CN110718632A - Method for preparing large-area perovskite layer and perovskite solar cell - Google Patents
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Abstract
The invention discloses a method for preparing a large-area perovskite layer and a perovskite solar cell, wherein the method comprises the following steps: coating a perovskite precursor solution on a substrate to form a perovskite precursor layer; adding a mixed anti-solvent, and annealing to obtain a perovskite layer; the mixed anti-solvent is formed by mixing a solvent A and a solvent B, wherein the solvent A is selected from any one of toluene, chlorobenzene, dichloromethane, ethyl acetate, anisole and diethyl ether, the solvent B is selected from any one of toluene, chlorobenzene, dichloromethane, ethyl acetate, anisole and monohydric alcohol with 3-6 carbon atoms, the solvent A and the solvent B are different, and the solvent A accounts for 10-90% of the volume ratio of the mixed anti-solvent. The invention utilizes the mixed anti-solvent to reduce the supersaturation degree of the perovskite precursor liquid in the crystallization process, so that crystallization nucleation sites are uniformly generated, and finally the perovskite thin film with uniform film formation and large grain size is obtained.
Description
Technical Field
The invention relates to the technical field of solar cells, in particular to a method for preparing a large-area perovskite layer and a perovskite solar cell.
Background
Solar energy is renewable clean energy, and the development of efficient and low-cost solar cells becomes an effective means for people to fully utilize the solar energy. The silicon-based solar cell is widely applied to the market due to the mature preparation process and occupies the leading low position of the market. However, since the silicon-based solar cell has a high energy consumption and high cost of the manufacturing process, the development of a novel thin film solar cell with high efficiency and low cost is an urgent need in the market.
Perovskite solar cells utilize organometallic halide semiconductors as light absorbing materials, which have attracted extensive research interest due to their excellent carrier mobility, high absorption coefficient, and low cost solution processing characteristics. The perovskite solar cell has the photoelectric conversion efficiency of 3.8% in 2009 to more than 25% in 2019, and is close to the efficiency of the traditional crystalline silicon solar cell and a cadmium telluride (CdTe) thin film solar cell, and the perovskite solar cell has the advantages of excellent photoelectric conversion performance and low-cost preparation, has received great attention from the industry, and becomes a novel thin film solar cell with great market potential.
In the preparation of the perovskite solar cell, the crystallization film formation of the perovskite active layer is critical, and particularly for the film formation of a large-area device, the realization of a large-area continuous perovskite layer is a key factor for restricting the large-scale production of the perovskite solar cell. The common perovskite film solution preparation method comprises a one-step method and a two-step method, wherein the two-step perovskite film preparation process is not suitable for large-area preparation of perovskite films due to the defects of multiple steps, incomplete reaction, poor repeatability and the like. The one-step method has the advantages that the anti-solvent is added immediately at the later stage of coating the perovskite solution to quickly saturate the perovskite solution, then crystal nuclei are formed and the film is formed through crystallization. There is a need to find a method for producing a perovskite layer that can be formed uniformly over a large area.
Disclosure of Invention
The invention aims to provide a method for preparing a large-area perovskite layer and a perovskite solar cell.
The technical scheme adopted by the invention is as follows:
the invention provides a method for preparing a large-area perovskite layer, which comprises the following steps:
coating a perovskite precursor solution on a substrate to form a perovskite precursor layer;
adding a mixed anti-solvent into the perovskite precursor layer, and annealing to obtain a perovskite layer;
the mixed anti-solvent is a mixed solvent formed by mixing a solvent A and a solvent B, wherein the solvent A is selected from any one of toluene, chlorobenzene, dichloromethane, ethyl acetate, anisole and diethyl ether, the solvent B is selected from any one of toluene, chlorobenzene, dichloromethane, ethyl acetate, anisole and monohydric alcohol with 3-6 carbon atoms, the solvent A and the solvent B are different, and the solvent A accounts for 10-90% of the mixed anti-solvent in volume ratio. When different solvents A and B are selected to form different mixed anti-solvents, the volume ratio ranges of the solvents A capable of improving the large-area film forming uniformity of the perovskite layer are different, and the optimal volume ratio range can be determined through experiments.
The mixed anti-solvent is a solvent which is difficult to dissolve the perovskite and does not react with the perovskite. The function of the "substrate" is to provide a platform for coating the perovskite precursor solution, and the material is not limited, and can be changed according to different actual requirements.
Preferably, the monohydric alcohol of 3-6 carbon atoms includes but is not limited to isopropanol, sec-amyl alcohol, and the like, while methanol and ethanol have destructive effects on the perovskite layer.
Preferably, the area of the perovskite layer is more than or equal to 100cm2。
Preferably, the thickness of the perovskite layer is 200-1000 nm.
Preferably, the perovskite material in the perovskite layer is ABX3The perovskite type comprises A and B, wherein A comprises at least one of methylamine, formamidine, cesium, rubidium, potassium and sodium, B comprises at least one of lead, tin, germanium and bismuth, and X comprises at least one of iodine, bromine and chlorine.
The invention also provides a perovskite layer which is prepared by the method for preparing the large-area perovskite layer.
The invention also provides a perovskite solar cell which comprises the perovskite layer.
Preferably, the perovskite solar cell comprises a substrate, a transparent conductive electrode, an electron transport layer, the perovskite layer and a carbon electrode which are sequentially stacked; or the perovskite solar cell comprises a substrate, a transparent conductive electrode, an electron transport layer, the perovskite layer, a hole transport layer and a metal electrode which are sequentially stacked.
Preferably, the electron transport layer is selected from one or two of titanium dioxide, zinc dioxide, tin dioxide, graphene and PCBM.
Preferably, the hole transport layer is selected from the group consisting of Spiro-OMeTAD, PEDOT PSS, TPD, PTAA, P3HT, PCPDTBT, NixO、V2O5、CuI、MoO3、CuO、Cu2Any one of O.
More preferably, the thickness of the electron transport layer is 5 to 100 nm.
Preferably, the transparent conductive electrode is Indium Tin Oxide (ITO), fluorine-doped tin oxide (FTO), or aluminum-doped zinc oxide (AZO).
Preferably, the substrate may be a flexible substrate, and the material thereof includes, but is not limited to, polyimide, polyethylene terephthalate or polyethersulfone resin, and the like. The substrate may also be a rigid substrate, the material of which includes, but is not limited to, glass, and the like.
The invention has the beneficial effects that:
when a large-area perovskite layer is prepared, the research of the embodiment of the invention finds that the problem of nonuniform film formation is easily caused by using a single anti-solvent, and the use of a mixed anti-solvent with a certain mixing ratio can reduce the supersaturation degree of the perovskite precursor liquid in the crystallization process, so that crystallization nucleation sites are uniformly generated, and finally, the perovskite thin film with uniform film formation and large grain size is obtained, the efficiency and the stability of a large-area device are improved, and the invention has good application prospect in the field of preparing large-area perovskite devices.
Drawings
FIG. 1 shows 100cm for example 1 and comparative example 12Scanning electron microscope pictures of different region positions in the perovskite thin film region;
fig. 2 is a graph of the performance of a series carbon electrode perovskite solar cell in example 2 as a function of the volume fraction of ethyl acetate.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
Example 1
This example provides a perovskite solar cell, prepared according to the following steps:
preparing 40nm dense titanium dioxide on an FTO glass substrate with the area of 10cm multiplied by 10cm by spray pyrolysis, and spin-coating a mesoporous layer TiO with the thickness of 300nm2. Then spin coating MAPbI3Precursor solution in which MAPbI is dissolved3The solvent of the precursor is a mixed solvent of DMSO and DMF, a mixed anti-solvent of toluene and ethyl acetate (toluene: ethyl acetate volume ratio is 1: 1) is dripped 15s before the spin coating is finished, and the mixture is annealed at 100 ℃ for 30min to obtain a compact perovskite thin film with the thickness of 500 nm. And mixing graphite, carbon black, polymethyl methacrylate and isopropanol to form carbon slurry, and coating the carbon slurry on the prepared perovskite thin film to form a carbon electrode, so as to prepare the carbon electrode perovskite solar cell.
Comparative example 1: comparative example 1 provides a carbon electrode perovskite solar cell, which is fabricated by the same procedure as in example 1, except that a perovskite thin film is fabricated using only toluene as an anti-solvent.
The perovskite thin films obtained in example 1 and comparative example 1 were subjected to surface morphology characterization by 100cm2Scanning electron micrographs of different region positions in the perovskite thin film region are shown in FIG. 1, in which a in FIG. 1 represents the scanning electron micrographs of different region positions of the perovskite thin film prepared using toluene alone as an anti-solvent in comparative example 1, b represents the scanning electron micrographs of different region positions of the perovskite thin film prepared using a mixed anti-solvent formed of toluene and ethyl acetate in example 1, and c represents 100cm2Position schematic of different region positions in the perovskite thin film region. As can be seen from fig. 1, the perovskite thin film formed by using only toluene as the anti-solvent in comparative example 1 has very different film formation in different region positions (the region positions are respectively the corner, the middle, the center and the edge), while the perovskite thin film formed by using the mixed anti-solvent in example 1 has very uniform film formation and almost consistent SEM morphology at different region positions. The result shows that the method of using the mixed anti-solvent can improve the uniformity and the grain size of the large-area film formation of the perovskite layer, and has great significance for preparing large-area perovskite devices.
The carbon electrode perovskite solar cell prepared by only using toluene as an anti-solvent and obtained in the comparative example 1 is taken for testing, and the photoelectric conversion efficiency of the solar cell is 6.7%. The test of the carbon electrode perovskite solar cell obtained by the mixed anti-solvent of toluene and ethyl acetate (volume ratio 1: 1) in the embodiment shows that the photoelectric conversion efficiency is 9.7%, and the experiment shows that the photoelectric conversion efficiency of the solar cell can be improved by the treatment of the mixed anti-solvent.
When the stability of the solar cell obtained by the treatment of the mixed anti-solvent of toluene and ethyl acetate (volume ratio of 1: 1) in the example in the air is measured under the non-packaging condition, the photoelectric conversion efficiency of the non-packaged device is only reduced by 5% after 500 hours, while the photoelectric conversion efficiency of the solar cell obtained by the treatment of the anti-solvent of toluene in the comparative example 1 is reduced by 51% after 500 hours, which indicates that the stability of the solar cell treated by the mixed anti-solvent of toluene and ethyl acetate is also greatly improved.
Example 2
To investigate the effect of different solvent ratios in a mixed anti-solvent formed of two solvents on the performance of the devices formed, this example provides a series of carbon electrode perovskite solar cells, which were prepared in the same manner as in example 1, except that the volume ratios of EA in the mixed anti-solvent formed using Ethyl Acetate (EA) and toluene (Tol) were 0, 0.2, 0.4, 0.5, 0.6, 0.8, and 1.0, respectively.
The prepared series of carbon-based solar cells are tested, and the Photoelectric Conversion Efficiency (PCE) and the short-circuit current density (J) of the series of carbon-based solar cells are obtainedSC) As shown in fig. 2, when the EA/(EA + Tol) is 0.8, the photoelectric conversion efficiency of the formed perovskite solar cell with the large-area carbon electrode is the lowest, and the perovskite solar cell with the large-area carbon electrode is the descending trend, the embodiment of the invention further researches and discovers that the photoelectric conversion efficiency of the formed perovskite solar cell with the large-area carbon electrode is the highest and the performance of the perovskite solar cell is improved when EA/(EA + Tol) is 0.5.
Example 3
Preparing 40nm dense titanium dioxide on an FTO glass substrate with the area of 10cm multiplied by 10cm by spray pyrolysis, and spin-coating a mesoporous layer TiO with the thickness of 300nm2. Then spin coating MAPbI3Precursor solution in which MAPbI is dissolved3The solvent of the precursor is a mixed solvent of DMSO and DMF, a mixed anti-solvent of chlorobenzene and ethyl acetate (chlorobenzene: ethyl acetate volume ratio is 5: 1) is dripped 15s before the spin coating is finished, and the compact perovskite thin film with the thickness of 500nm is obtained after annealing at 100 ℃ for 30 min. Mixing graphite, carbon black, polymethyl methacrylate and isopropanol to form carbon slurry, and blade-coating carbon on the prepared perovskite filmThe slurry is used as a carbon electrode to prepare and form the carbon electrode perovskite solar cell.
Comparative example 2: comparative example 2 provides a carbon electrode perovskite solar cell, which was fabricated by the same procedure as in example 3, except that a perovskite thin film was fabricated using only toluene as an anti-solvent.
The carbon electrode perovskite solar cell prepared by only using chlorobenzene as an anti-solvent and obtained in the comparative example 2 is tested, and the photoelectric conversion efficiency of the solar cell is 5.8%. The carbon electrode perovskite solar cell obtained by the mixed anti-solvent of chlorobenzene and ethyl acetate (volume ratio is 5: 1) in the embodiment is tested, the photoelectric conversion efficiency of the carbon electrode perovskite solar cell is 7.6%, and experiments show that the photoelectric conversion efficiency of the solar cell can be improved by using the mixed anti-solvent for treatment.
When the stability of the solar cell obtained by the mixed anti-solvent treatment of chlorobenzene and ethyl acetate (volume ratio of 5: 1) in the embodiment in the air is measured under the non-packaging condition, the photoelectric conversion efficiency of the non-packaged device is only reduced by 16% after 500 hours, while the photoelectric conversion efficiency of the solar cell obtained by the comparative example 1 by only using chlorobenzene as the anti-solvent treatment is reduced by 48% after 500 hours, which indicates that the stability of the solar cell treated by the mixed anti-solvent of chlorobenzene and ethyl acetate is also greatly improved.
Example 4
Preparing 40nm dense titanium dioxide on an FTO glass substrate with the area of 10cm multiplied by 10cm by spray pyrolysis, and spin-coating a mesoporous layer TiO with the thickness of 300nm2. Then spin coating MAPbI3Precursor solution in which MAPbI is dissolved3The solvent of the precursor is a mixed solvent of DMSO and DMF, an anti-solvent of anisole and isopropanol (the volume ratio of anisole to isopropanol is 4: 1) is added dropwise 15s before the spin coating is finished, and the mixture is annealed at 100 ℃ for 30min to obtain a compact perovskite thin film with the thickness of 400 nm. And mixing graphite, carbon black, polymethyl methacrylate and isopropanol to form carbon slurry, and coating the carbon slurry on the prepared perovskite thin film to form a carbon electrode, so as to prepare the carbon electrode perovskite solar cell.
Comparative example 3: comparative example 3 provides a carbon electrode perovskite solar cell, which was fabricated by the same procedure as in example 4, except that the perovskite thin film was fabricated using only anisole as an anti-solvent.
The carbon electrode perovskite solar cell prepared by only using anisole as an anti-solvent and obtained in the comparative example 3 is taken for testing, and the photoelectric conversion efficiency of the solar cell is 5.9%. The carbon electrode perovskite solar cell obtained by the mixed anti-solvent of anisole and isopropanol (volume ratio is 4: 1) in the embodiment is tested, the photoelectric conversion efficiency of the carbon electrode perovskite solar cell is 8.2%, and experiments show that the photoelectric conversion efficiency of the solar cell can be improved by using the mixed anti-solvent treatment.
When the stability of the solar cell obtained by the mixed anti-solvent treatment of anisole and isopropanol (volume ratio 4: 1) in the example in the air is measured under the non-packaging condition, the photoelectric conversion efficiency of the non-packaged device is only reduced by 16% after 500 hours, while the photoelectric conversion efficiency of the solar cell obtained by the comparative example 1 by only using the anisole as the anti-solvent treatment is reduced by 57% after 500 hours, which indicates that the stability of the solar cell treated by the mixed anti-solvent treatment of anisole and isopropanol is also greatly improved.
Example 5
Preparing 40nm dense titanium dioxide on an FTO glass substrate with the area of 10cm multiplied by 10cm by spray pyrolysis, and spin-coating a mesoporous layer TiO with the thickness of 300nm2. Then spin coating MAPbI3Precursor solution in which MAPbI is dissolved3The solvent of the precursor is a mixed solvent of DMSO and DMF, a mixed anti-solvent of toluene and ethyl acetate (toluene: ethyl acetate volume ratio is 1: 1) is dripped 15s before the spin coating is finished, and the mixture is annealed at 100 ℃ for 30min to obtain a compact perovskite thin film with the thickness of 500 nm. And spin-coating PTAA with the thickness of 50nm on the perovskite thin film to be used as a hole transport layer, and then evaporating a silver electrode to prepare and form the perovskite solar cell.
Comparative example 4: comparative example 4 provides a perovskite solar cell, which was fabricated by the same procedure as in example 5, except that a perovskite thin film was fabricated using only toluene as an anti-solvent.
The perovskite solar cell obtained in the comparative example 4 and prepared by only using toluene as an anti-solvent is tested, and the photoelectric conversion efficiency of the solar cell is 10.8%. The perovskite solar cell obtained by the mixed anti-solvent of toluene and ethyl acetate (volume ratio 1: 1) in the embodiment is tested, the photoelectric conversion efficiency of the perovskite solar cell is 14.6%, and experiments show that the photoelectric conversion efficiency of the perovskite solar cell can be improved by the mixed anti-solvent treatment.
When the stability of the solar cell obtained by the treatment of the mixed anti-solvent of toluene and ethyl acetate (volume ratio of 1: 1) in the example in the air under the non-packaging condition is measured, the photoelectric conversion efficiency of the non-packaged device is only reduced by 11% after 500 hours, while the photoelectric conversion efficiency of the solar cell obtained by the treatment of the anti-solvent of toluene only in the comparative example 1 is reduced by 42% after 500 hours, which indicates that the stability of the solar cell treated by the mixed anti-solvent of toluene and ethyl acetate is also greatly improved.
Example 6
Preparing 40nm zinc oxide on an ITO glass substrate with an area of 15cm multiplied by 15cm by spray pyrolysis, and then spin-coating MAPbBr3Precursor solution in which MAPbBr is dissolved3The solvent of the precursor is a mixed solvent of DMSO and DMF, a mixed anti-solvent of toluene and ethyl acetate (toluene: ethyl acetate volume ratio is 1: 1) is dripped 15s before the spin coating is finished, and the compact perovskite thin film with the thickness of 800nm is obtained after annealing at 100 ℃ for 30 min. And spin-coating PTAA with the thickness of 50nm on the perovskite thin film to be used as a hole transport layer, and then evaporating a silver electrode to prepare and form the perovskite solar cell.
Comparative example 5: comparative example 5 provides a perovskite solar cell, which was fabricated by the same procedure as in example 6, except that a perovskite thin film was fabricated using only toluene as an anti-solvent.
The perovskite solar cell obtained in the comparative example 5 and prepared by only using toluene as an anti-solvent and the perovskite solar cell in the embodiment are tested, and through the test, the perovskite solar cell obtained in the embodiment has higher photoelectric conversion efficiency and stability than the perovskite solar cell in the comparative example 5.
Claims (10)
1. A method of producing a large area perovskite layer comprising the steps of:
coating a perovskite precursor solution on a substrate to form a perovskite precursor layer;
adding a mixed anti-solvent into the perovskite precursor layer, and annealing to obtain a perovskite layer;
the mixed anti-solvent is a mixed solvent formed by mixing a solvent A and a solvent B, wherein the solvent A is selected from any one of toluene, chlorobenzene, dichloromethane, ethyl acetate, anisole and diethyl ether, the solvent B is selected from any one of toluene, chlorobenzene, dichloromethane, ethyl acetate, anisole and monohydric alcohol with 3-6 carbon atoms, the solvent A and the solvent B are different, and the solvent A accounts for 10-90% of the mixed anti-solvent in volume ratio.
2. The method of claim 1, wherein the area of the perovskite layer is 100cm or more2。
3. The method of producing a large area perovskite layer as claimed in claim 1, wherein the thickness of the perovskite layer is 200 to 1000 nm.
4. The method of producing large area perovskite layer as claimed in claim 1, wherein the perovskite material in the perovskite layer is ABX3The perovskite type comprises A and B, wherein A comprises at least one of methylamine, formamidine, cesium, rubidium, potassium and sodium, B comprises at least one of lead, tin, germanium and bismuth, and X comprises at least one of iodine, bromine and chlorine.
5. A perovskite layer obtained by the method for producing a large-area perovskite layer according to any one of claims 1 to 4.
6. A perovskite solar cell comprising the perovskite layer as defined in claim 5.
7. The perovskite solar cell according to claim 6, comprising a substrate, a transparent conductive electrode, an electron transport layer, the perovskite layer of claim 5 and a carbon electrode, in that order, stacked; or the perovskite solar cell comprises a substrate, a transparent conductive electrode, an electron transport layer, the perovskite layer of claim 5, a hole transport layer and a metal electrode which are sequentially stacked.
8. The perovskite solar cell of claim 7, wherein the electron transport layer is selected from one or two of titanium dioxide, zinc dioxide, tin dioxide, graphene, PCBM.
9. The perovskite solar cell according to claim 7, wherein the hole transport layer is selected from the group consisting of Spiro-OMeTAD, PEDOT PSS, TPD, PTAA, P3HT, PCPDTBT, NixO、V2O5、CuI、MoO3、CuO、Cu2Any one of O.
10. The perovskite solar cell of claim 7, wherein the transparent conductive electrode is indium tin oxide, fluorine doped tin oxide, or aluminum doped zinc oxide.
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| CN111799382A (en) * | 2020-06-30 | 2020-10-20 | 厦门大学 | Preparation method of perovskite precursor containing methylamine molecules |
| CN112735945A (en) * | 2021-02-02 | 2021-04-30 | 河南大学 | Stannous chloride doped inorganic perovskite thin film, preparation method and application thereof |
| CN113571651A (en) * | 2021-07-21 | 2021-10-29 | 北京大学 | Solution medium annealing method for preparing perovskite thin film photoelectric device |
| WO2023051494A1 (en) | 2021-09-28 | 2023-04-06 | 天合光能股份有限公司 | Large-area perovskite layer and preparation method therefor |
| WO2024119873A1 (en) * | 2022-12-08 | 2024-06-13 | 隆基绿能科技股份有限公司 | Method and system for selecting anti-solvent for use in preparation of perovskite absorber layer |
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| CN111370579A (en) * | 2020-03-31 | 2020-07-03 | 天津师范大学 | Preparation method of metal organic hybrid perovskite ferroelectric film |
| CN111370579B (en) * | 2020-03-31 | 2023-04-18 | 天津师范大学 | Preparation method of metal organic hybrid perovskite ferroelectric film |
| CN111490166A (en) * | 2020-04-24 | 2020-08-04 | 电子科技大学 | Flexible perovskite photoelectric detector based on novel polymer hole transport layer and preparation method thereof |
| CN111490166B (en) * | 2020-04-24 | 2023-07-04 | 电子科技大学 | Flexible perovskite photoelectric detector based on polymer hole transport layer and preparation method thereof |
| CN111799382A (en) * | 2020-06-30 | 2020-10-20 | 厦门大学 | Preparation method of perovskite precursor containing methylamine molecules |
| CN112735945A (en) * | 2021-02-02 | 2021-04-30 | 河南大学 | Stannous chloride doped inorganic perovskite thin film, preparation method and application thereof |
| CN113571651A (en) * | 2021-07-21 | 2021-10-29 | 北京大学 | Solution medium annealing method for preparing perovskite thin film photoelectric device |
| CN113571651B (en) * | 2021-07-21 | 2023-10-20 | 北京大学 | Solution medium annealing method for preparing perovskite thin film photoelectric device |
| WO2023051494A1 (en) | 2021-09-28 | 2023-04-06 | 天合光能股份有限公司 | Large-area perovskite layer and preparation method therefor |
| WO2024119873A1 (en) * | 2022-12-08 | 2024-06-13 | 隆基绿能科技股份有限公司 | Method and system for selecting anti-solvent for use in preparation of perovskite absorber layer |
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