CN111446370B - Method for growing large-area quasi-single crystal perovskite film in situ in cavity confinement - Google Patents
Method for growing large-area quasi-single crystal perovskite film in situ in cavity confinement Download PDFInfo
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Abstract
The invention discloses a preparation method of a cavity confinement in-situ growth large-area quasi-single crystal perovskite film, which comprises the steps of firstly constructing a metal cavity electrode with specific shape and specification on a large-area transparent conductive substrate to reduce the internal resistance of a device, then preparing a carrier transmission layer on the surface of the device, depositing functionalized graphene quantum dots on the carrier transmission layer, finally growing the perovskite film in the cavity confinement in-situ, and promoting the uniform and rapid growth of quasi-single crystal perovskite by using a poor solvent standing method to prepare the large-area quasi-single crystal perovskite film. The quasi-monocrystalline perovskite thin film obtained by the method has the advantages of large area, few grain 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, because the organic-inorganic hybrid perovskite material has unique photoelectric property and low preparation cost, perovskite Solar Cells (PSCs) attract wide attention in academia and industry, and bring new development opportunities to the photovoltaic field. From 2009 to date, the laboratory photoelectric conversion efficiency of PSC has been refreshed from 3.8% in 2009 to 25.2% in 2019. However, the high efficiency PSCs of these authentications or reports are mostly based on a relatively small area (typically 0.1cm 2 Some of which are smaller to 0.03cm 2 ). The spin coating technology is a technology with low cost and easy operation, and can realize the total area of the device of 100cm 2 (effective area 50.6 cm) 2 ) Preparation of photoelectric conversion efficiency 13% but area exceeding 100cm 2 It is difficult to obtain a uniform film. Accordingly, researchers have also developed other solution-based techniques such as knife coating, nip-extrusion coating, meniscus-assisted solution printing, screen printing, spray coating, soft film blanket deposition, ink jet printing, and the like. However, perovskite prepared based on the solution methodThe polycrystalline perovskite structure has a large number of grain boundaries and defects, which is unfavorable for obtaining a PSC device with high efficiency and stability. Compared to the polycrystalline thin film of perovskite, the single crystal perovskite without grain boundaries has better thermal stability, wider light absorption range, lower hole concentration and higher carrier mobility. Currently, the preparation method of the single crystal perovskite mainly comprises an antisolvent method, a cooling crystallization method, a heating crystallization method, a top seed crystal solution growth method, a slow solvent evaporation 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 required, 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 defects of the quasi-single crystal perovskite are obviously smaller than those of the polycrystalline perovskite, and the preparation requirements and the cost of the quasi-single crystal perovskite are smaller than those of the single crystal perovskite. It has been found by search that patent CN 110534654A discloses a method of quasi-monocrystalline perovskite thin film, which is to prepare small grain perovskite on a substrate first, then place it in a closed device containing saturated AX atmosphere and prepare the quasi-monocrystalline perovskite thin film by hot pressing method. However, the method is not to grow a quasi-single crystal perovskite film in situ on the carrier transport layer, and a buried metal electrode is not constructed in advance, so that the internal resistance of the film is high, and an additional hot-pressing sealing device is needed. Patent CN107093671a discloses a method for preparing a single crystal perovskite organic metal halide film, which grows a single crystal perovskite film on a carrier transmission layer, an antisolvent is added in the growth process to promote perovskite crystallization, and the film is spin-dried after the growth is finished, so that the preparation of a large-area uniform high-quality film is not facilitated, an embedded metal electrode is not constructed in advance, the internal resistance of the film is high, and the photoelectric conversion efficiency is low; patent CN 107460535a discloses a method for preparing an in-situ grown single crystal perovskite organic metal halide film, which grows a single crystal perovskite film on a carrier transport layer, a temperature gradient is set in a single crystal growth area to promote perovskite crystallization, an additional device is needed, an embedded metal electrode is not constructed in advance, the internal resistance of the film is large, the area of the single crystal perovskite film is limited, and the photoelectric conversion efficiency is low. Patent CN108023017a discloses a single crystal film of organic-inorganic composite perovskite material, a preparation method and application thereof, and the method utilizes a two-dimensional finite field 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 transport layer, namely, a single crystal perovskite film is not directly grown in situ on the surface of the carrier transport layer; the substrate is combined into a two-dimensional domain-limiting structure, and the single crystal perovskite film grows between two substrates and has the same binding force with the two substrates, so that the single crystal perovskite film is not easy to remove from a certain substrate; in addition, the large-area substrate material does not contain embedded metal electrodes, is directly applied to a photovoltaic device, has very large resistance and is not beneficial to obtaining a high-efficiency device. Therefore, in-situ growth of large-area high-quality (uniform, few grain boundaries, few defects and low internal resistance) quasi-monocrystalline perovskite thin films on carrier transport layers is critical for preparing high-performance stable large-area photovoltaic devices.
Disclosure of Invention
The invention aims to provide a preparation method for a cavity-limited in-situ growth large-area quasi-single crystal perovskite film, which can prepare a perovskite film with an area larger than 200cm 2 The quasi-single crystal perovskite film has few grain boundaries, few defects, controllable thickness and low internal resistance, and can be directly applied to photovoltaic devices.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a preparation method of a cavity confinement in-situ growth large-area quasi-single crystal perovskite film comprises the following steps:
（1）ABX 3 preparing perovskite precursor liquid: AX and BX 2 Adding the mixture into a solvent in an equimolar ratio, stirring for 1-24 hours at 30-100 ℃ to prepare the ABX with the concentration of 0.5-2.5mol/L 3 Perovskite precursor liquid;
(2) Constructing a substrate containing functionalized graphene quantum dots: preparing a metal cavity electrode with a specific shape and specification by using a mask plate on a clean large-area transparent conductive substrate with the thickness of 15cm multiplied by 15cm to 35cm multiplied by 35cm by adopting a vacuum thermal evaporation method; then preparing a carrier transmission layer on the surface of the formed metal cavity electrode by adopting a vacuum thermal evaporation method; finally, depositing functionalized graphene quantum dots on the surface of the carrier transport layer by adopting an electrophoresis method;
(3) Cavity confinement in-situ growth of quasi-single crystal perovskite thin films: 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 container 3 Placing the perovskite precursor liquid and the sealed container on a heating panel to perform cavity confinement in-situ growth of the perovskite film; 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; removal of unreacted ABX 3 And cleaning the perovskite precursor liquid 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.
Step (1) the ABX 3 A in perovskite is CH 3 NH 3 + 、HC(NH 2 ) 2 + 、(CH 3 ) 4 N + 、C 7 H 7 + 、Rb + And Cs + One or more of the following; b is Ge 2+ 、Sn 2+ And Pb 2+ One or more of the following; x is I - 、Br - And Cl - One or more of the following;
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 specific shape and specification is triangular, quadrilateral or hexagonal, preferably square or regular hexagon, and has a side length of 1-20 mm, a stem width of 5-100 micrometers and a stem height of 50-500 nanometers.
The metal in the step (2) 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 nm.
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, methylene dichloride and carbon disulfide; the poor solvent with low density is one or more of chlorobenzene, toluene, anisole, diethyl ether and C3-C6 monohydric alcohol.
The temperature of the hollow cavity limited-area in-situ growth in the step (3) is 50-200 ℃ and the time is 6-48 hours; the annealing temperature is 50-200 ℃ and the annealing time is 5-120 minutes.
The thickness of the obtained large-area quasi-single crystal perovskite film is 0.5-1.2 micrometers.
The invention has the beneficial effects that:
(1) According to the invention, the quasi-monocrystalline perovskite film is prepared on the carrier transmission layer in situ, so that the grain boundary and defects can be remarkably reduced, the thickness of the perovskite film is controllable, and the obtained perovskite 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 domain-limited structure, the internal resistance of the large-area photovoltaic device can be remarkably reduced, the formed embedded metal electrode is beneficial to the collection and transmission of carriers, and meanwhile, the embedded metal electrode is beneficial to the vertical growth of quasi-single crystal perovskite and the rapid removal of precursor solvent.
(3) According to the invention, after the cavity limited region of the perovskite film grows in situ, the perovskite film is treated by adopting a poor solvent standing method, so that the uniform and rapid growth of the quasi-monocrystalline perovskite can be promoted, and the generated quasi-monocrystalline perovskite film can be protected.
(4) The invention can prepare the material with the area larger than 200cm 2 The quasi-single crystal perovskite thin film is favorable for preparing large-area photovoltaic devices, has a lattice structure, can reduce the generation of grain boundaries and defects, further improves the performance and long-term stability of the photovoltaic devices, and simultaneously has a macro-structureThe trapezoid structure can generate a light trapping effect, so that the utilization rate of sunlight is improved.
(5) The preparation method has mild and controllable preparation conditions, is simple and effective, has low cost and is beneficial to commercial mass production. The thin film prepared by the method is used for preparing a large-area perovskite solar cell when the area of the thin film is 200cm 2 When the solar cell is used, the highest photoelectric conversion efficiency can reach 15.60%, 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 view of a metal cavity electrode formed by using the mask.
Detailed Description
In order to make the contents of the present invention more easily understood, the technical scheme of the present invention will be further described with reference to the following specific embodiments in conjunction with the accompanying drawings, but the present invention is not limited thereto.
Example 1
（1）FA 0.85 MA 0.15 PbI 2.55 Br 0.45 Preparing perovskite precursor liquid: 1.02mol of FAI and 1.02mol of PbI 2 0.18mol MABr and 0.18mol PbBr 2 Adding into 1L gamma-butyrolactone, stirring at 80deg.C for 6 hr to obtain FA with total concentration of 1.2mol/L 0.85 MA 0.15 PbI 2.55 Br 0.45 Perovskite precursor liquid (wherein, MA + Is CH 3 NH 3 + ，FA + For HC (NH) 2 ) 2 + ）；
(2) Construction of a substrate containing amino graphene quantum dots: preparing square tin metal cavity electrodes on a clean transparent conductive substrate with the length of 15cm multiplied by 15cm by using a square mask plate with the side length of 10 mm and the stem width of 0.05 mm by adopting a vacuum thermal evaporation method, wherein the side length, the stem width and the stem height are respectively 10 mm, 0.05 mm and 300 nm; then adopting a vacuum thermal evaporation method (without a mask) to prepare a tin dioxide electron transport layer with the thickness of 100 nanometers on the surface of the tin metal cavity electrode; finally, depositing aminated graphene quantum dots on the surface of the tin dioxide electron transport layer by adopting an electrophoresis method;
(3) Cavity confinement in-situ growth of quasi-single crystal perovskite thin films: placing the substrate containing the amino graphene quantum dots prepared in the step (2) into a perovskite growth container, and adding the FA prepared in the step (1) into the container 0.85 MA 0.15 PbI 2.55 Br 0.45 Sealing the container, placing the container on a heating panel at 150 ℃ and heating the upper cavity of the panel to limit the field for in-situ growth for 12 hours; then cooling to room temperature, slowly adding carbon tetrachloride to completely submerge the substrate, and standing for 4 hours; removing unreacted FA 0.85 MA 0.15 PbI 2.55 Br 0.45 Cleaning the perovskite film 3 times by using isopropanol; the prepared FA with the thickness of about 800 nanometers is taken out 0.85 MA 0.15 PbI 2.55 Br 0.45 The quasi-single crystal perovskite thin film substrate was placed on a heating panel at 135℃for annealing for 30 minutes.
Further passivating the surface of the single crystal perovskite film, vapor depositing a hole transport layer, vacuum thermally evaporating a silver electrode, and sealing with paraffin wax to obtain an effective area of 200cm 2 Is a quasi-monocrystalline perovskite solar cell. When the light intensity is 100mW cm -2 The cell photocurrent density was 21.75mA.cm -2 The open circuit voltage is 1.01V, the filling factor is 0.71, and the photoelectric conversion efficiency reaches 15.60%. Under the same conditions, the perovskite film which grows in an unconfined way has very many grain boundaries and defects, 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 100 mW.cm -2 The photocurrent density of the battery was 5.22mA cm -2 The open circuit voltage was 0.74V, the fill factor was 0.31, and the photoelectric conversion efficiency was 1.20%.
Example 2
（1）FA 0.85 MA 0.15 PbI 2.55 Br 0.45 Preparing perovskite precursor liquid: 1.02mol of FAI and 1.02mol of PbI 2 0.18mol MABr and 0.18mol PbBr 2 Adding into 1L gamma-butyrolactone, stirring at 80deg.C for 6 hr to obtain FA with total concentration of 1.2mol/L 0.85 MA 0.15 PbI 2.55 Br 0.45 Perovskite precursor liquid (wherein, MA + Is CH 3 NH 3 + ，FA + For HC (NH) 2 ) 2 + ）；
(2) Construction of a substrate containing sulfhydryl graphene quantum dots: preparing a regular hexagonal titanium metal cavity electrode on a clean transparent conductive substrate with the length of 15cm multiplied by 15cm by using a regular hexagonal mask plate with the side length of 10 mm and the stem width of 0.05 mm by adopting a vacuum thermal evaporation method, wherein the side length, the stem width and the stem height are respectively 10 mm, 0.05 mm and 300 nm; then adopting a vacuum thermal evaporation method (without a mask) to prepare a titanium dioxide electron transport layer with the thickness of 100 nanometers on the surface of the titanium metal cavity electrode; finally, depositing sulfhydrylated graphene quantum dots on the surface of the titanium dioxide electron transport layer by adopting an electrophoresis method;
(3) Cavity confinement in-situ growth of quasi-single crystal perovskite thin films: placing the substrate containing the mercapto graphene quantum dots prepared in the step (2) into a perovskite growth container, and adding the FA prepared in the step (1) into the container 0.85 MA 0.15 PbI 2.55 Br 0.45 Placing the sealed container in a heating panel at 150 ℃ to perform cavity confinement in-situ growth for 12 hours; then cooling to room temperature, slowly adding carbon tetrachloride to completely submerge the substrate, and standing for 4 hours; removing unreacted FA 0.85 MA 0.15 PbI 2.55 Br 0.45 Cleaning the perovskite film 3 times by using isopropanol; the prepared FA with the thickness of about 800 nanometers is taken out 0.85 MA 0.15 PbI 2.55 Br 0.45 The quasi-single crystal perovskite thin film substrate was placed on a heating panel at 135℃for annealing for 30 minutes.
Further passivating the surface of the single crystal perovskite film, vapor depositing a hole transport layer, vacuum thermally evaporating a silver electrode, and sealing with paraffin wax to obtain an effective area of 200cm 2 Is a quasi-monocrystalline perovskite solar cell. When the light intensity is 100mW cm -2 The photocurrent density of the battery was 20.43mA cm -2 Open circuit voltage of 1.02V, fill factor of 0.70, photoelectric conversion efficiencyUp to 14.59%. Under the same conditions, the perovskite film which grows in an unconfined way has very many grain boundaries and defects, 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 100 mW.cm -2 The photocurrent density of the battery was 4.95mA cm -2 The open circuit voltage was 0.71V, the fill factor was 0.29, and the photoelectric conversion efficiency was 1.02%.
Example 3
（1）MAPbI 3 Preparing perovskite precursor liquid: MAI and PbI 2 Adding the mixture into a mixed solvent of N, N-dimethylformamide and dimethyl sulfoxide in a volume ratio of 4:1 according to an equimolar ratio, and stirring for 6 hours at 70 ℃ to prepare MAPbI with a concentration of 1.2mol/L 3 Perovskite precursor liquid (wherein, MA + Is CH 3 NH 3 + ）；
(2) Construction of a substrate containing amino graphene quantum dots: preparing square tin metal cavity electrode with side length, stem width and stem height of 10 mm, 0.05 mm and 200 nm respectively by vacuum thermal evaporation on clean transparent conductive substrate with 15cm×15cm and square mask plate with side length of 10 mm and stem width of 0.05 mm (shown in figure 1); then adopting a vacuum thermal evaporation method (without a mask) to prepare a tin dioxide electron transport layer with the thickness of 100 nanometers on the surface of the tin metal cavity electrode; finally, depositing aminated graphene quantum dots on the surface of the tin dioxide electron transport layer by adopting an electrophoresis method;
(3) Cavity confinement in-situ growth of quasi-single crystal perovskite thin films: placing the substrate containing the amino graphene quantum dots prepared in the step (2) in a perovskite growth container, and adding the MAPbI prepared in the step (1) into the container 3 Sealing the container with perovskite precursor liquid, and placing the container on a heating panel at 135 ℃ to perform cavity confinement in-situ growth for 10 hours; then cooling to room temperature, slowly adding carbon tetrachloride to completely submerge the substrate, and standing for 4 hours; removing unreacted MAPbI 3 Cleaning the perovskite film 3 times by using isopropanol; removing the prepared MAPbI with the thickness of about 600 nanometers 3 Quasi-single crystal perovskite thinThe film substrate was placed on a heated panel at 105℃for 15 minutes of annealing.
Further passivating the surface of the single crystal perovskite film, vapor depositing a hole transport layer, vacuum thermally evaporating a silver electrode, and sealing with paraffin wax to obtain an effective area of 200cm 2 Is a perovskite solar cell of the formula (I). When the light intensity is 100mW cm -2 The photocurrent density of the battery is 19.87mA cm -2 The open circuit voltage is 0.99V, the filling factor is 0.73, and the photoelectric conversion efficiency reaches 14.36%. Under the same conditions, the perovskite film which grows in an unconfined way has very many grain boundaries and defects, 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 100 mW.cm -2 The photocurrent density of the battery was 4.70mA cm -2 The open circuit voltage was 0.69V, the fill factor was 0.30, and the photoelectric conversion efficiency was 0.97%.
Example 4
（1）MAPbI 3 Preparing perovskite precursor liquid: MAI and PbI 2 Adding the mixture into a mixed solvent of N, N-dimethylformamide and dimethyl sulfoxide in a volume ratio of 4:1 according to an equimolar ratio, and stirring for 6 hours at 70 ℃ to prepare MAPbI with a concentration of 1.2mol/L 3 Perovskite precursor liquid (wherein, MA + Is CH 3 NH 3 + ）；
(2) Constructing a substrate containing carboxylated graphene quantum dots: preparing a regular hexagonal tin metal cavity electrode on a clean transparent conductive substrate with the length of 15cm multiplied by 15cm by using a regular hexagonal mask plate with the side length of 10 mm and the stem width of 0.05 mm by adopting a vacuum thermal evaporation method, wherein the side length, the stem width and the stem height are respectively 10 mm, 0.05 mm and 300 nm; then adopting a vacuum thermal evaporation method (without a mask) to prepare a tin dioxide electron transport layer with the thickness of 100 nanometers on the surface of the tin metal cavity electrode; finally, depositing carboxylated graphene quantum dots on the surface of the tin dioxide electron transport layer by adopting an electrophoresis method;
(3) Cavity confinement in-situ growth of quasi-single crystal perovskite thin films: placing the substrate containing carboxylated graphene quantum dots prepared in the step (2) in a perovskite growth container, and introducing the substrate into the containerAdding the MAPbI prepared in the step (1) into a reactor 3 Sealing the container, placing the perovskite precursor liquid on a heating panel at 135 ℃ and growing in situ in a cavity limited area for 18 hours; then cooling to room temperature, slowly adding carbon trichloride to fully submerge the substrate, and standing for 5 hours; removing unreacted MAPbI 3 Cleaning the perovskite film 3 times by using isopropanol; removing the prepared MAPbI with the thickness of about 700 nanometers 3 The quasi-single crystal perovskite thin film substrate was placed on a heating panel at 105℃for annealing for 15 minutes.
Further passivating the surface of the single crystal perovskite film, vapor depositing a hole transport layer, vacuum thermally evaporating a silver electrode, and sealing with paraffin wax to obtain an effective area of 200cm 2 Is a perovskite solar cell of the formula (I). When the light intensity is 100mW cm -2 The photocurrent density of the battery was 20.16mA cm -2 The open circuit voltage is 1.00V, the filling factor is 0.71, and the photoelectric conversion efficiency reaches 14.31%. Under the same conditions, the perovskite film which grows in an unconfined way has very many grain boundaries and defects, 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 100 mW.cm -2 The photocurrent density of the battery was 4.66mA cm -2 The open circuit voltage was 0.68V, the fill factor was 0.30, and the photoelectric conversion efficiency was 0.95%.
The foregoing description is only of the preferred embodiments of the invention, and all changes and modifications that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (8)
1. A preparation method for a large-area quasi-single crystal perovskite film grown in situ in a cavity limited area is characterized by comprising the following steps: the method comprises the following steps:
（1）ABX 3 preparing perovskite precursor liquid: AX and BX 2 Adding the mixture into a solvent in an equimolar ratio, stirring for 1-24 hours at 30-100 ℃ to prepare the ABX with the concentration of 0.5-2.5mol/L 3 Perovskite precursor liquid;
(2) Constructing a substrate containing functionalized graphene quantum dots: preparing a metal cavity electrode with a specific shape and specification by using a mask plate on a clean large-area transparent conductive substrate with the thickness of 15cm multiplied by 15cm to 35cm multiplied by 35cm by adopting a vacuum thermal evaporation method; then preparing a carrier transmission layer on the surface of the formed metal cavity electrode by adopting a vacuum thermal evaporation method; finally, depositing functionalized graphene quantum dots on the surface of the carrier transport layer by adopting an electrophoresis method;
(3) Cavity confinement in-situ growth of quasi-single crystal perovskite thin films: 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) 3 Placing the perovskite precursor liquid and the sealed container on a heating panel to perform cavity confinement in-situ growth of the perovskite film; 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; removal of unreacted ABX 3 Cleaning the perovskite precursor liquid 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;
step (1) the ABX 3 A in perovskite is CH 3 NH 3 + 、HC(NH 2 ) 2 + 、(CH 3 ) 4 N + 、C 7 H 7 + 、Rb + And Cs + One or more of the following; b is Ge 2+ 、Sn 2+ And Pb 2+ One or more of the following; x is I - 、Br - And Cl - One or more of the following;
the poor solvent with high density in the step (3) is one or more of carbon tetrachloride, carbon trichloride, methylene dichloride and carbon disulfide; the poor solvent with low density is one or more of chlorobenzene, toluene, anisole, diethyl ether and C3-C6 monohydric alcohol.
2. The method for preparing the cavity-confined in-situ grown large-area quasi-single crystal perovskite thin film according to claim 1, which is characterized by comprising the following steps: the solvent in the step (1) is one or more of gamma-butyrolactone, N-dimethylformamide, dimethyl sulfoxide and N-methyl-2-pyrrolidone.
3. The method for preparing the cavity-confined in-situ grown large-area quasi-single crystal perovskite thin film according to claim 1, which is characterized by comprising the following steps: 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 specific shape and specification is triangular, quadrilateral or hexagonal, and has a side length of 1-20 mm, a stem width of 5-100 micrometers and a stem height of 50-500 nanometers.
4. The method for preparing the cavity-confined in-situ grown large-area quasi-single crystal perovskite thin film according to claim 1, which is characterized by comprising the following steps: the metal in the step (2) is any one of tin, titanium, zinc, aluminum, nickel and molybdenum.
5. The method for preparing the cavity-confined in-situ grown large-area quasi-single crystal perovskite thin film according to claim 1, which is characterized by comprising the following steps: the thickness of the carrier transport layer prepared in the step (2) is 50-500 nm.
6. The method for preparing the cavity-confined in-situ grown large-area quasi-single crystal perovskite thin film according to claim 1, which is characterized by comprising the following steps: the functionalization in step (2) is one or more of amination, sulfhydrylation, carboxylation and halogenation.
7. The method for preparing the cavity-confined in-situ grown large-area quasi-single crystal perovskite thin film according to claim 1, which is characterized by comprising the following steps: the temperature of the hollow cavity limited-area in-situ growth in the step (3) is 50-200 ℃ and the time is 6-48 hours; the annealing temperature is 50-200 ℃ and the annealing time is 5-120 minutes.
8. The method for preparing the cavity-confined in-situ grown large-area quasi-single crystal perovskite thin film according to claim 1, which is characterized by comprising the following steps: the thickness of the obtained large-area quasi-single crystal perovskite film is 0.5-1.2 micrometers.
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| CN106410032A (en) * | 2016-08-25 | 2017-02-15 | 中国科学院重庆绿色智能技术研究院 | Flexible perovskite solar cell with metal grid graphene composite electrode and preparation method thereof |
| CN106960883A (en) * | 2017-03-24 | 2017-07-18 | 华中科技大学 | A kind of full-inorganic perovskite solar cell and preparation method thereof |
| CN108987586A (en) * | 2017-06-02 | 2018-12-11 | 颜步 | A kind of perovskite solar cell module and preparation method thereof |
| CN109659437A (en) * | 2018-11-23 | 2019-04-19 | 上海工程技术大学 | Based on the perovskite solar battery of low temperature graphene aerogel and its preparation |
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| JP2016143708A (en) * | 2015-01-30 | 2016-08-08 | 株式会社リコー | Perovskite type solar battery module |
| CN106410032A (en) * | 2016-08-25 | 2017-02-15 | 中国科学院重庆绿色智能技术研究院 | Flexible perovskite solar cell with metal grid graphene composite electrode and preparation method thereof |
| CN106960883A (en) * | 2017-03-24 | 2017-07-18 | 华中科技大学 | A kind of full-inorganic perovskite solar cell and preparation method thereof |
| CN108987586A (en) * | 2017-06-02 | 2018-12-11 | 颜步 | A kind of perovskite solar cell module and preparation method thereof |
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