3 minutes;
step 2.2, fixing the scraper and adjusting the included angle between the scraper and the horizontal substrate to be 85 degrees;
and 2.3, in an air environment with humidity lower than 50%, at the temperature of 210 ℃, moving a scraper horizontally in a single direction at the speed of 1700mm/min, and dragging the perovskite solution to form a film on the electron transport layer to obtain the perovskite film.
Annealing the perovskite thin film to obtain the perovskite absorption layer, wherein the annealing condition is 100 ℃ for 9 minutes.
Step 3, printing on the perovskite absorption layer by adopting a blade coating method to obtain a Spiro-OMTeAD film; and (3) at the temperature of 60 ℃, moving a scraper horizontally in a single direction at the speed of 1800mm/min, and dragging the Spiro-OMTeAD solution to form a film on the perovskite absorption layer to obtain the hole transport layer.
Example 12
On the basis that any one of the embodiments 1 to 8 adopts a full-green solvent and can be operated in an air environment at normal temperature, a blade coating method is matched to realize the green full-printing preparation of the perovskite device, and on the basis of the green solvent disclosed in the embodiment 1, the specific blade coating process is adopted as follows, and the slit distance of a scraper is 80 microns.
In the step 1, printing on a substrate by adopting a blade coating method to prepare a tin oxide film; fixing the scraper, adjusting the included angle between the scraper and the horizontal substrate to be 70 degrees, and moving the scraper horizontally in a single direction at the speed of 110mm/s at the temperature of 100 ℃ to drag the tin oxide solution to form a film on the substrate to obtain the tin oxide film.
And annealing the tin oxide film to obtain the electron transport layer, wherein the annealing temperature is 120 ℃, and the annealing time is 26 minutes.
Step 2, printing on the electron transmission layer by adopting a blade coating method to obtain a perovskite thin film; comprises the following steps of preparing a mixture of a plurality of raw materials,
step 2.1, preheating the electron transport layer at 195 ℃ for 3 minutes;
step 2.2, fixing the scraper and adjusting the included angle between the scraper and the horizontal substrate to be 50 degrees;
and 2.3, in an air environment with humidity lower than 50%, at the temperature of 195 ℃, moving a scraper horizontally in a single direction at the speed of 1500mm/min, and dragging the perovskite solution to form a film on the electron transmission layer to obtain the perovskite film.
Annealing the perovskite thin film to obtain the perovskite absorption layer, wherein the annealing condition is 100 ℃ for 8 minutes.
Step 3, printing on the perovskite absorption layer by adopting a blade coating method to obtain a Spiro-OMTeAD film; and (3) at the temperature of 55 ℃, moving a scraper horizontally in a single direction at the speed of 700mm/min, and dragging the Spiro-OMTeAD solution to form a film on the perovskite absorption layer to obtain the hole transport layer.
Example 13
On the basis that any one of the embodiments 1 to 8 adopts a full-green solvent and can be operated in an air environment at normal temperature, a blade coating method is matched to realize the green full-printing preparation of the perovskite device, and on the basis of the green solvent disclosed in the embodiment 1, the specific blade coating process is adopted as follows, and the slit distance of a scraper is 50 microns.
In the step 1, printing on a substrate by adopting a blade coating method to prepare a tin oxide film; fixing the scraper, adjusting the included angle between the scraper and the horizontal substrate to be 85 degrees, and moving the scraper horizontally in a single direction at the speed of 60mm/s at the temperature of 100 ℃ to drag the tin oxide solution to form a film on the substrate to obtain the tin oxide film.
And annealing the tin oxide film to obtain the electron transport layer, wherein the annealing temperature is 130 ℃, and the annealing time is 27 minutes.
Step 2, printing on the electron transmission layer by adopting a blade coating method to obtain a perovskite thin film; comprises the following steps of preparing a mixture of a plurality of raw materials,
step 2.1, preheating the electron transport layer at 205 ℃ for 3 minutes;
step 2.2, fixing the scraper and adjusting the included angle between the scraper and the horizontal substrate to be 80 degrees;
and 2.3, in an air environment with humidity lower than 50%, at the temperature of 205 ℃, moving a scraper horizontally in a single direction at the speed of 1800mm/min, and dragging the perovskite solution to form a film on the electron transport layer to obtain the perovskite film.
Annealing the perovskite thin film to obtain the perovskite absorption layer, wherein the annealing condition is 100 ℃ for 6 minutes.
Step 3, printing on the perovskite absorption layer by adopting a blade coating method to obtain a Spiro-OMTeAD film; and (3) at the temperature of 45 ℃, moving a scraper horizontally in a single direction at the speed of 1300mm/min, and dragging the Spiro-OMTeAD solution to form a film on the perovskite absorption layer to obtain the hole transport layer.
Example 14
On the basis that any one of the embodiments 1 to 8 adopts a full-green solvent and can be operated in an air environment at normal temperature, a blade coating method is matched to realize the green full-printing preparation of the perovskite device, and on the basis of the green solvent disclosed in the embodiment 1, the specific blade coating process is adopted as follows, and the slit distance of a scraper is 90 mu m.
In the step 1, printing on a substrate by adopting a blade coating method to prepare a tin oxide film; fixing the scraper, adjusting the included angle between the scraper and the horizontal substrate to be 75 degrees, and moving the scraper horizontally in a single direction at the speed of 140mm/s at the temperature of 100 ℃ to drag the tin oxide solution to form a film on the substrate to obtain the tin oxide film.
And annealing the tin oxide film to obtain the electron transport layer, wherein the annealing temperature is 160 ℃, and the annealing time is 28 minutes.
Step 2, printing on the electron transmission layer by adopting a blade coating method to obtain a perovskite thin film; comprises the following steps of preparing a mixture of a plurality of raw materials,
step 2.1, preheating the electron transport layer at the temperature of 200 ℃ for 3 minutes;
step 2.2, fixing the scraper and adjusting the included angle between the scraper and the horizontal substrate to be 5560 degrees;
and 2.3, in an air environment with humidity lower than 50%, at the temperature of 200 ℃, moving a scraper horizontally in a single direction at the speed of 800mm/min, and dragging the perovskite solution to form a film on the electron transmission layer to obtain the perovskite film.
Annealing the perovskite thin film to obtain the perovskite absorption layer, wherein the annealing condition is 100 ℃ for 8 minutes.
Step 3, printing on the perovskite absorption layer by adopting a blade coating method to obtain a Spiro-OMTeAD film; and (3) at the temperature of 35 ℃, moving a scraper horizontally in a single direction at the speed of 1200mm/min, and dragging the Spiro-OMTeAD solution to form a film on the perovskite absorption layer to obtain the hole transport layer.
Example 15
On the basis that any one of the embodiments 1 to 8 adopts a full-green solvent and can be operated in an air environment at normal temperature, a blade coating method is matched to realize the green full-printing preparation of the perovskite device, and on the basis of the green solvent disclosed in the embodiment 1, the specific blade coating process is adopted as follows, and the slit distance of a scraper is 120 mu m.
In the step 1, printing on a substrate by adopting a blade coating method to prepare a tin oxide film; fixing the scraper, adjusting the included angle between the scraper and the horizontal substrate to be 90 degrees, and moving the scraper horizontally in a single direction at the speed of 50mm/s at the temperature of 100 ℃ to drag the tin oxide solution to form a film on the substrate to obtain the tin oxide film.
And annealing the tin oxide film to obtain the electron transport layer, wherein the annealing temperature is 150 ℃, and the annealing time is 29 minutes.
Step 2, printing on the electron transmission layer by adopting a blade coating method to obtain a perovskite thin film; comprises the following steps of preparing a mixture of a plurality of raw materials,
step 2.1, preheating the electron transport layer at the temperature of 200 ℃ for 3 minutes;
step 2.2, fixing the scraper and adjusting the included angle between the scraper and the horizontal substrate to be 65 degrees;
and 2.3, in an air environment with humidity lower than 50%, at the temperature of 200 ℃, moving a scraper horizontally in a single direction at the speed of 1100mm/min, and dragging the perovskite solution to form a film on the electron transmission layer to obtain the perovskite film.
Annealing the perovskite thin film to obtain the perovskite absorption layer, wherein the annealing condition is 100 ℃ for 12 minutes.
Step 3, printing on the perovskite absorption layer by adopting a blade coating method to obtain a Spiro-OMTeAD film; and (3) at the temperature of 25 ℃, moving a scraper horizontally in a single direction at the speed of 1100mm/min, and dragging the Spiro-OMTeAD solution to form a film on the perovskite absorption layer to obtain the hole transport layer.
Example 16
On the basis that any one of the embodiments 1 to 8 adopts a full-green solvent and can be operated in an air environment at normal temperature, a blade coating method is matched to realize the green full-printing preparation of the perovskite device, and on the basis of the green solvent disclosed in the embodiment 1, the specific blade coating process is adopted as follows, and the slit distance of a scraper is 150 microns.
In the step 1, printing on a substrate by adopting a blade coating method to prepare a tin oxide film; fixing the scraper, adjusting the included angle between the scraper and the horizontal substrate to be 85 degrees, and moving the scraper horizontally in a single direction at the speed of 70mm/s at the temperature of 100 ℃ to drag the tin oxide solution to form a film on the substrate to obtain the tin oxide film.
And annealing the tin oxide film to obtain the electron transport layer, wherein the annealing temperature is 140 ℃, and the annealing time is 30 minutes.
Step 2, printing on the electron transmission layer by adopting a blade coating method to obtain a perovskite thin film; comprises the following steps of preparing a mixture of a plurality of raw materials,
step 2.1, preheating the electron transport layer at the temperature of 206 ℃ for 3 minutes;
step 2.2, fixing the scraper and adjusting the included angle between the scraper and the horizontal substrate to be 80 degrees;
and 2.3, in an air environment with humidity lower than 50%, at the temperature of 206 ℃, moving a scraper horizontally in a single direction at the speed of 1400mm/min, and dragging the perovskite solution to form a film on the electron transmission layer to obtain the perovskite film.
Annealing the perovskite thin film to obtain the perovskite absorption layer, wherein the annealing condition is 100 ℃ for 7 minutes.
Step 3, printing on the perovskite absorption layer by adopting a blade coating method to obtain a Spiro-OMTeAD film; and (3) at the temperature of 70 ℃, moving a scraper horizontally in a single direction at the speed of 1600mm/min, and dragging the Spiro-OMTeAD solution to form a film on the perovskite absorption layer to obtain the hole transport layer.
Example 17
On the basis that any one of the embodiments 1 to 8 adopts a full-green solvent and can be operated in an air environment at normal temperature, a doctor blade method is matched to realize the green full-printing preparation of the perovskite device, and on the basis of the green solvent disclosed in the embodiment 1, the specific doctor blade process is adopted as follows, and the slit distance of a doctor blade is 110 microns.
In the step 1, printing on a substrate by adopting a blade coating method to prepare a tin oxide film; fixing the scraper, adjusting the included angle between the scraper and the horizontal substrate to be 60 degrees, and moving the scraper horizontally in a single direction at the speed of 90mm/s at the temperature of 100 ℃ to drag the tin oxide solution to form a film on the substrate to obtain the tin oxide film.
And annealing the tin oxide film to obtain the electron transport layer, wherein the annealing temperature is 180 ℃, and the annealing time is 25 minutes.
Step 2, printing on the electron transmission layer by adopting a blade coating method to obtain a perovskite thin film; comprises the following steps of preparing a mixture of a plurality of raw materials,
step 2.1, preheating the electron transport layer at the temperature of 200 ℃ for 3 minutes;
step 2.2, fixing the scraper and adjusting the included angle between the scraper and the horizontal substrate to be 90 degrees;
and 2.3, in an air environment with humidity lower than 50%, at the temperature of 200 ℃, moving a scraper horizontally in a single direction at the speed of 600mm/min, and dragging the perovskite solution to form a film on the electron transmission layer to obtain the perovskite film.
Annealing the perovskite thin film to obtain the perovskite absorption layer, wherein the annealing condition is 100 ℃ for 8 minutes.
Step 3, printing on the perovskite absorption layer by adopting a blade coating method to obtain a Spiro-OMTeAD film; and (3) at the temperature of 65 ℃, moving a scraper horizontally in a single direction at the speed of 800mm/min, and dragging the Spiro-OMTeAD solution to form a film on the perovskite absorption layer to obtain the hole transport layer.
Example 18
On the basis that any one of the embodiments 1 to 8 adopts a full-green solvent and can be operated in an air environment at normal temperature, a doctor blade method is matched to realize the green full-printing preparation of the perovskite device, and on the basis of the green solvent disclosed in the embodiment 1, the specific doctor blade process is adopted as follows, and the slit distance of a doctor blade is 130 mu m.
In the step 1, printing on a substrate by adopting a blade coating method to prepare a tin oxide film; fixing the scraper, adjusting the included angle between the scraper and the horizontal substrate to be 60 degrees, and moving the scraper horizontally in a single direction at the speed of 80mm/s at the temperature of 100 ℃ to drag the tin oxide solution to form a film on the substrate to obtain the tin oxide film.
And annealing the tin oxide film to obtain the electron transport layer, wherein the annealing temperature is 170 ℃, and the annealing time is 25 minutes.
Step 2, printing on the electron transmission layer by adopting a blade coating method to obtain a perovskite thin film; comprises the following steps of preparing a mixture of a plurality of raw materials,
step 2.1, preheating the electron transport layer at 193 ℃ for 3 minutes;
step 2.2, fixing the scraper and adjusting the included angle between the scraper and the horizontal substrate to be 75 degrees;
and 2.3, in an air environment with humidity lower than 50%, at the temperature of 193 ℃, moving a scraper horizontally in a single direction at the speed of 1600mm/min, and dragging the perovskite solution to form a film on the electron transmission layer to obtain the perovskite film.
Annealing the perovskite thin film to obtain the perovskite absorption layer, wherein the annealing condition is 100 ℃ for 11 minutes.
Step 3, printing on the perovskite absorption layer by adopting a blade coating method to obtain a Spiro-OMTeAD film; and (3) at the temperature of 30 ℃, moving a scraper horizontally in a single direction at the speed of 900mm/min, and dragging the Spiro-OMTeAD solution to form a film on the perovskite absorption layer to obtain the hole transport layer.
Example 19
On the basis that any one of the embodiments 1 to 8 adopts a full-green solvent and can be operated in an air environment at normal temperature, a blade coating method is matched to realize the green full-printing preparation of the perovskite device, and on the basis of the green solvent disclosed in the embodiment 1, the specific blade coating process is adopted as follows, and the slit distance of a scraper is 80 microns.
In the step 1, printing on a substrate by adopting a blade coating method to prepare a tin oxide film; fixing the scraper, adjusting the included angle between the scraper and the horizontal substrate to be 60 degrees, and moving the scraper horizontally in a single direction at the speed of 130mm/s at the temperature of 100 ℃ to drag the tin oxide solution to form a film on the substrate to obtain the tin oxide film.
And annealing the tin oxide film to obtain the electron transport layer, wherein the annealing temperature is 110 ℃, and the annealing time is 25 minutes.
Step 2, printing on the electron transmission layer by adopting a blade coating method to obtain a perovskite thin film; comprises the following steps of preparing a mixture of a plurality of raw materials,
step 2.1, preheating the electron transport layer at the temperature of 200 ℃ for 3 minutes;
step 2.2, fixing the scraper and adjusting the included angle between the scraper and the horizontal substrate to be 60 degrees;
and 2.3, in an air environment with humidity lower than 50%, moving a scraper horizontally in a single direction at the temperature of 200 ℃ and at the speed of 1200mm/min, and dragging the perovskite solution to form a film on the electron transport layer to obtain the perovskite film.
Annealing the perovskite thin film to obtain the perovskite absorption layer, wherein the annealing condition is 100 ℃ for 8 minutes.
Step 3, printing on the perovskite absorption layer by adopting a blade coating method to obtain a Spiro-OMTeAD film; and (3) at the temperature of 35 ℃, moving a scraper horizontally in a single direction at the speed of 1500mm/min, and dragging the Spiro-OMTeAD solution to form a film on the perovskite absorption layer to obtain the hole transport layer.
Example 20
On the basis that any one of the embodiments 1 to 8 adopts a full-green solvent and can be operated in an air environment at normal temperature, a doctor blade method is matched to realize the green full-printing preparation of the perovskite device, and on the basis of the green solvent disclosed in the embodiment 1, the specific doctor blade process is adopted as follows, and the slit distance of a doctor blade is 100 mu m.
In the step 1, printing on a substrate by adopting a blade coating method to prepare a tin oxide film; fixing the scraper, adjusting the included angle between the scraper and the horizontal substrate to be 60 degrees, and moving the scraper horizontally in a single direction at the speed of 100mm/s at the temperature of 100 ℃ to drag the tin oxide solution to form a film on the substrate to obtain the tin oxide film.
And annealing the tin oxide film to obtain the electron transport layer, wherein the annealing temperature is 150 ℃, and the annealing time is 25 minutes.
Step 2, printing on the electron transmission layer by adopting a blade coating method to obtain a perovskite thin film; comprises the following steps of preparing a mixture of a plurality of raw materials,
step 2.1, preheating the electron transport layer at the temperature of 200 ℃ for 3 minutes;
step 2.2, fixing the scraper and adjusting the included angle between the scraper and the horizontal substrate to be 60 degrees;
and 2.3, under the air environment with the humidity lower than 50 percent and at the temperature of 200 ℃, moving a scraper horizontally in a single direction at the speed of 900mm/min, and dragging the perovskite solution to form a film on the electron transmission layer to obtain the perovskite film.
Annealing the perovskite thin film to obtain the perovskite absorption layer, wherein the annealing condition is 100 ℃ for 8 minutes.
Step 3, printing on the perovskite absorption layer by adopting a blade coating method to obtain a Spiro-OMTeAD film; and (3) at the temperature of 35 ℃, moving a scraper horizontally in a single direction at the speed of 1700mm/min, and dragging the Spiro-OMTeAD solution to form a film on the perovskite absorption layer to obtain the hole transport layer.
Example 21
On the basis that any one of the embodiments 1 to 8 adopts a full-green solvent and can be operated in an air environment at normal temperature, a blade coating method is matched to realize the green full-printing preparation of the perovskite device, and on the basis of the green solvent disclosed in the embodiment 1, the specific blade coating process is adopted as follows, and the slit distance of a scraper is 80 microns.
In the step 1, printing on a substrate by adopting a blade coating method to prepare a tin oxide film; fixing the scraper, adjusting the included angle between the scraper and the horizontal substrate to be 60 degrees, and moving the scraper horizontally in a single direction at the speed of 100mm/s at the temperature of 100 ℃ to drag the tin oxide solution to form a film on the substrate to obtain the tin oxide film.
And annealing the tin oxide film to obtain the electron transport layer, wherein the annealing temperature is 150 ℃, and the annealing time is 25 minutes.
Step 2, printing on the electron transmission layer by adopting a blade coating method to obtain a perovskite thin film; comprises the following steps of preparing a mixture of a plurality of raw materials,
step 2.1, preheating the electron transport layer at the temperature of 200 ℃ for 3 minutes;
step 2.2, fixing the scraper and adjusting the included angle between the scraper and the horizontal substrate to be 60 degrees;
and 2.3, in an air environment with humidity lower than 50%, at the temperature of 200 ℃, moving a scraper horizontally in a single direction at the speed of 700mm/min, and dragging the perovskite solution to form a film on the electron transmission layer to obtain the perovskite film.
Annealing the perovskite thin film to obtain the perovskite absorption layer, wherein the annealing condition is 100 ℃ for 8 minutes.
Step 3, printing on the perovskite absorption layer by adopting a blade coating method to obtain a Spiro-OMTeAD film; and (3) at the temperature of 35 ℃, moving a scraper horizontally in a single direction at the speed of 1400mm/min, and dragging the Spiro-OMTeAD solution to form a film on the perovskite absorption layer to obtain the hole transport layer.

Claims (9)

1. A method of manufacturing a perovskite device, comprising the steps of,
step 1, diluting a hydrogel tin oxide dispersion liquid to obtain a tin oxide solution, preparing a tin oxide film on a substrate by using the tin oxide solution, and performing heat treatment on the tin oxide film to obtain an electron transport layer; wherein, a blade coating method is adopted to print on a substrate to prepare a tin oxide film;
step 2, adding an organic-inorganic halogen perovskite precursor into an organic solvent DMI, stirring and filtering to obtain a perovskite solution, preparing a perovskite thin film on an electron transport layer by adopting the perovskite solution, and treating the perovskite thin film to obtain a perovskite absorption layer; printing on the electron transmission layer by adopting a blade coating method to obtain a perovskite thin film;
in step 2, the organic-inorganic halogen perovskite precursor adopts MAI and Pb (Ac)2·3H2O, mixing the precursors MAI and Pb (Ac) in a molar ratio of 3:12·3H2Adding O into organic solvent DMI, mixing, stirring at 40 deg.C for more than 6 hr, and filtering with 0.45 μ M-pore polytetrafluoroethylene filter membrane to obtain 1.2M organic-inorganic halogen perovskite MAPbI3A solution;
step 3, preparing a Spiro-OMTeAD film on the electron transport layer by adopting the Spiro-OMTeAD solution to serve as a hole transport layer; printing on the perovskite absorption layer by adopting a blade coating method to obtain a Spiro-OMTeAD film;
and 4, preparing an electrode on the hole transport layer to obtain the perovskite device.
2. The preparation method of the perovskite device as claimed in claim 1, wherein in the step 1, when preparing the tin oxide solution, 1mL of 15% mass fraction hydrogel tin oxide dispersion is diluted by 8-10 times and stirred at normal temperature for 5h to prepare the tin oxide solution; when the tin oxide film is prepared, the volume ratio of the tin oxide solution to the area of the film is 0.7-2 mu L/cm2。
3. The method for preparing a perovskite device according to claim 1, wherein in the step 1, a tin oxide film is prepared by printing on the substrate by a doctor blade method; fixing the scraper, adjusting the included angle between the scraper and the horizontal substrate to be 50-90 degrees, and unidirectionally and horizontally moving the scraper at the speed of 50-150mm/s at the temperature of 100 ℃ to drag the tin oxide solution to form a film on the substrate to obtain the tin oxide film.
4. The method for preparing a perovskite device as claimed in claim 1, wherein in step 1, the tin oxide thin film is annealed to obtain the electron transport layer, wherein the annealing temperature is 110-180 ℃, and the annealing time is 20-30 minutes.
5. The method for preparing a perovskite device according to claim 1, wherein in step 2, the perovskite thin film is prepared by printing on the electron transport layer by a doctor blade method,
step 2.1, preheating the electron transport layer for 3 minutes at the temperature of 190-;
step 2.2, fixing the scraper and adjusting the included angle between the scraper and the horizontal substrate to be 50-90 degrees;
and 2.3, in an air environment with humidity lower than 50%, and at the temperature of 190-.
6. The method for preparing a perovskite device according to claim 1, wherein in the step 2, the perovskite thin film is annealed to obtain the perovskite absorption layer, and the annealing condition is 100 ℃ for 6-12 minutes.
7. The method of claim 1, wherein in step 3, when preparing the Spiro-OMTeAD solution, 0.45mg of Spiro-OMTeAD is weighed and dissolved in 1mL of 99.9% pure ultra-dry ethyl acetate solution, and stirred until the solution is completely dissolved, 22 μ L of 520mg/mL lithium salt solution and 36 μ L of TBP are added, and stirred at room temperature for 10 minutes to obtain the Spiro-OMTeAD solution.
8. The method for preparing a perovskite device according to claim 1, wherein in step 3, a doctor blade method is adopted to print and prepare a Spiro-OMTeAD film on the perovskite absorption layer; and (3) at the temperature of 25-70 ℃, moving a scraper horizontally at the speed of 600-.
9. A perovskite device, characterized in that it is obtained by a method according to any one of claims 1 to 8.
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Phase Transition Control for High-Performance Blade-Coated Perovskite Solar Cells;Li J , Munir R , Fan Y , et al.;《Joule》;20180507;第2卷(第7期);全文 *

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