CN113285027A - Two-dimensional perovskite thin film material, solar cell and preparation method thereof - Google Patents

Two-dimensional perovskite thin film material, solar cell and preparation method thereof Download PDF

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CN113285027A
CN113285027A CN202110549860.0A CN202110549860A CN113285027A CN 113285027 A CN113285027 A CN 113285027A CN 202110549860 A CN202110549860 A CN 202110549860A CN 113285027 A CN113285027 A CN 113285027A
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thin film
solar cell
perovskite
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dimensional perovskite
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CN113285027B (en
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曹晖
朱荣志
刘洋洋
刘旭豪
刘路杰
徐晨鑫
陶涛
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Nanjing University of Information Science and Technology
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    • H—ELECTRICITY
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/321—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]
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Abstract

The invention discloses a two-dimensional perovskite thin film material, a solar cell and a preparation method thereof. The perovskite precursor solution is prepared by taking lead iodide, iodoformamidine, chloromethane, calcium bromide and calcium iodide as raw materials and taking dimethylformamide and dimethyl sulfoxide as a mixed solvent, and the thin film material is obtained by annealing after spin coating. The solar cell sequentially comprises a conductive substrate, an electron transport layer and a perovskite light absorption layer, the perovskite precursor solution is coated on the conductive substrate coated with the electron transport layer in a spin coating mode, and the two-dimensional perovskite solar cell is prepared after annealing. The two-dimensional perovskite thin film material is used as a perovskite light absorption layer material in a solar cell. The chemical composition of the two-dimensional perovskite thin film is (CaBr)2(FA)n‑1PbnI3n+1Wherein FA is a formamidine cation. The present invention providesThe preparation method can obtain the two-dimensional perovskite thin film material with higher crystallinity and better performance, thereby improving the photoelectric performance and efficiency of the perovskite solar cell.

Description

Two-dimensional perovskite thin film material, solar cell and preparation method thereof
Technical Field
The invention belongs to the technical field of perovskite thin film materials, and particularly relates to a two-dimensional perovskite thin film material, a solar cell and a preparation method of the two-dimensional perovskite thin film material.
Background
Perovskite materials have excellent photoelectric properties and are receiving much attention from researchers. Perovskite solar cells are developed very rapidly, the efficiency is improved from 3.8% to more than 25% in short decades, and in perovskite solar cell light absorption layer materials, most researchers select three-dimensional CH3NH3PbI3(MAPbI3) Perovskite materials have outstanding natural advantages such as high absorption coefficient, good bipolar transport performance of electrons and holes, tunable band gap, small exciton binding energy, higher carrier diffusion length and the like, and thus, the perovskite materials also have wide application in the fields of light-emitting diodes, lasers, photodetectors, transistors and the like. If the perovskite thin film has a smooth surface and larger grains, the properties of high-efficiency light capture capability, ultra-fast carrier transport capability, ion migration inhibition and the like can be obtained, and the properties of the perovskite thin film can be further improved.
At present, research on perovskite is greatly advanced, and particularly, when three-dimensional perovskite is used as a light absorption layer material, the photoelectric conversion efficiency of the perovskite breaks through 25%, but the device has poor stability, poor stability to water, light and heat, and is not beneficial to large-scale production, and the realization of commercialization of the perovskite is greatly hindered. For commercial applications of perovskites, not only high efficiency but also long-term stability is critical. Therefore, it is extremely important to research and develop a new photoelectric material that is inherently stable. In recent years, two-dimensional perovskites have attracted attention from a wide range of researchers, and have better light, moisture and heat stability, as short as several years (BA)2(MA)nPbn+1I3n+1The (n ═ 1 ∞) system efficiency is about 17 percent, and the excellent photoelectric property makes the system the most potential in the futureOne of the optoelectronic materials.
In the two-dimensional perovskite material, some cations with larger volume and two-dimensional inorganic perovskites alternately form a layered structure, so that a bilayer of monovalent cations can form a relatively weaker van der waals gap with two adjacent two-dimensional inorganic perovskite sheet structures, the stability of the two-dimensional perovskite material is obviously greater than that of a three-dimensional perovskite just due to the van der waals gap, in addition, the larger cations block the ion motion in the perovskite, and a proper organic part can be introduced into the perovskite material through design to bring certain hydrophobicity to the light-absorbing layer material, so that the stability of the material is improved. Since 2014, research on two-dimensional perovskite materials has been greatly advanced, and the highest efficiency reaches 18%. The 2014 Karunadasa et al led to the adoption of larger phenethyl ammonium cations (PEA)+And MA+Cation combination is carried out to prepare a two-dimensional perovskite material with n equal to 3, and then argent and the like research the structure and the performance of the two-dimensional perovskite when n is 20, 40 and 60. In addition, the research finds that n-Butylamine (BAI) can also be used as an organic large cation in a two-dimensional perovskite material. However, due to the wide band gap, the large exciton binding energy and the poor electron transport capability of the two-dimensional perovskite, the efficiency of the two-dimensional perovskite has a certain gap compared with that of the three-dimensional perovskite, and the two-dimensional perovskite has a great progress space.
At present, the two-dimensional perovskite solar cell mainly takes organic large cations as main materials, and the organic cation perovskite cell commonly used at present is (NH)3-R-NH3)BX4And (R-NH)3)2BX4. The tail of the organic part of the organic large cation enables the whole structure to be stable through Van der Waals interaction force, but hydrogen atoms on amino groups at two ends of the organic part in the cation are connected with the two-dimensional inorganic perovskite sheet structure through hydrogen bonds, so that Van der Waals gaps between layers are eliminated, and the performance of the perovskite material is influenced. Compared with organic large cations, the inorganic cations can form stronger interaction with the inorganic layer, and the two-dimensional perovskite material prepared by the inorganic cations has better thermal stability, so the inorganic cations (CaBr) are discovered in the invention+Can also be used as twoThe material of the perovskite thin film and is used in perovskite solar cells.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a two-dimensional perovskite thin film material, the preparation method is characterized in that amitraz, lead iodide, chloromethane, calcium bromide and calcium iodide are used as raw materials, and the molar ratio of the raw materials is n-1: n:0.4n:1:1, adding iodoformamidine, lead iodide, chloromethane, calcium bromide and calcium iodide into a mixed solvent of dimethylformamide and dimethyl sulfoxide, stirring to obtain a uniform, clear and transparent precursor solution, wherein the volume ratio of the dimethyl formamide to the dimethyl sulfoxide is 1:4, the concentration of the lead iodide in the mixed solvent is 1.8mol/L, after the precursor solution is spin-coated to form a film, removing the solvent remained in the film, and annealing to obtain the two-dimensional perovskite film material, wherein the annealing temperature is 110-170 ℃, the annealing time is 10-20 min, and the chemical composition of the film material is (CaBr).2(FA)n-1PbnI3n+1N is 1 to infinity, wherein FA is a formamidine cation; the prepared perovskite thin film material can be prepared by independently spin-coating a precursor solution on spin-coating equipment, but the thin film material needs to be used as a light absorption layer material of a perovskite solar cell, and the application of the thin film material can be realized only by spin-coating the precursor solution on an electron transport layer of the cell.
The invention also provides a two-dimensional perovskite solar cell which is characterized in that the perovskite solar cell prepared by the invention is a half cell, and the cell structure sequentially comprises the following components from bottom to top: the electronic transmission layer sequentially comprises a compact thin film layer and a mesoporous thin film layer, and the perovskite light absorption layer is the two-dimensional perovskite thin film material.
Further, the compact thin film layer is prepared by taking diisopropoxy diacetone titanium and anhydrous n-butyl alcohol as raw materials, wherein the volume ratio of the diisopropoxy diacetone titanium to the anhydrous n-butyl alcohol is 1 (16-20), the two raw materials are uniformly mixed and then spin-coated on the surface of the conductive substrate to form a film, and the compact thin film layer is obtained through annealing treatment at the annealing temperature of 400-550 ℃ for 40-60 min.
Further, the mesoporous thin film layer takes titanium dioxide and absolute ethyl alcohol as raw materials, the mass ratio of the titanium dioxide to the absolute ethyl alcohol is 1 (2-8), the two raw materials are mixed into a uniform and non-layered suspension, the surface of the compact thin film layer is coated with a film in a spinning mode, the compact thin film layer is obtained through annealing treatment, the annealing temperature is 100-130 ℃, and the annealing time is 10-20 min.
In order to achieve the above object, the present invention provides a method for manufacturing a two-dimensional perovskite solar cell, comprising the steps of:
step 1: pretreating the conductive substrate;
step 2: preparing a compact film layer;
and step 3: preparing a mesoporous thin film layer;
and 4, step 4: preparing a perovskite light absorption layer precursor solution;
and 5: and preparing the perovskite light absorption layer.
Further, the specific method of step 1 is as follows: ultrasonically cleaning a conductive substrate by sequentially adopting acetone, isopropanol, ethanol and deionized water, wherein the time for treating the conductive substrate by each solvent is 30min, drying after cleaning, and carrying out ultraviolet-ozone treatment; the conductive substrate is FTO conductive glass.
Further, the specific method of step 2 is as follows: adding diisopropoxy-diacetone titanium into anhydrous n-butyl alcohol, wherein the volume ratio of the diisopropoxy-diacetone titanium to the anhydrous n-butyl alcohol is 1 (16-20), uniformly mixing, spin-coating on the conductive substrate, and annealing to obtain a compact thin film layer; the annealing temperature is 100-130 ℃, and the annealing time is 10-20 min.
Further, the specific method of step 3 is as follows: preparing uniform suspension from titanium dioxide and absolute ethyl alcohol, wherein the mass ratio of the titanium dioxide to the absolute ethyl alcohol is 1 (2-8), spin-coating the suspension on the compact thin film layer, and annealing to obtain the mesoporous thin film layer, wherein the annealing temperature is 400-550 ℃, and the annealing time is 40-60 min.
Further, the specific method of step 4 is as follows: the preparation method comprises the steps of adding iodoformamidine, lead iodide, chloromethane, calcium bromide and calcium iodide into a mixed solvent of dimethyl formamide and dimethyl sulfoxide according to the proportion of n-1: n:0.4n:1:1, wherein the chloromethane and the calcium iodide are used as additives of a perovskite light absorption layer material, so that the crystallization quality of the perovskite light absorption layer can be improved, the grain size of the perovskite light absorption layer is larger, and the performance of a solar cell is better. The concentration of lead iodide in the mixed solvent is 1.8mol/L, the volume ratio of dimethyl formamide to dimethyl sulfoxide is 1:4, iodoformamidine, lead iodide, chloromethane, calcium bromide and calcium iodide are mixed with the mixed solvent, the mixture is stirred after magnetic oscillation for 10min until the solution is uniform, clear and transparent, and the precursor solution of the perovskite light absorption layer is obtained.
Further, the specific method of step 5 is as follows: the perovskite precursor solution is spin-coated on the mesoporous thin film layer, 1mL of diethyl ether is dropwise added in the spin-coating process, the diethyl ether is used as an anti-solvent, the mixed solvent can be quickly evaporated, and the preparation time of the perovskite light absorption layer material is shortened; after spin coating, placing the two-dimensional perovskite thin film material in a vacuum environment to remove a solvent, and then annealing to obtain the two-dimensional perovskite thin film material, wherein the annealing temperature is 110-170 ℃, and the annealing time is 10-20 min.
The invention has the beneficial effects that: the invention provides a two-dimensional perovskite thin film material, a solar cell and a preparation method thereof. The annealing process of the perovskite light absorption layer material can be used for preparing a two-dimensional perovskite thin film material and a solar cell which are good in crystal orientation, large in grain size, uniform and compact and completely covered by gloss, the better the crystal orientation is, the smoother the surface of the material is, the larger the grain size is, the more light can be absorbed by the perovskite light absorption layer, the longer the service life of a carrier is, more electrons and holes are decomposed, and the better the performance of the cell is. The prepared two-dimensional perovskite thin film material and the solar cell have good stability and photoelectric property, and have good application prospect in the photoelectric field. In addition, the film material and the battery prepared by the invention can be prepared in the air in the whole process without any gas protection, and have great guiding significance and commercial value prospect for the industrialization of the two-dimensional perovskite film material and the perovskite solar battery.
Drawings
FIG. 1 is an X-ray diffraction pattern of a two-dimensional perovskite thin film material prepared in comparative example 1 and examples 1-2 of the present invention;
FIG. 2 is a steady state photoluminescence spectrum of a two-dimensional perovskite solar cell prepared in examples 3-5 of the present invention;
FIG. 3 is a transient photoluminescence spectrum of a two-dimensional perovskite solar cell prepared in examples 3-5 of the present invention;
fig. 4 is a picture of a sample of a two-dimensional perovskite solar cell prepared according to the present invention.
Detailed Description
The present invention will now be described in further detail with reference to the accompanying drawings.
Example 1
A two-dimensional perovskite thin film material, wherein n is equal to 1, and the chemical composition of the perovskite thin film material is (CaBr)2PbI4Preparing 0.05mL of dimethyl sulfoxide and 0.2mL of dimethylformamide into a mixed solvent, adding 0.45mmol of lead iodide, 0.18mmol of chloromethane, 0.45mmol of calcium bromide and 0.45mmol of calcium iodide into the mixed solvent, magnetically shaking for 10min, stirring for 12 h to obtain a precursor solution, independently forming a film on the surface of a spin-coating instrument at 5000rpm, dropwise adding 1mL of diethyl ether 20s before the spin-coating is finished, and annealing on a heating table at 110 ℃ for 20min to finally obtain a chemical composition (CaBr)2PbI4The two-dimensional perovskite thin film material.
Example 2
A two-dimensional perovskite thin film material, wherein n is equal to 1, and the chemical composition of the perovskite thin film material is (CaBr)2PbI4Preparing 0.05mL of dimethyl sulfoxide and 0.2mL of dimethylformamide into a mixed solvent, adding 0.45mmol of lead iodide, 0.18mmol of chloromethane, 0.45mmol of calcium bromide and 0.45mmol of calcium iodide into the mixed solvent, magnetically shaking for 10min, stirring for 12 hours to obtain a precursor solution, and independently forming the precursor solution on the surface of a spin-coating instrument at the speed of 5000rpmThe film is added with 1mL of diethyl ether 20s before the spin coating is finished and is placed on a heating table at 130 ℃ for annealing for 20min, and finally the chemical composition (CaBr) is obtained2PbI4The two-dimensional perovskite thin film material.
Example 3
Method for producing a two-dimensional perovskite solar cell, wherein the chemical composition of the perovskite light-absorbing layer material is (CaBr)2FA19Pb20I61The method specifically comprises the following steps:
step 1, cleaning the FTO conductive glass, namely ultrasonically cleaning the FTO conductive glass by using acetone, isopropanol, ethanol and deionized water in sequence, wherein the cleaning time of each solvent is 30 minutes, transferring the FTO conductive glass to a 120-DEG C oven to be fully dried to remove surface moisture and impurities after cleaning is finished, and then treating the dried FTO conductive glass for 30 minutes by using an ultraviolet-ozone device to wait for later use.
And 2, preparing a compact thin film layer, adding 160 mu L of diisopropoxy bis (acetylacetone) titanium into 1mL of anhydrous n-butanol, shaking up, spin-coating the mixed solution onto FTO conductive glass at the speed of 2000rpm, and annealing at the temperature of 120 ℃ for 10 min.
And 3, preparing a mesoporous thin film layer, preparing titanium dioxide and absolute ethyl alcohol into a solution according to the mass ratio of 1:4, stirring for 12 hours, spin-coating the surface of the material prepared in the step 2 at 6000rpm, paving the whole surface with the titanium dioxide, and annealing for 50min at 500 ℃.
Step 4, preparing perovskite light absorption layer precursor solution, preparing 0.05mL of dimethyl sulfoxide and 0.2mL of dimethylformamide into a mixed solvent, adding 0.4275mmol of iodoformamidine, 0.45mmol of lead iodide, 0.18mmol of chloromethylamine, 0.0225mmol of calcium bromide and 0.0225mmol of calcium iodide into the mixed solvent, magnetically shaking for 10min, and stirring for 12 hours to obtain uniform, clear and transparent (CaBr)2FA19Pb20I61A perovskite precursor solution.
Step 5, preparing a perovskite light absorption layer, spin-coating the precursor solution obtained by the step 4 on the surface of the material prepared in the step 3 at the speed of 5000rpm, and dropwise adding 1m for 20s before the spin-coating is finishedThe solvent on the surface of the spin coating can be quickly evaporated by using L-diethyl ether and diethyl ether as anti-solvents, the spin coating is carried out, the residual solvent is pumped out in a vacuum environment, the mixture is placed on a heating table at 130 ℃ for annealing for 20min, and finally the chemical composition (CaBr) of the light absorption layer is obtained2FA19Pb20I61The two-dimensional perovskite solar cell of (1).
Example 4
Method for producing a two-dimensional perovskite solar cell, wherein the chemical composition of the perovskite light-absorbing layer material is (CaBr)2FA39Pb40I121The method comprises the following steps:
step 1, cleaning the FTO conductive glass, namely ultrasonically cleaning the FTO conductive glass by using acetone, isopropanol, ethanol and deionized water in sequence, wherein the cleaning time of each solvent is 30 minutes, transferring the FTO conductive glass to a 120-DEG C oven to be fully dried to remove surface moisture and impurities after cleaning is finished, and then treating the dried FTO conductive glass for 30 minutes by using an ultraviolet-ozone device to wait for later use.
And 2, preparing a compact thin film layer, adding 160 mu L of diisopropoxy bis (acetylacetone) titanium into 1mL of anhydrous n-butanol, shaking up, spin-coating the mixed solution onto FTO conductive glass at the speed of 2000rpm, and annealing at the temperature of 120 ℃ for 10 min.
And 3, preparing a mesoporous thin film layer, preparing titanium dioxide and absolute ethyl alcohol into a solution according to the mass ratio of 1:4, stirring for 12 hours, spin-coating the surface of the material prepared in the step 2 at 6000rpm, paving the whole surface with the titanium dioxide, and annealing at the temperature of 500 ℃ for 50 minutes.
Step 4, preparing perovskite light absorption layer precursor solution, preparing 0.05mL of dimethyl sulfoxide and 0.2mL of dimethylformamide into a mixed solvent, adding 0.43875mmol of iodoformamidine, 0.45mmol of lead iodide, 0.18mmol of chloromethylamine, 0.01125mmol of calcium bromide and 0.01125mmol of calcium iodide into the mixed solvent, stirring for 12 hours after magnetic force oscillation is carried out for 10 minutes, and obtaining uniform, clear and transparent (CaBr)2FA39Pb40I121A perovskite precursor solution.
Step 5, preparing a perovskite light absorption layerSpin-coating the precursor solution obtained by the step 4 on the surface of the material prepared in the step 3 at the speed of 5000rpm, dropwise adding 1mL of diethyl ether 20s before the spin-coating is finished, wherein the diethyl ether is used as an anti-solvent and can quickly evaporate the solvent on the surface of the spin-coating, placing the spin-coating solution in a vacuum environment after the spin-coating, removing the residual solvent, placing the spin-coating solution on a heating table at 130 ℃ for annealing for 20min, and finally obtaining the chemical composition (CaBr) of the light absorption layer2FA39Pb40I121The two-dimensional perovskite solar cell of (1).
Example 5
A method for preparing a two-dimensional perovskite solar cell, wherein the perovskite light-absorbing layer material has the chemical composition of (CaBr)2FA59Pb60I181The method comprises the following steps:
step 1, cleaning the FTO conductive glass, namely ultrasonically cleaning the FTO conductive glass by using acetone, isopropanol, ethanol and deionized water in sequence, wherein the cleaning time of each solvent is 30 minutes, transferring the FTO conductive glass to a 120-DEG C oven to be fully dried to remove surface moisture and impurities after cleaning is finished, and then treating the dried FTO conductive glass for 30 minutes by using an ultraviolet-ozone device to wait for later use.
And 2, preparing a compact thin film layer, adding 160 mu L of diisopropoxy bis (acetylacetone) titanium into 1mL of anhydrous n-butanol, shaking up, spin-coating the mixed solution onto FTO conductive glass at the speed of 2000rpm, and annealing at the temperature of 120 ℃ for 10 min.
And 3, preparing a mesoporous thin film layer, preparing titanium dioxide and absolute ethyl alcohol into a solution according to the mass ratio of 1:4, stirring for 12 hours, spin-coating the surface of the material prepared in the step 2 at 6000rpm, paving the whole surface with the titanium dioxide, and annealing at the temperature of 500 ℃ for 50 minutes.
Step 4, preparing a perovskite light absorption layer precursor solution, preparing 0.05mL of dimethyl sulfoxide and 0.2mL of dimethylformamide into a mixed solvent, adding 0.4425mmol of iodoformamidine, 0.45mmol of lead iodide, 0.18mmol of chloromethylamine, 0.0075mmol of calcium bromide and 0.0075mmol of calcium iodide into the mixed solvent, stirring for 12 hours after magnetic force oscillation is carried out for 10 minutes, and obtaining uniform, clear and transparent (CaBr)2FA59Pb60I181A perovskite precursor solution.
Step 5, preparing a perovskite light absorption layer, spin-coating the precursor solution obtained by the treatment in the step 4 on the surface of the material prepared in the step 3 at the speed of 5000rpm, dropwise adding 1mL of diethyl ether 20s before the spin-coating is finished, placing the material in a vacuum environment after the spin-coating to remove the residual solvent, placing the material on a heating table at 130 ℃ for annealing for 20min, and finally obtaining the light absorption layer chemical composition (CaBr)2FA59Pb60I181The two-dimensional perovskite solar cell of (1).
Example 6
A two-dimensional perovskite thin film material, wherein n is equal to 40, and the chemical composition of the perovskite thin film material is (CaBr)2FA39Pb40I121Preparing 0.05mL of dimethyl sulfoxide and 0.2mL of dimethylformamide into a mixed solvent, adding 0.43875mmol of iodoformamidine, 0.45mmol of lead iodide, 0.18mmol of chloromethylamine, 0.01125mmol of calcium bromide and 0.01125mmol of calcium iodide into the mixed solvent, magnetically shaking for 10min, stirring for 12 h to obtain a precursor solution, directly spin-coating the precursor solution on the surface of a spin-coating instrument at the speed of 5000rpm to form a film, dropwise adding 1mL of diethyl ether 20s before the spin-coating is finished, placing the film on a heating table at the temperature of 170 ℃ for annealing for 10min, and finally obtaining the chemical composition (CaBr)2FA39Pb40I121The two-dimensional perovskite thin film material.
Example 7
A two-dimensional perovskite thin film material, wherein n is equal to 60, and the chemical composition of the perovskite thin film material is (CaBr)2FA59Pb60I181Preparing 0.05mL of dimethyl sulfoxide and 0.2mL of dimethylformamide into a mixed solvent, adding 0.4425mmol of iodoformamidine, 0.45mmol of lead iodide, 0.18mmol of chloromethylamine, 0.0075mmol of calcium bromide and 0.0075mmol of calcium iodide into the mixed solvent, magnetically shaking for 10min, stirring for 12 h to obtain a precursor solution, directly spin-coating the precursor solution on the surface of a spin-coating instrument at 5000rpm to form a film, dropwise adding 1mL of diethyl ether 20s before the spin-coating is finished, placing the film on a heating table at 150 ℃ for annealing for 15min, and finally obtaining the chemical composition (CaBr)2FA59Pb60I181The two-dimensional perovskite thin film material.
Example 8
Method for producing a two-dimensional perovskite solar cell, wherein the chemical composition of the perovskite light-absorbing layer material is (CaBr)2FA29Pb30I91The method specifically comprises the following steps:
step 1, cleaning the FTO conductive glass, namely ultrasonically cleaning the FTO conductive glass by using acetone, isopropanol, ethanol and deionized water in sequence, wherein the cleaning time of each solvent is 30 minutes, transferring the FTO conductive glass to a 120-DEG C oven to be fully dried to remove surface moisture and impurities after cleaning is finished, and then treating the dried FTO conductive glass for 30 minutes by using an ultraviolet-ozone device to wait for later use.
And 2, preparing a compact thin film layer, adding 160 mu L of diisopropoxy bis (acetylacetone) titanium into 1mL of anhydrous n-butanol, shaking up, spin-coating the mixed solution onto FTO conductive glass at the speed of 2000rpm, and annealing at the temperature of 120 ℃ for 15 min.
And 3, preparing a mesoporous thin film layer, preparing titanium dioxide and absolute ethyl alcohol into a solution according to the mass ratio of 1:2, stirring for 12 hours, spin-coating the surface of the material prepared in the step 2 at 6000rpm, paving the whole surface with the titanium dioxide, and annealing for 60min at 400 ℃.
Step 4, preparing perovskite light absorption layer precursor solution, preparing 0.05mL of dimethyl sulfoxide and 0.2mL of dimethylformamide into a mixed solvent, adding 0.435mmol of iodoformamidine, 0.45mmol of lead iodide, 0.18mmol of chloromethylamine, 0.015mmol of calcium bromide and 0.015mmol of calcium iodide into the mixed solvent, and stirring for 12 hours by magnetic force oscillation for 10min to obtain uniform, clear and transparent (CaBr)2FA29Pb30I91A perovskite precursor solution.
Step 5, preparing a perovskite light absorption layer, spin-coating the precursor solution obtained by the treatment in the step 4 on the surface of the material prepared in the step 3 at the speed of 5000rpm, dropwise adding 1mL of diethyl ether 20s before the spin-coating is finished, using the diethyl ether as an anti-solvent to quickly evaporate the solvent on the spin-coated surface, placing the spin-coated surface in a vacuum environment to remove the residual solvent, placing the spin-coated surface on a heating table at 150 ℃ for annealing for 15min, and finally obtaining the perovskite light absorption layerThe chemical composition of the light absorption layer is (CaBr)2FA29Pb30I91The two-dimensional perovskite solar cell of (1).
Example 9
Method for preparing a two-dimensional perovskite solar cell, wherein the chemical composition of the perovskite light absorbing layer material is the same as the composition of the two-dimensional perovskite thin film material in this example, in particular (CaBr)2FA59Pb60I181The method comprises the following steps:
step 1, cleaning the FTO conductive glass, namely ultrasonically cleaning the FTO conductive glass by using acetone, isopropanol, ethanol and deionized water in sequence, wherein the cleaning time of each solvent is 30 minutes, transferring the FTO conductive glass to a 120-DEG C oven to be fully dried to remove surface moisture and impurities after cleaning is finished, and then treating the dried FTO conductive glass for 30 minutes by using an ultraviolet-ozone device to wait for later use.
And 2, preparing a compact thin film layer, adding 180 mu L of diisopropoxy-diacetone titanium into 1mL of anhydrous n-butyl alcohol, shaking up, spin-coating the mixed solution onto FTO conductive glass at the speed of 2000rpm, and annealing at the temperature of 100 ℃ for 20 min.
And 3, preparing a mesoporous thin film layer, preparing titanium dioxide and absolute ethyl alcohol into a solution according to the mass ratio of 1:8, stirring for 12 hours, spin-coating the surface of the material prepared in the step 2 at 6000rpm, paving the whole surface with the titanium dioxide, and annealing at 550 ℃ for 40 min.
Step 4, preparing a perovskite light absorption layer precursor solution, preparing 0.05mL of dimethyl sulfoxide and 0.2mL of dimethylformamide into a mixed solvent, adding 0.4425mmol of iodoformamidine, 0.45mmol of lead iodide, 0.18mmol of chloromethylamine, 0.0075mmol of calcium bromide and 0.0075mmol of calcium iodide into the mixed solvent, stirring for 12 hours after magnetic force oscillation is carried out for 10 minutes, and obtaining uniform, clear and transparent (CaBr)2FA59Pb60I181A perovskite precursor solution.
Step 5, preparing a perovskite light absorption layer, spin-coating the precursor solution obtained by the step 4 on the surface of the material prepared in the step 3 at the speed of 5000rpm for 20s before the spin-coating is finishedDropwise adding 1mL of diethyl ether which is used as an anti-solvent and can quickly evaporate the solvent on the spin-coating surface, placing the spin-coated solution in a vacuum environment to remove the residual solvent, placing the solution on a heating table at 110 ℃ for annealing for 20min, and finally obtaining the chemical composition (CaBr) of the light absorption layer2FA59Pb60I181The two-dimensional perovskite solar cell of (1).
Comparative example 1
A two-dimensional perovskite thin film material, wherein n is equal to 1, and the chemical composition of the perovskite thin film material is (CaBr)2PbI4Preparing 0.05mL of dimethyl sulfoxide and 0.2mL of dimethylformamide into a mixed solvent, adding 0.45mmol of lead iodide, 0.18mmol of chloromethane, 0.45mmol of calcium bromide and 0.45mmol of calcium iodide into the mixed solvent, magnetically shaking for 10min, stirring for 12 h to obtain a precursor solution, independently forming a film on the surface of a spin-coating instrument at the speed of 5000rpm, dropwise adding 1mL of diethyl ether 20s before the spin-coating is finished, placing the solution on a heating table at 90 ℃ for annealing for 20min to finally obtain a chemical composition (CaBr)2PbI4The two-dimensional perovskite thin film material.
As shown in FIG. 1, XRD patterns of the two-dimensional perovskite thin film materials prepared in comparative example 1 and examples 1-2 were obtained at annealing temperatures of 90 deg.C, 110 deg.C, and 130 deg.C (CaBr) in comparative example 1 and examples 1-2, respectively2PbI4Two-dimensional perovskite thin film material, as can be seen from FIG. 1, the characteristic diffraction peak of 5-10 degrees represents (CaBr)2FAn-1PbnI3n+1The two-dimensional perovskite thin film structure of (1) shows diffraction peak intensity of the two-dimensional perovskite thin film material prepared in comparative example 1 is significantly lower than that of examples 1 and 2, and therefore, the two-dimensional perovskite thin film material prepared at 90 ℃ annealing temperature (CaBr)2PbI4The grain size of the two-dimensional perovskite thin film material is obviously smaller than that of the thin film material prepared by adopting the annealing temperatures of 110 ℃ and 130 ℃, which indicates that the too low annealing temperature hinders the grain growth of the perovskite thin film and is not beneficial to being used as a light absorption layer material to absorb more light, so that the annealing temperature of the perovskite light absorption layer is required to be controlled to be more than 110 ℃;
as shown in fig. 2, which shows the steady-state photoluminescence spectra of the two-dimensional perovskite solar cells prepared in examples 3 to 5, perovskite solar cells were prepared in examples 3 to 5, respectively, and the values of n of the light-absorbing layer materials were 20, 40, and 60, respectively. It can be seen from fig. 2 that the peak intensity of the spectrum gradually increases with the gradual increase of the n value, which indicates that the non-radiative recombination of the perovskite solar cell gradually decreases and the light absorption capability is stronger, so that the carrier concentration of the perovskite light absorption layer increases, the carrier lifetime is improved, and the performance stability of the cell is better;
as shown in fig. 3, which is the transient photoluminescence spectrum of the two-dimensional perovskite solar cells prepared in examples 3 to 5, it can be seen from fig. 3 that the decay time is gradually longer as the n value is gradually increased, which indicates that the lifetime of the carriers is longer when the perovskite solar cell is operated, which also means that the grain size is gradually increased as the n value is increased, and it can also be indicated that the better the performance of the solar cell is, the higher the quality of the light absorbing layer thin film material is.
It should be noted that the terms "upper", "lower", "left", "right", "front", "back", etc. used in the present invention are for clarity of description only, and are not intended to limit the scope of the present invention, and the relative relationship between the terms and the terms is not limited by the technical contents of the essential changes.
The above is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above-mentioned embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention.

Claims (10)

1. A two-dimensional perovskite thin film material is characterized in that iodoformamidine, lead iodide, chloromethane, calcium bromide and calcium iodide are used as raw materials, the molar ratio of the raw materials is n-1: n:0.4n:1:1, the iodoformamidine, the lead iodide, the chloromethane, the calcium bromide and the calcium iodide are added into a mixed solvent of dimethylformamide and dimethyl sulfoxide, stirring is carried out to obtain a uniform, clear and transparent precursor solution, the volume ratio of the dimethylformamide to the dimethyl sulfoxide is 1:4, and the lead iodide is addedThe concentration of the precursor solution in the mixed solvent is 1.8mol/L, the solvent remained in the film is removed after the precursor solution is spin-coated to form the film, the two-dimensional perovskite film material is obtained after annealing treatment, the annealing temperature is 110-170 ℃, the annealing time is 10-20 min, and the chemical composition of the film material is (CaBr)2(FA)n- 1PbnI3n+1And n is 1 to infinity, wherein FA is formamidine cation.
2. A two-dimensional perovskite solar cell, characterized in that the perovskite solar cell comprises in order: the electronic transmission layer sequentially comprises a compact thin film layer and a mesoporous thin film layer, and the perovskite light absorption layer is the two-dimensional perovskite thin film material as claimed in claim 1.
3. The two-dimensional perovskite solar cell according to claim 2, wherein the dense thin film layer is prepared by taking diisopropoxy diacetone titanium and anhydrous n-butanol as raw materials, the volume ratio of the diisopropoxy diacetone titanium to the anhydrous n-butanol is 1 (16-20), the two raw materials are uniformly mixed and then spin-coated on the surface of a conductive substrate to form a film, and the dense thin film layer is obtained through annealing treatment at 400-550 ℃ for 40-60 min.
4. The two-dimensional perovskite solar cell according to claim 2, wherein the mesoporous thin film layer is prepared from titanium dioxide and absolute ethyl alcohol in a mass ratio of 1 (2-8), the two raw materials are mixed into a uniform and non-layered suspension, the surface of the dense thin film layer is subjected to spin coating to form a film, the dense thin film layer is obtained through annealing treatment, the annealing temperature is 100-130 ℃, and the annealing time is 10-20 min.
5. A method of manufacturing a two-dimensional perovskite solar cell as defined in any one of claims 2 to 4, comprising the steps of:
step 1: pretreating the conductive substrate;
step 2: preparing a compact film layer;
and step 3: preparing a mesoporous thin film layer;
and 4, step 4: preparing a perovskite light absorption layer precursor solution;
and 5: and preparing the perovskite light absorption layer.
6. The method for preparing a two-dimensional perovskite solar cell according to claim 5, wherein the specific method in the step 1 is as follows: ultrasonically cleaning a conductive substrate by sequentially adopting acetone, isopropanol, ethanol and deionized water, wherein the time for treating the conductive substrate by each solvent is 30min, drying after cleaning, and carrying out ultraviolet-ozone treatment; the conductive substrate is FTO conductive glass.
7. The method for preparing a two-dimensional perovskite solar cell according to claim 5, wherein the specific method in the step 2 is as follows: adding diisopropoxy-diacetone titanium into anhydrous n-butyl alcohol, wherein the volume ratio of the diisopropoxy-diacetone titanium to the anhydrous n-butyl alcohol is 1 (16-20), uniformly mixing, spin-coating on the conductive substrate, and annealing to obtain a compact thin film layer; the annealing temperature is 100-130 ℃, and the annealing time is 10-20 min.
8. The method for preparing a two-dimensional perovskite solar cell according to claim 5, wherein the specific method in the step 3 is as follows: preparing uniform suspension from titanium dioxide and absolute ethyl alcohol, wherein the mass ratio of the titanium dioxide to the absolute ethyl alcohol is 1 (2-8), spin-coating the suspension on the compact thin film layer, and annealing to obtain the mesoporous thin film layer, wherein the annealing temperature is 400-550 ℃, and the annealing time is 40-60 min.
9. The method for preparing a two-dimensional perovskite solar cell according to claim 5, wherein the specific method of the step 4 is as follows: adding iodoformamidine, lead iodide, chloromethane, calcium bromide and calcium iodide into a mixed solvent of dimethylformamide and dimethyl sulfoxide according to the proportion of n-1: n:0.4n:1:1, wherein the concentration of lead iodide in the mixed solvent is 1.8mol/L, and the volume ratio of dimethylformamide to dimethyl sulfoxide is 1:4, mixing the iodoformamidine, lead iodide, chloromethane, calcium bromide and calcium iodide with the mixed solvent, vibrating by magnetic force for 10min, and stirring until the solution is uniform, clear and transparent to obtain a perovskite light absorption layer precursor solution.
10. The method for preparing a two-dimensional perovskite solar cell according to claim 5, wherein the specific method of the step 5 is as follows: spin-coating a perovskite precursor solution on the mesoporous thin film layer, dropwise adding 1mL of diethyl ether in the spin-coating process, placing the film in a vacuum environment after spin-coating to remove a solvent, and annealing to obtain the two-dimensional perovskite thin film material, wherein the annealing temperature is 110-170 ℃, and the annealing time is 10-20 min.
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