CN111446370A - Preparation method of large-area quasi-single crystal perovskite film by cavity limited-area in-situ growth - Google Patents
Preparation method of large-area quasi-single crystal perovskite film by cavity limited-area in-situ growth Download PDFInfo
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Abstract
The invention discloses a preparation method of a large-area quasi-single crystal perovskite thin film by cavity limited in-situ growth, which comprises the steps of firstly constructing a metal cavity electrode with a specific shape and specification on a large-area transparent conductive substrate to reduce the internal resistance of a device, then preparing a current carrier transmission layer on the surface of the metal cavity electrode, then depositing functionalized graphene quantum dots on the metal cavity electrode, finally growing the perovskite thin film by cavity limited in-situ growth, and promoting the uniform and rapid growth of the quasi-single crystal perovskite by using a poor solvent standing method to prepare the large-area quasi-single crystal perovskite thin film. The quasi-single crystal perovskite thin film obtained by the invention has large area, few crystal boundaries, few defects, controllable thickness and low internal resistance, and can be directly applied to photovoltaic devices.
Description
Technical Field
The invention belongs to the technical field of thin-film solar cells, and particularly relates to a preparation method of a large-area quasi-single-crystal perovskite thin film grown in situ in a cavity limited area.
Background
In recent years, Perovskite Solar Cells (PSC) have attracted academia and industry due to unique optoelectronic properties and low preparation cost of organic-inorganic hybrid perovskite materialsBrings new development opportunities for the photovoltaic field. From 2009 to date, the laboratory photoelectric conversion efficiency of PSCs has been refreshed from 3.8% in 2009 to a certified efficiency of 25.2% in 2019. However, most of these certified or reported efficient PSCs are based on relatively small areas (typically 0.1 cm)2And some smaller to 0.03cm2). The spin coating technology is low in cost and easy to operate, and can realize the total area of the device of 100cm2(effective area 50.6 cm)2) Preparation of photoelectric conversion efficiency of 13%, but area exceeding 100cm2It is difficult to obtain a uniform film. Therefore, other solution-based techniques, such as knife coating, slot die coating, meniscus assisted solution printing, screen printing, spray coating, soft film blanket deposition, and ink jet printing, have also been developed by researchers. However, the perovskites prepared by the solution method are all of polycrystalline perovskite structures, and a large number of grain boundaries and defects exist, so that the method is not favorable for obtaining efficient and stable PSC devices. Compared with a polycrystalline thin film of perovskite, the crystal boundary-free single crystal perovskite has better thermal stability, wider light absorption range, lower hole concentration and higher carrier mobility. At present, the preparation method of the single crystal perovskite mainly comprises an anti-solvent method, a cooling crystallization method, a heating crystallization method, a top seed crystal solution growth method, a slow evaporation solvent method, a Bridgman method and the like. However, the single crystal perovskite particles obtained by the preparation method of the single crystal perovskite are further applied to photovoltaic devices, a complex single crystal thinning process is needed, microcracks are easily introduced in the thinning process, and the device performance of the solar cell is reduced.
The quasi-single crystal perovskite is between the polycrystalline perovskite and the single crystal perovskite, the grain boundary and the defect of the quasi-single crystal perovskite are obviously smaller than those of the polycrystalline perovskite, and the preparation requirement and the cost of the quasi-single crystal perovskite are smaller than those of the single crystal perovskite. Through search, patent CN 110534654A discloses a method for preparing quasi-single crystal perovskite film, which is to prepare small crystal perovskite on a substrate, then put the perovskite in a closed device containing saturated AX atmosphere and prepare the quasi-single crystal perovskite film through a hot pressing method. However, the method does not grow the quasi-single crystal perovskite thin film on the carrier transport layer in situ, and does not construct the embedded metal electrode in advance, so that the thin film has high internal resistance and needs an additional hot-pressing sealing device. Patent CN 107093671A discloses a method for preparing a single crystal perovskite organic metal halide film, which comprises the steps of growing a single crystal perovskite film on a carrier transmission layer, adding an anti-solvent in the growing process to promote perovskite crystallization, and spin-drying the film after the growth is finished, so that the method is not beneficial to preparing a large-area uniform high-quality film, an embedded metal electrode is not constructed in advance, the internal resistance of the film is large, and the photoelectric conversion efficiency is not high; patent CN 107460535a discloses a method for preparing an in-situ grown single crystal perovskite organic metal halide thin film, the method grows a single crystal perovskite thin film on a carrier transport layer, a temperature gradient is set in a single crystal growth region to promote perovskite crystallization, an additional device is needed, an embedded metal electrode is not constructed in advance, the internal resistance of the thin film is large, the area of the single crystal perovskite thin film is limited, and the photoelectric conversion efficiency is not high. Patent CN 108023017A discloses a single crystal film of organic-inorganic composite perovskite material, a preparation method and application thereof, wherein the method utilizes a two-dimensional limited domain induction solution to prepare the organic-inorganic composite large-area perovskite single crystal film. However, the substrate material adopted by the method does not contain a carrier transmission layer, namely, a single crystal perovskite thin film is not directly grown in situ on the surface of the carrier transmission layer; the method adopts a two-dimensional limited domain structure formed by combining substrates, the single crystal perovskite thin film grows between two substrates, and the single crystal perovskite thin film has the same binding force with the two substrates, so that the single crystal perovskite thin film is not beneficial to being removed from one substrate; in addition, the large-area substrate material does not contain an embedded metal electrode, is directly applied to a photovoltaic device, has very large resistance and is not beneficial to obtaining a high-efficiency device. Therefore, the in-situ growth of the large-area high-quality (uniform, few grain boundaries, few defects and low internal resistance) quasi-single crystal perovskite thin film on the carrier transport layer is very important for preparing a high-performance stable large-area photovoltaic device.
Disclosure of Invention
The invention aims to provide a preparation method for a large-area quasi-single crystal perovskite film with cavity limited-area in-situ growth, which can prepare a large-area quasi-single crystal perovskite film with the area larger than 200cm2The quasi-single crystal perovskite thin film has the advantages of few crystal boundaries, few defects, controllable thickness and low internal resistance, and can be directly applied to photovoltaic devices.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a large-area quasi-single crystal perovskite film with cavity limited-area in-situ growth comprises the following steps:
（1）ABX3preparing a perovskite precursor solution: mixing AX and BX2Adding into solvent at equal molar ratio, stirring at 30-100 deg.C for 1-24 hr to obtain ABX with concentration of 0.5-2.5 mol/L3A perovskite precursor liquid;
(2) the method comprises the steps of preparing a metal cavity electrode with a specific shape and specification on a clean large-area transparent conductive substrate with the thickness of 15cm × 15 cm-35 cm × 35cm by using a mask plate through a vacuum thermal evaporation method, preparing a current carrier transmission layer on the surface of the formed metal cavity electrode through the vacuum thermal evaporation method, and finally depositing functionalized graphene quantum dots on the surface of the current carrier transmission layer through an electrophoresis method;
(3) and (3) carrying out cavity limited in-situ growth of the quasi-single crystal perovskite film: placing the substrate containing the functionalized graphene quantum dots prepared in the step (2) into a perovskite growth container, and adding the ABX prepared in the step (1) into the container3The perovskite precursor liquid is placed on a heating panel to carry out cavity limited in-situ growth of the perovskite film in a sealed container; then cooling to room temperature, slowly adding a poor solvent with high density until the substrate is completely immersed, and standing for 1-12 hours; removing unreacted ABX3Cleaning the perovskite precursor solution and the poor solvent with high density for 2-3 times by using the poor solvent with low density, and annealing to obtain the substrate containing the large-area quasi-single crystal perovskite film.
ABX described in step (1)3In the perovskite, A is CH3NH3 +、HC(NH2)2 +、(CH3)4N+、C7H7 +、Rb+And Cs+One ofOr a plurality thereof; b is Ge2+、Sn2+And Pb2+One or more of (a); x is I-、Br-And Cl-One or more of;
the solvent is one or more of gamma-butyrolactone, N-dimethylformamide, dimethyl sulfoxide and N-methyl-2-pyrrolidone.
The transparent conductive substrate in the step (2) is any one of FTO conductive glass, ITO/PEN flexible substrate and ITO/PET flexible substrate; the metal cavity electrode with the specific shape and specification is triangular, quadrangular or hexagonal, preferably square or regular hexagonal, and has the specification of 1-20 mm of side length, 5-100 microns of stem width and 50-500 nm of stem height.
In the step (2), the metal is any one of tin, titanium, zinc, aluminum, nickel and molybdenum.
The thickness of the carrier transport layer prepared in the step (2) is 50-500 nanometers.
The functionalization in step (2) is one or more of amination, sulfhydrylation, carboxylation and halogenation.
The poor solvent with high density in the step (3) is one or more of carbon tetrachloride, carbon trichloride, dichloromethane and carbon disulfide; the poor solvent with low density is one or more of chlorobenzene, toluene, anisole, diethyl ether and C3-C6 monohydric alcohol.
In the step (3), the temperature of the cavity limited-area in-situ growth is 50-200 ℃, and the time is 6-48 hours; the annealing temperature is 50-200 deg.C, and the annealing time is 5-120 min.
The thickness of the obtained large-area quasi-single crystal perovskite thin film is 0.5-1.2 microns.
The invention has the beneficial effects that:
(1) the quasi-single crystal perovskite thin film is prepared in situ on the current carrier transmission layer, so that the crystal boundary and the defects can be obviously reduced, the thickness of the quasi-single crystal perovskite thin film is controllable, and the perovskite thin film can be directly applied to a photovoltaic device without crystal thinning.
(2) According to the invention, by constructing the cavity metal electrode with the three-dimensional confinement structure, the internal resistance of a large-area photovoltaic device can be remarkably reduced, and the formed embedded metal electrode is beneficial to the collection and transmission of current carriers, meanwhile, the embedded metal electrode is beneficial to the vertical growth of quasi-single crystal perovskite, and is beneficial to the rapid removal of a precursor solvent.
(3) After the cavity limited in-situ growth of the perovskite thin film, the poor solvent standing method is adopted for processing, so that the uniform and rapid growth of the quasi-single crystal perovskite can be promoted, and the generated quasi-single crystal perovskite thin film can be protected.
(4) The invention can prepare the product with the area larger than 200cm2The quasi-single crystal perovskite thin film is beneficial to preparing a large-area photovoltaic device, has a lattice structure, can reduce crystal boundaries and defects, and further improves the performance and long-term stability of the photovoltaic device, and meanwhile, the large-area quasi-single crystal perovskite lattice structure has a macroscopic trapezoidal structure, can produce a light trapping effect, and further improves the utilization rate of sunlight.
(5) The preparation method has the advantages of mild and controllable preparation conditions, simplicity, effectiveness and low cost, and is favorable for commercial large-scale production. The film prepared by the method is used for preparing a large-area perovskite solar cell, and when the area of the film is 200cm2And the highest photoelectric conversion efficiency can reach 15.60 percent, and the application requirement of the solar cell can be completely met.
Drawings
Fig. 1 is a schematic diagram of a mask used in embodiment 1 of the present invention and a schematic cross-sectional diagram of a metal cavity electrode formed by using the mask.
Detailed Description
In order to make the content of the present invention easier to understand, the following description will be made with reference to the specific embodiments and accompanying drawings, but the present invention is not limited thereto.
Example 1
（1）FA0.85MA0.15PbI2.55Br0.45Preparing a perovskite precursor solution: 1.02mol of FAI and 1.02mol of PbI20.18mol of MABr and 0.18mol of PbBr2Adding into 1L gamma-butylIn the ester, the mixture was stirred at 80 ℃ for 6 hours to prepare FA at a total concentration of 1.2 mol/L0.85MA0.15PbI2.55Br0.45Perovskite precursor liquid (among others, MA)+Is CH3NH3 +，FA+Is HC (NH)2)2 +）；
(2) Constructing a substrate containing aminated graphene quantum dots, namely preparing a square tin metal cavity electrode on a clean transparent conductive substrate of 15cm × 15cm by using a vacuum thermal evaporation method and a square mask plate with the side length of 10 mm and the stem width of 0.05 mm, wherein the side length, the stem width and the stem height of the square tin metal cavity electrode are respectively 10 mm, 0.05 mm and 300 nm;
(3) and (3) carrying out cavity limited in-situ growth of the quasi-single crystal perovskite film: placing the substrate containing the aminated graphene quantum dots prepared in the step (2) into a perovskite growth container, and adding the FA prepared in the step (1) into the container0.85MA0.15PbI2.55Br0.45Sealing the container of the perovskite precursor solution, and placing the container on a heating panel at 150 ℃ to carry out in-situ growth in a cavity limited area for 12 hours; then cooling to room temperature, slowly adding carbon tetrachloride to completely immerse the substrate, and standing for 4 hours; removing unreacted FA0.85MA0.15PbI2.55Br0.45Cleaning the perovskite film for 3 times by isopropanol with perovskite precursor liquid and carbon tetrachloride; extracting prepared FA with the thickness of about 800 nanometers0.85MA0.15PbI2.55Br0.45The pseudo-single crystal perovskite thin film substrate is placed on a heating panel with the temperature of 135 ℃ for annealing for 30 minutes.
Further carrying out passivation, vapor deposition of a hole transport layer, vacuum thermal evaporation of a silver electrode and paraffin sealing on the surface of the single crystal perovskite film to assemble the film with the effective area of 200cm2The quasi-single crystal perovskite solar cell. When the light intensity is 100mW cm-2The cell photocurrent density was 21.75mA·cm-2The open-circuit voltage is 1.01V, the fill factor is 0.71, and the photoelectric conversion efficiency reaches 15.60%. Under the same condition, the perovskite thin film growing in an unlimited region has very many crystal boundaries and defects and very large internal resistance, can not be effectively assembled into a perovskite solar cell, has very low photoelectric conversion efficiency, and has the light intensity of 100mW cm-2When the cell is used, the photocurrent density of the cell is 5.22mA cm-2The open circuit voltage was 0.74V, the fill factor was 0.31, and the photoelectric conversion efficiency was 1.20%.
Example 2
（1）FA0.85MA0.15PbI2.55Br0.45Preparing a perovskite precursor solution: 1.02mol of FAI and 1.02mol of PbI20.18mol of MABr and 0.18mol of PbBr2Adding into 1L gamma-butyrolactone, stirring at 80 deg.C for 6 hr to obtain FA with total concentration of 1.2 mol/L0.85MA0.15PbI2.55Br0.45Perovskite precursor liquid (among others, MA)+Is CH3NH3 +，FA+Is HC (NH)2)2 +）；
(2) Constructing a substrate containing sulfhydrylation graphene quantum dots, namely preparing a regular-hexagon titanium metal cavity electrode on a clean transparent conductive substrate of 15cm × 15cm by using a regular-hexagon mask plate with the side length of 10 mm and the stem width of 0.05 mm by using a vacuum thermal evaporation method, wherein the side length, the stem width and the stem height of the regular-hexagon mask plate are respectively 10 mm, 0.05 mm and 300 nm;
(3) and (3) carrying out cavity limited in-situ growth of the quasi-single crystal perovskite film: placing the substrate containing the sulfhydrylation graphene quantum dots prepared in the step (2) into a perovskite growth container, and adding the FA prepared in the step (1) into the container0.85MA0.15PbI2.55Br0.45Placing a sealed container in a cavity on a heating panel at 150 ℃ to grow in situ for 12 hours; then coolingCooling to room temperature, slowly adding carbon tetrachloride to completely immerse the substrate, and standing for 4 hours; removing unreacted FA0.85MA0.15PbI2.55Br0.45Cleaning the perovskite film for 3 times by isopropanol with perovskite precursor liquid and carbon tetrachloride; extracting prepared FA with the thickness of about 800 nanometers0.85MA0.15PbI2.55Br0.45The pseudo-single crystal perovskite thin film substrate is placed on a heating panel with the temperature of 135 ℃ for annealing for 30 minutes.
Further carrying out passivation, vapor deposition of a hole transport layer, vacuum thermal evaporation of a silver electrode and paraffin sealing on the surface of the single crystal perovskite film to assemble the film with the effective area of 200cm2The quasi-single crystal perovskite solar cell. When the light intensity is 100mW cm-2When the cell is used, the photocurrent density of the cell is 20.43mA cm-2The open-circuit voltage is 1.02V, the fill factor is 0.70, and the photoelectric conversion efficiency reaches 14.59%. Under the same condition, the perovskite thin film growing in an unlimited region has very many crystal boundaries and defects and very large internal resistance, can not be effectively assembled into a perovskite solar cell, has very low photoelectric conversion efficiency, and has the light intensity of 100mW cm-2When the cell is used, the photocurrent density of the cell is 4.95mA cm-2The open circuit voltage was 0.71V, the fill factor was 0.29, and the photoelectric conversion efficiency was 1.02%.
Example 3
（1）MAPbI3Preparing a perovskite precursor solution: mixing MAI and PbI2Adding the mixture into a mixed solvent of N, N-dimethylformamide and dimethyl sulfoxide with the volume ratio of 4:1 according to an equimolar ratio, stirring the mixture for 6 hours at 70 ℃, and preparing MAPbI with the concentration of 1.2 mol/L3Perovskite precursor liquid (among others, MA)+Is CH3NH3 +）；
(2) Constructing a substrate containing aminated graphene quantum dots, namely preparing a square tin metal cavity electrode on a clean transparent conductive substrate of 15cm × 15cm by using a vacuum thermal evaporation method and a square mask (shown in figure 1) with the side length of 10 mm and the stem width of 0.05 mm, preparing a tin dioxide electron transport layer with the thickness of 100 nm on the surface of the tin metal cavity electrode by using a vacuum thermal evaporation method (without the mask), and finally depositing the aminated graphene quantum dots on the surface of the tin dioxide electron transport layer by using an electrophoresis method;
(3) and (3) carrying out cavity limited in-situ growth of the quasi-single crystal perovskite film: placing the substrate containing the aminated graphene quantum dots prepared in the step (2) into a perovskite growth container, and adding the MAPbI prepared in the step (1) into the container3Sealing the container of the perovskite precursor solution, and placing the container on a heating panel at 135 ℃ for in-situ growth in a cavity limited area for 10 hours; then cooling to room temperature, slowly adding carbon tetrachloride to completely immerse the substrate, and standing for 4 hours; removing unreacted MAPbI3Cleaning the perovskite film for 3 times by isopropanol with perovskite precursor liquid and carbon tetrachloride; removing the prepared MAPbI with the thickness of about 600 nm3The pseudo-single crystal perovskite thin film substrate is placed on a heating panel at 105 ℃ for annealing for 15 minutes.
Further carrying out passivation, vapor deposition of a hole transport layer, vacuum thermal evaporation of a silver electrode and paraffin sealing on the surface of the single crystal perovskite film to assemble the film with the effective area of 200cm2The perovskite solar cell of (1). When the light intensity is 100mW cm-2When the cell is used, the photocurrent density of the cell is 19.87mA cm-2The open-circuit voltage is 0.99V, the fill factor is 0.73, and the photoelectric conversion efficiency reaches 14.36%. Under the same condition, the perovskite thin film growing in an unlimited region has very many crystal boundaries and defects and very large internal resistance, can not be effectively assembled into a perovskite solar cell, has very low photoelectric conversion efficiency, and has the light intensity of 100mW cm-2When the cell is used, the photocurrent density of the cell is 4.70mA cm-2The open circuit voltage was 0.69V, the fill factor was 0.30, and the photoelectric conversion efficiency was 0.97%.
Example 4
（1）MAPbI3Preparing a perovskite precursor solution: mixing MAI and PbI2Adding the mixture into a mixed solvent of N, N-dimethylformamide and dimethyl sulfoxide with the volume ratio of 4:1 according to an equimolar ratio, stirring the mixture for 6 hours at 70 ℃, and preparing MAPbI with the concentration of 1.2 mol/L3Perovskite precursor liquid (among others, MA)+Is CH3NH3 +）；
(2) Constructing a substrate containing carboxylated graphene quantum dots, namely preparing a regular-hexagon tin metal cavity electrode on a clean 15cm × 15cm transparent conductive substrate by using a vacuum thermal evaporation method and using a regular-hexagon mask plate with the side length of 10 mm and the stem width of 0.05 mm, wherein the side length, the stem width and the stem height of the regular-hexagon tin metal cavity electrode are respectively 10 mm, 0.05 mm and 300 nm;
(3) and (3) carrying out cavity limited in-situ growth of the quasi-single crystal perovskite film: placing the substrate containing the carboxylated graphene quantum dots prepared in the step (2) into a perovskite growth container, and adding the MAPbI prepared in the step (1) into the container3Sealing the container of the perovskite precursor solution, and placing the container on a heating panel at 135 ℃ for limited-area in-situ growth for 18 hours; then cooling to room temperature, slowly adding carbon trichloride to completely immerse the substrate, and standing for 5 hours; removing unreacted MAPbI3Cleaning the perovskite film for 3 times by isopropanol in the perovskite precursor solution and carbon trichloride; removing the prepared MAPbI with the thickness of about 700 nm3The pseudo-single crystal perovskite thin film substrate is placed on a heating panel at 105 ℃ for annealing for 15 minutes.
Further carrying out passivation, vapor deposition of a hole transport layer, vacuum thermal evaporation of a silver electrode and paraffin sealing on the surface of the single crystal perovskite film to assemble the film with the effective area of 200cm2The perovskite solar cell of (1). When the light intensity is 100mW cm-2When the cell is used, the photocurrent density of the cell is 20.16mA cm-2The open-circuit voltage is 1.00V, the fill factor is 0.71, and the photoelectric conversion efficiency reaches 14.31%. Under the same condition, the perovskite thin film growing in an unlimited region has very many crystal boundaries and defects and very large internal resistance, can not be effectively assembled into a perovskite solar cell, has very low photoelectric conversion efficiency, and has the light intensity of 100mW cm-2When the cell is used, the photocurrent density of the cell is 4.66mA cm-2Open circuit voltage of 068V, a fill factor of 0.30, and a photoelectric conversion efficiency of 0.95%.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (9)
1. A preparation method of a large-area quasi-single crystal perovskite film with cavity limited-area in-situ growth is characterized by comprising the following steps: the method comprises the following steps:
（1）ABX3preparing a perovskite precursor solution: mixing AX and BX2Adding into solvent at equal molar ratio, stirring at 30-100 deg.C for 1-24 hr to obtain ABX with concentration of 0.5-2.5 mol/L3A perovskite precursor liquid;
(2) the method comprises the steps of preparing a metal cavity electrode with a specific shape and specification on a clean large-area transparent conductive substrate with the thickness of 15cm × 15 cm-35 cm × 35cm by using a mask plate through a vacuum thermal evaporation method, preparing a current carrier transmission layer on the surface of the formed metal cavity electrode through the vacuum thermal evaporation method, and finally depositing functionalized graphene quantum dots on the surface of the current carrier transmission layer through an electrophoresis method;
(3) and (3) carrying out cavity limited in-situ growth of the quasi-single crystal perovskite film: placing the substrate containing the functionalized graphene quantum dots prepared in the step (2) into a container, and adding the ABX prepared in the step (1)3The perovskite precursor liquid is placed on a heating panel to carry out cavity limited in-situ growth of the perovskite film in a sealed container; then cooling to room temperature, slowly adding a poor solvent with high density until the substrate is completely immersed, and standing for 1-12 hours; removing unreacted ABX3Cleaning the perovskite precursor solution and the poor solvent with high density for 2-3 times by using the poor solvent with low density, and annealing to prepare the substrate containing the large-area quasi-single crystal perovskite film.
2. The preparation method of the cavity-limited in-situ grown large-area quasi-single crystal perovskite thin film according to claim 1, which is characterized in that: ABX described in step (1)3In the perovskite, A is CH3NH3 +、HC(NH2)2 +、(CH3)4N+、C7H7 +、Rb+And Cs+One or more of; b is Ge2+、Sn2+And Pb2+One or more of (a); x is I-、Br-And Cl-One or more of;
the solvent is one or more of gamma-butyrolactone, N-dimethylformamide, dimethyl sulfoxide and N-methyl-2-pyrrolidone.
3. The preparation method of the cavity-limited in-situ grown large-area quasi-single crystal perovskite thin film according to claim 1, which is characterized in that: the transparent conductive substrate in the step (2) is any one of FTO conductive glass, ITO/PEN flexible substrate and ITO/PET flexible substrate; the metal cavity electrode with the specific shape and specification is triangular, quadrangular or hexagonal, and has the specification of 1-20 mm of side length, 5-100 microns of stem width and 50-500 nanometers of stem height.
4. The preparation method of the cavity-limited in-situ grown large-area quasi-single crystal perovskite thin film according to claim 1, which is characterized in that: in the step (2), the metal is any one of tin, titanium, zinc, aluminum, nickel and molybdenum.
5. The preparation method of the cavity-limited in-situ grown large-area quasi-single crystal perovskite thin film according to claim 1, which is characterized in that: the thickness of the carrier transport layer prepared in the step (2) is 50-500 nanometers.
6. The preparation method of the cavity-limited in-situ grown large-area quasi-single crystal perovskite thin film according to claim 1, which is characterized in that: the functionalization in step (2) is one or more of amination, sulfhydrylation, carboxylation and halogenation.
7. The preparation method of the cavity-limited in-situ grown large-area quasi-single crystal perovskite thin film according to claim 1, which is characterized in that: the poor solvent with high density in the step (3) is one or more of carbon tetrachloride, carbon trichloride, dichloromethane and carbon disulfide; the poor solvent with low density is one or more of chlorobenzene, toluene, anisole, diethyl ether and C3-C6 monohydric alcohol.
8. The preparation method of the cavity-limited in-situ grown large-area quasi-single crystal perovskite thin film according to claim 1, which is characterized in that: in the step (3), the temperature of the cavity limited-area in-situ growth is 50-200 ℃, and the time is 6-48 hours; the annealing temperature is 50-200 deg.C, and the annealing time is 5-120 min.
9. The preparation method of the cavity-limited in-situ grown large-area quasi-single crystal perovskite thin film according to claim 1, which is characterized in that: the thickness of the obtained large-area quasi-single crystal perovskite thin film is 0.5-1.2 microns.
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| CN114447231A (en) * | 2021-11-15 | 2022-05-06 | 电子科技大学 | Preparation method and application of patterned single crystal perovskite array film |
| WO2024139360A1 (en) * | 2022-12-29 | 2024-07-04 | 隆基绿能科技股份有限公司 | Single-crystal perovskite cell preparation method and single-crystal perovskite cell prepared using same |
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