Preparation method of laminated perovskite thin film and laminated perovskite thin film

Abstract

The invention discloses a preparation method of a laminated perovskite thin film and the laminated perovskite thin film, and the method comprises the steps: S100, selecting a transparent substrate coated with ITO or FTO, and depositing a charge transmission layer on the ITO or FTO; s200, treating in an air plasma environment, and transferring into a glove box; s300, depositing and forming a two-dimensional perovskite precursor thin film on the charge transport layer; s400, the transparent substrate is transferred to a heating table to be annealed, a layer is deposited through thermal evaporation, and then the transparent substrate is covered with a layer through atomic layer deposition; s500, preparing a three-dimensional perovskite solution, uniformly spreading the three-dimensional perovskite solution, and spin-coating the three-dimensional perovskite solution on the layer to form a three-dimensional perovskite layer; s600, the step S400 is repeated, and the layers are deposited again through thermal evaporation; and S700, scraping off the perovskite layer on the surface by using a scraper to expose part of the ITO or FTO layer, and depositing the metal electrode layer by using thermal evaporation. The method has remarkable advantages in the aspects of structural design, interface engineering and device performance, and an ordered laminated structure of two-dimensional and three-dimensional perovskite layers is realized through layer-by-layer deposition.

Description

Technical Field

[0001] This invention belongs to the field of perovskite thin film technology, and more specifically, relates to a method for preparing a multilayer perovskite thin film and the multilayer perovskite thin film. Background Technology

[0002] Over the past decade, organic-inorganic hybrid perovskite materials have demonstrated enormous potential in photovoltaics and photodetectors, driving the development of optoelectronic devices towards higher efficiency and lower costs. Perovskite thin films are renowned for their high absorption coefficients, long carrier diffusion lengths, and tunable band structures, and their solution-based fabrication methods enable flexible, large-area fabrication. However, traditional monolayer perovskite thin films generally suffer from numerous crystal defects, interfacial instability, and ion migration problems. These factors lead to severe carrier recombination and poor device stability, severely limiting their application in high-performance optoelectronic devices.

[0003] To address the aforementioned issues, researchers proposed constructing a hybrid two-dimensional / three-dimensional layered perovskite structure to balance high photoelectric performance with environmental stability. Two-dimensional perovskites typically consist of organic macromolecules and inorganic layered structures, exhibiting strong hydrophobicity and chemical stability, effectively passivating underlying defects and preventing water and oxygen erosion. Three-dimensional perovskites, on the other hand, possess excellent carrier mobility and light absorption, providing high photogenerated current output. By organically combining these two elements through layer-by-layer deposition, a vertical band gradient structure can be formed at the microscopic level, achieving efficient photogenerated carrier separation and transport, thus theoretically improving both device efficiency and stability simultaneously.

[0004] Despite the promising prospects of these two-dimensional / three-dimensional stacked structures, several challenges remain to be addressed in current research. First, interlayer interface compatibility is insufficient. Significant lattice mismatches often exist between two-dimensional and three-dimensional perovskite lattices, easily leading to carrier traps at the interfaces and reducing the open-circuit voltage and fill factor of the devices. Second, interface modulation mechanisms are still incomplete. Current research focuses primarily on the crystallization control of the perovskite host layer, while studies on energy level matching and interfacial dipole effects between the charge transport layer (HTL / ETL) and the stacked structure are relatively weak, limiting efficient charge transport in multilayer structures. Third, stability and integration remain bottlenecks. Due to the presence of organic cations or residual solvents, devices are still prone to degradation under thermal, humid, and light-induced conditions. Furthermore, the application of stacked perovskites in optoelectronic dual-functional or multi-port integrated devices is still in its early stages, and a systematic approach to system design and process optimization has not yet been established. Summary of the Invention

[0005] To address the aforementioned deficiencies or improvement needs of existing technologies, this invention provides a method for preparing a stacked perovskite thin film and the stacked perovskite thin film itself, offering significant advantages in structural design, interface engineering, and device performance. An ordered stacked structure of two-dimensional and three-dimensional perovskite layers is achieved through layer-by-layer deposition. The bottom two-dimensional layer, based on a layered structure constructed from long-chain organic cations, possesses excellent density and hydrophobicity, effectively passivating defects and inhibiting ion migration and moisture erosion. The upper three-dimensional layer promotes grain orientation growth through dynamic solvent annealing, reducing grain boundary defect density and significantly improving the film's crystallinity and surface smoothness. The synergistic effect of the two-dimensional buffer layer and the three-dimensional main layer significantly enhances the continuity of the film structure and its mechanical stability.

[0006] To achieve the above objectives, according to a first aspect of the present invention, a method for preparing a multilayer perovskite thin film is provided, specifically comprising the following steps: S100: Select a transparent substrate coated with ITO or FTO, and ultrasonically clean it sequentially with detergent, deionized water, and ethanol. After treatment in a UV ozone environment, a layer is deposited on the ITO or FTO. Charge transport layer; S200, deposited The transparent substrate of the charge transport layer is processed in an air plasma environment and then transferred to a glove box; S300, prepare a mixed solution containing long-chain organic amines and metal halide precursors, and... A two-dimensional perovskite precursor film is deposited on the charge transport layer; S400: After annealing the transparent substrate on a hot plate, thermal evaporation deposition is performed. Layers, and deposited through atomic layers on Cover with another layer layer; S500: A three-dimensional perovskite solution is prepared using mixed cations and halides as precursors and GBL or DMF / DMSO as solvent. The three-dimensional perovskite solution is then uniformly spread and spin-coated onto... A three-dimensional perovskite layer is formed on the layer; S600, Repeat step S400 again to deposit via thermal evaporation. Layers and layer; S700: Use a scraper to remove the surface perovskite layer to expose part of the ITO or FTO layer, then use thermal evaporation to deposit the metal electrode layer.

[0007] Further, in step S100, the transparent substrate has a size of 2.5cm × 2.5cm, and it is ultrasonically cleaned with detergent, deionized water and ethanol for 30-45 minutes, and treated in an ozone environment with ultraviolet ozone for 10-30 minutes.

[0008] Furthermore, a layer is deposited on ITO or FTO. The specific operation of the charge transport layer is as follows: equip it with 5-15 mg / ml of... An aqueous solution is deposited on a transparent substrate surface by spin coating at a rate of 1000-3000 rpm. Charge transport layer.

[0009] Furthermore, sediments were deposited. The transparent substrate of the charge transport layer is treated in an air plasma environment for 10-30 minutes.

[0010] Furthermore, the long-chain organic amine includes , Or a mixture of both, the metal halide precursor includes In the mixed solution, the molar ratio of long-chain organic amine to metal halide precursor is 3:1 to 1:1.

[0011] Furthermore, in step S300, at When a two-dimensional perovskite precursor film is deposited on the charge transport layer, it is formed by spin coating at a rate of 2000-4000 rpm.

[0012] Furthermore, in step S400, when the transparent substrate is annealed on the hot plate, the annealing temperature is 100-120°C and the annealing time is 5-10 minutes. The The thickness of the layer is 30-60 nm, the On the layer The layer thickness is 50-70nm.

[0013] Further, in step S500, the mixed cations include , as well as Organic or inorganic ions, including the halide, are , ; The concentration of solute in the three-dimensional perovskite solution is 1.5-3 mol / L.

[0014] Further, in step S500, when spin-coating the three-dimensional perovskite layer, the three-dimensional perovskite solution used is 250-300uL, the total spin-coating time is set to 60-70s, the spin-coating speed is 500-1000rpm for the first 30-40s, the spin-coating speed is 2000-3000rpm for the second part, and 100-200uL of chlorobenzene is added as an anti-solvent 10-20s before the end of spin-coating; After spin coating is completed, place the spin-coated film on a hot plate and anneal it in a nitrogen atmosphere at 90-100℃ for 10-20 minutes. Then stop the gas supply and raise the temperature of the hot plate to 100-120℃ for annealing for 1-3 hours.

[0015] According to a second aspect of the present invention, a multilayer perovskite thin film is provided, comprising a transparent substrate, wherein a carrier transport layer is disposed on the transparent substrate, and the carrier transport layer is coated with ITO or FTO. The surface of the charge carrier transport layer is provided with a charge transport layer, which is... Deposited on the carrier transport layer; A two-dimensional perovskite layer is disposed on the surface of the charge transport layer, and the surface of the two-dimensional perovskite layer is sequentially deposited upwards with... Protective layer and Protective layer, the A three-dimensional perovskite layer is provided on the protective layer, and the surface of the three-dimensional perovskite layer is also sequentially deposited upwards with... Protective layer and Protective layer, the The protective layer has a metal electrode layer on its surface; Furthermore, a notch is cut downward along one side of the three-dimensional perovskite layer, extending to the surface of the carrier transport layer, and a metal electrode layer is provided on the carrier transport layer at the notch.

[0016] In summary, compared with the prior art, the above-described technical solutions conceived by this invention can achieve the following beneficial effects: 1. The method for preparing the multilayer perovskite thin film of the present invention has significant advantages in terms of structural design, interface engineering, and device performance. An ordered multilayer structure of two-dimensional and three-dimensional perovskite layers is achieved through layer-by-layer deposition. The bottom two-dimensional layer is based on a layered structure constructed from long-chain organic cations, possessing excellent compactness and hydrophobicity, effectively passivating defects and inhibiting ion migration and moisture erosion. The upper three-dimensional layer promotes grain orientation growth through dynamic solvent annealing, reduces grain boundary defect density, and significantly improves the crystallinity and surface smoothness of the film. The synergistic effect of the two-dimensional buffer layer and the three-dimensional main layer significantly improves the continuity of the film structure and its mechanical stability.

[0017] 2. The stacked structure of this invention achieves optimized vertical energy level gradient and interface energy level matching in the band structure. The relatively wide band gap of the two-dimensional layer facilitates the directional separation of photogenerated carriers and reduces the interface barrier. After interface modification, the energy levels of the hole and electron transport layers are well matched, significantly improving carrier extraction efficiency. This structure exhibits significantly improved carrier mobility compared to conventional three-dimensional perovskite films, with a markedly reduced nonradiative recombination rate, thus enhancing the photoelectric conversion efficiency of the device. Short-circuit current density and fill factor are also significantly improved, and the response time is shortened, demonstrating superior transient optical response characteristics. The two-dimensional layer provides an effective physical and chemical protective barrier, suppressing water and oxygen permeation and ion diffusion, thereby improving the environmental and light-induced stability of the stacked film.

[0018] 3. The multilayer perovskite thin film of this invention, after 1000 hours of continuous operation at 85°C and 60% relative humidity, still maintains over 90% of its initial efficiency, while traditional 3D thin film devices typically experience significant performance degradation within 400 hours. This fully demonstrates the outstanding advantages of this invention in terms of thermal, humidity, and optical stability. Furthermore, this invention exhibits strong process compatibility and scalability. Layer-by-layer deposition is compatible with spin coating, blade coating, and trench coating technologies, making it suitable for various applications. , , Various cationic systems and , The isohalogen system enables large-area preparation and industrial-scale production.

[0019] 4. The multilayer perovskite thin film of the present invention provides a new platform for multifunctional optoelectronic integrated devices. While maintaining high photoelectric conversion efficiency, it possesses excellent photoelectric response characteristics, and can be extended to photovoltaic-photodetector dual-function devices and self-powered integrated systems, demonstrating broad application prospects in the field of high-performance, long-life optoelectronics. Attached Figure Description

[0020] Figure 1 This is a schematic flowchart of a method for preparing a multilayer perovskite thin film according to an embodiment of the present invention; Figure 2 This is a schematic diagram of the structure of a multilayer perovskite thin film according to an embodiment of the present invention; Figure 3 This is a schematic diagram illustrating the change in the response current density of a multilayer perovskite thin film under three identical X-ray dose irradiations according to an embodiment of the present invention. Figure 4 This is a two-dimensional SEM image of a cross-sectional perovskite layer of a multilayer perovskite thin film according to an embodiment of the present invention; Figure 5 This is a three-dimensional SEM image of a perovskite layer cross-section of a multilayer perovskite thin film according to an embodiment of the present invention.

[0021] In all the accompanying drawings, the same reference numerals denote the same technical features, specifically: 1-transparent substrate, 2-carrier transport layer, 3-charge transport layer, 4-two-dimensional perovskite layer, 5-C 60 Protective layer, 6-SnO2 protective layer, 7-three-dimensional perovskite layer, 8-metal electrode layer. Detailed Implementation

[0022] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention. Furthermore, the technical features involved in the various embodiments of this invention described below can be combined with each other as long as they do not conflict with each other.

[0023] Example 1 like Figure 1 As shown, this embodiment of the invention provides a method for preparing a multilayer perovskite thin film, specifically including the following steps: S100: Select a transparent substrate coated with ITO or FTO, and ultrasonically clean it sequentially with detergent, deionized water, and ethanol. After treatment in a UV ozone environment, a layer is deposited on the ITO or FTO. Charge transport layer; S200, deposited The transparent substrate of the charge transport layer is processed in an air plasma environment and then transferred to a glove box; S300, prepare a mixed solution containing long-chain organic amines and metal halide precursors, and... A two-dimensional perovskite precursor film is deposited on the charge transport layer; S400: After annealing the transparent substrate on a hot plate, thermal evaporation deposition is performed. Layers, and deposited through atomic layers on Cover with another layer layer; S500: A three-dimensional perovskite solution is prepared using mixed cations and halides as precursors and GBL or DMF / DMSO as solvent. The three-dimensional perovskite solution is then uniformly spread and spin-coated onto... A three-dimensional perovskite layer is formed on the layer; S600, Repeat step S400 again to deposit via thermal evaporation. Layers and layer; S700: Use a scraper to remove the surface perovskite layer to expose part of the ITO or FTO layer, then use thermal evaporation to deposit the metal electrode layer.

[0024] In step S100, the transparent substrate has a size of 2.5cm × 2.5cm, and it is ultrasonically cleaned with detergent, deionized water and ethanol for 30 minutes, and treated in an ozone environment with ultraviolet ozone for 10 minutes.

[0025] In step S100, a layer is deposited on ITO or FTO. The specific operation of the charge transport layer is as follows: equip it with 5 mg / ml of... An aqueous solution was deposited on a transparent substrate by spin coating at a rate of 1000 rpm. Charge transport layer.

[0026] In step S200, deposited The transparent substrate of the charge transport layer was treated in an air plasma environment for 10 minutes.

[0027] In step S300, the long-chain organic amine includes , Or a mixture of both, the metal halide precursor includes In the mixed solution, the molar ratio of long-chain organic amine to metal halide precursor is 3:1.

[0028] In step S300, at When a two-dimensional perovskite precursor film is deposited on the charge transport layer, it is formed by spin coating at a rate of 2000 rpm.

[0029] In step S400, when the transparent substrate is annealed on the hot plate, the annealing temperature is 100°C and the annealing time is 5 minutes.

[0030] In step S400, the The thickness of the layer is 30nm, the On the layer The layer thickness is 50nm.

[0031] In step S500, the mixed cations include , as well as Organic or inorganic ions, including the halide, are , The concentration of the solute in the three-dimensional perovskite solution is 1.5 mol / L.

[0032] In step S500, when spin-coating the three-dimensional perovskite layer, the three-dimensional perovskite solution used is 250uL, the total spin-coating time is set to 60s, the spin-coating speed is 500rpm for the first 30s, the spin-coating speed is 2000rpm for the second 30s, and 100uL of chlorobenzene is added as an anti-solvent 10s before the end of spin-coating.

[0033] In step S500, after spin coating is completed, the spin-coated film is placed on a hot stage and annealed in a nitrogen atmosphere at 90°C for 10 minutes. Then, the gas supply is stopped, and the hot stage is heated to 100°C for annealing for 1 hour.

[0034] In step S700, the metal electrode layer is Cu or Au, and its thickness is 100 nm.

[0035] Example 2 A method for preparing a multilayer perovskite thin film specifically includes the following steps: S100: Select a transparent substrate coated with ITO or FTO, and ultrasonically clean it sequentially with detergent, deionized water, and ethanol. After treatment in a UV ozone environment, a layer is deposited on the ITO or FTO. Charge transport layer; S200, deposited The transparent substrate of the charge transport layer is processed in an air plasma environment and then transferred to a glove box; S300, prepare a mixed solution containing long-chain organic amines and metal halide precursors, and... A two-dimensional perovskite precursor film is deposited on the charge transport layer; S400: After annealing the transparent substrate on a hot plate, thermal evaporation deposition is performed. Layers, and deposited through atomic layers on Cover with another layer layer; S500: A three-dimensional perovskite solution is prepared using mixed cations and halides as precursors and GBL or DMF / DMSO as solvent. The three-dimensional perovskite solution is then uniformly spread and spin-coated onto... A three-dimensional perovskite layer is formed on the layer; S600, Repeat step S400 again to deposit via thermal evaporation. Layers and layer; S700: Use a scraper to remove the surface perovskite layer to expose part of the ITO or FTO layer, then use thermal evaporation to deposit the metal electrode layer.

[0036] In step S100, the transparent substrate has a size of 2.5cm × 2.5cm, and it is ultrasonically cleaned with detergent, deionized water and ethanol for 45 minutes, and treated in an ozone environment with ultraviolet ozone for 30 minutes.

[0037] In step S100, a layer is deposited on ITO or FTO. The specific operation of the charge transport layer is as follows: It is equipped with 15 mg / ml of... An aqueous solution was deposited on a transparent substrate by spin coating at a rate of 3000 rpm. Charge transport layer.

[0038] In step S200, deposited The transparent substrate of the charge transport layer was treated in an air plasma environment for 30 minutes.

[0039] In step S300, the long-chain organic amine includes , Or a mixture of both, the metal halide precursor includes In the mixed solution, the molar ratio of long-chain organic amine to metal halide precursor is 1:1.

[0040] In step S300, at When a two-dimensional perovskite precursor film is deposited on the charge transport layer, it is formed by spin coating at a rate of 4000 rpm.

[0041] In step S400, when the transparent substrate is annealed on the hot plate, the annealing temperature is 120°C and the annealing time is 10 minutes.

[0042] In step S400, the The thickness of the layer is 60nm, the On the layer The layer thickness is 70nm.

[0043] In step S500, the mixed cations include , as well as Organic or inorganic ions, including the halide, are , The concentration of the solute in the three-dimensional perovskite solution is 3 mol / L.

[0044] In step S500, when spin-coating the three-dimensional perovskite layer, the three-dimensional perovskite solution used is 300uL, the total spin-coating time is set to 70s, the spin-coating speed is 1000rpm for the first 40s, the spin-coating speed is 3000rpm for the second 40s, and 200uL of chlorobenzene is added as an anti-solvent 20s before the end of spin-coating.

[0045] In step S500, after spin coating is completed, the spin-coated film is placed on a hot stage and annealed in a nitrogen atmosphere at 100°C for 20 minutes. Then, the gas supply is stopped, and the hot stage is heated to 120°C for annealing for 3 hours.

[0046] In step S700, the metal electrode layer is Cu or Au, and its thickness is 120 nm.

[0047] Example 3 A method for preparing a multilayer perovskite thin film specifically includes the following steps: S100: Select a transparent substrate coated with ITO or FTO, and ultrasonically clean it sequentially with detergent, deionized water, and ethanol. After treatment in a UV ozone environment, a layer is deposited on the ITO or FTO. Charge transport layer; S200, deposited The transparent substrate of the charge transport layer is processed in an air plasma environment and then transferred to a glove box; S300, prepare a mixed solution containing long-chain organic amines and metal halide precursors, and... A two-dimensional perovskite precursor film is deposited on the charge transport layer; S400: After annealing the transparent substrate on a hot plate, thermal evaporation deposition is performed. Layers, and deposited through atomic layers on Cover with another layer layer; S500: A three-dimensional perovskite solution is prepared using mixed cations and halides as precursors and GBL or DMF / DMSO as solvent. The three-dimensional perovskite solution is then uniformly spread and spin-coated onto... A three-dimensional perovskite layer is formed on the layer; S600, Repeat step S400 again to deposit via thermal evaporation. Layers and layer; S700: Use a scraper to remove the surface perovskite layer to expose part of the ITO or FTO layer, then use thermal evaporation to deposit the metal electrode layer.

[0048] In step S100, the transparent substrate has a size of 2.5cm × 2.5cm, and it is ultrasonically cleaned with detergent, deionized water and ethanol for 40 minutes, and treated in an ozone environment with ultraviolet ozone for 20 minutes.

[0049] In step S100, a layer is deposited on ITO or FTO. The specific operation of the charge transport layer is as follows: equip it with 10 mg / ml of... An aqueous solution was deposited on a transparent substrate surface by spin coating at a rate of 2000 rpm. Charge transport layer.

[0050] In step S200, deposited The transparent substrate of the charge transport layer was treated in an air plasma environment for 20 minutes.

[0051] In step S300, the long-chain organic amine includes , Or a mixture of both, the metal halide precursor includes In the mixed solution, the molar ratio of long-chain organic amine to metal halide precursor is 2:1.

[0052] In step S300, at When a two-dimensional perovskite precursor film is deposited on the charge transport layer, it is formed by spin coating at a rate of 3000 rpm.

[0053] In step S400, when the transparent substrate is annealed on the hot plate, the annealing temperature is 110°C and the annealing time is 7 minutes.

[0054] In step S400, the The thickness of the layer is 45 nm, the On the layer The layer thickness is 60nm.

[0055] In step S500, the mixed cations include , as well as Organic or inorganic ions, including the halide, are , The concentration of the solute in the three-dimensional perovskite solution is 2 mol / L.

[0056] In step S500, when spin-coating the three-dimensional perovskite layer, the three-dimensional perovskite solution used is 275uL, the total spin-coating time is set to 65s, the spin-coating speed for the first 35s is 750rpm, the spin-coating speed for the second 3s is 2500rpm, and 150uL of chlorobenzene is added as an anti-solvent 15s before the end of spin-coating.

[0057] In step S500, after spin coating is completed, the spin-coated film is placed on a hot stage and annealed in a nitrogen atmosphere at 95°C for 15 minutes. Then, the gas supply is stopped, and the hot stage is heated to 110°C for annealing for 2 hours.

[0058] In step S700, the metal electrode layer is Cu or Au, and its thickness is 110 nm.

[0059] Example 4 A method for preparing a multilayer perovskite thin film specifically includes the following steps: S100: Select a transparent substrate coated with ITO or FTO, and ultrasonically clean it sequentially with detergent, deionized water, and ethanol. After treatment in a UV ozone environment, a layer is deposited on the ITO or FTO. Charge transport layer; S200, deposited The transparent substrate of the charge transport layer is processed in an air plasma environment and then transferred to a glove box; S300, prepare a mixed solution containing long-chain organic amines and metal halide precursors, and... A two-dimensional perovskite precursor film is deposited on the charge transport layer; S400: After annealing the transparent substrate on a hot plate, thermal evaporation deposition is performed. Layers, and deposited through atomic layers on Cover with another layer layer; S500: A three-dimensional perovskite solution is prepared using mixed cations and halides as precursors and GBL or DMF / DMSO as solvent. The three-dimensional perovskite solution is then uniformly spread and spin-coated onto... A three-dimensional perovskite layer is formed on the layer; S600, Repeat step S400 again to deposit via thermal evaporation. Layers and layer; S700: Use a scraper to remove the surface perovskite layer to expose part of the ITO or FTO layer, then use thermal evaporation to deposit the metal electrode layer.

[0060] In step S100, the transparent substrate has a size of 2.5cm × 2.5cm, and it is ultrasonically cleaned with detergent, deionized water and ethanol for 32 minutes, and treated in an ozone environment with ultraviolet ozone for 15 minutes.

[0061] In step S100, a layer is deposited on ITO or FTO. The specific operation of the charge transport layer is as follows: It is equipped with 8 mg / ml of... An aqueous solution was deposited on a transparent substrate by spin coating at a rate of 1500 rpm. Charge transport layer.

[0062] In step S200, deposited The transparent substrate of the charge transport layer was treated in an air plasma environment for 25 minutes.

[0063] In step S300, the long-chain organic amine includes , Or a mixture of both, the metal halide precursor includes In the mixed solution, the molar ratio of long-chain organic amine to metal halide precursor is 2.5:1.

[0064] In step S300, at When a two-dimensional perovskite precursor film is deposited on the charge transport layer, it is formed by spin coating at a rate of 3500 rpm.

[0065] In step S400, when the transparent substrate is annealed on the hot plate, the annealing temperature is 105°C and the annealing time is 9 minutes.

[0066] In step S400, the The thickness of the layer is 40 nm, the On the layer The layer thickness is 65nm.

[0067] In step S500, the mixed cations include , as well as Organic or inorganic ions, including the halide, are , The concentration of the solute in the three-dimensional perovskite solution is 2.5 mol / L.

[0068] In step S500, when spin-coating the three-dimensional perovskite layer, the three-dimensional perovskite solution used is 285uL, the total spin-coating time is set to 60s, the spin-coating speed for the first 35s is 650rpm, the spin-coating speed for the second 3s is 2750rpm, and 175uL of chlorobenzene is added as an anti-solvent 12s before the end of spin-coating.

[0069] In step S500, after spin coating is completed, the spin-coated film is placed on a hot stage and annealed in a nitrogen atmosphere at 100°C for 12 minutes. Then, the gas supply is stopped, and the hot stage is heated to 110°C for annealing for 2 hours.

[0070] In step S700, the metal electrode layer is Cu or Au, and its thickness is 105 nm.

[0071] Example 5 A method for preparing a multilayer perovskite thin film specifically includes the following steps: S100: Select a transparent substrate coated with ITO or FTO, and ultrasonically clean it sequentially with detergent, deionized water, and ethanol. After treatment in a UV ozone environment, a layer is deposited on the ITO or FTO. Charge transport layer; S200, deposited The transparent substrate of the charge transport layer is processed in an air plasma environment and then transferred to a glove box; S300, prepare a mixed solution containing long-chain organic amines and metal halide precursors, and... A two-dimensional perovskite precursor film is deposited on the charge transport layer; S400: After annealing the transparent substrate on a hot plate, thermal evaporation deposition is performed. Layers, and deposited through atomic layers on Cover with another layer layer; S500: A three-dimensional perovskite solution is prepared using mixed cations and halides as precursors and GBL or DMF / DMSO as solvent. The three-dimensional perovskite solution is then uniformly spread and spin-coated onto... A three-dimensional perovskite layer is formed on the layer; S600, Repeat step S400 again to deposit via thermal evaporation. Layers and layer; S700: Use a scraper to remove the surface perovskite layer to expose part of the ITO or FTO layer, then use thermal evaporation to deposit the metal electrode layer.

[0072] In step S100, the transparent substrate has a size of 2.5cm × 2.5cm, and it is ultrasonically cleaned with detergent, deionized water and ethanol for 42 minutes, and treated in an ozone environment with ultraviolet ozone for 10 minutes.

[0073] In step S100, a layer is deposited on ITO or FTO. The specific operation of the charge transport layer is as follows: It is equipped with 12 mg / ml of... An aqueous solution was deposited on a transparent substrate by spin coating at a rate of 2500 rpm. Charge transport layer.

[0074] In step S200, deposited The transparent substrate of the charge transport layer was treated in an air plasma environment for 15 minutes.

[0075] In step S300, the long-chain organic amine includes , Or a mixture of both, the metal halide precursor includes In the mixed solution, the molar ratio of long-chain organic amine to metal halide precursor is 1.5:1.

[0076] In step S300, at When a two-dimensional perovskite precursor film is deposited on the charge transport layer, it is formed by spin coating at a rate of 3500 rpm.

[0077] In step S400, when the transparent substrate is annealed on the hot plate, the annealing temperature is 115°C and the annealing time is 10 minutes.

[0078] In step S400, the The thickness of the layer is 55 nm, the On the layer The layer thickness is 55nm.

[0079] In step S500, the mixed cations include , as well as Organic or inorganic ions, including the halide, are , The concentration of the solute in the three-dimensional perovskite solution is 1.8 mol / L.

[0080] In step S500, when spin-coating the three-dimensional perovskite layer, the three-dimensional perovskite solution used is 260uL, the total spin-coating time is set to 60s, the spin-coating speed for the first 32s is 850rpm, the spin-coating speed for the second 3s is 2250rpm, and 125uL of chlorobenzene is added as an anti-solvent 18s before the end of spin-coating.

[0081] In step S500, after spin coating is completed, the spin-coated film is placed on a hot stage and annealed in a nitrogen atmosphere at 100°C for 18 minutes. Then, the gas supply is stopped, and the hot stage is heated to 105°C for annealing for 2 hours.

[0082] In step S700, the metal electrode layer is Cu or Au, and its thickness is 115 nm.

[0083] Example 6 A method for preparing a multilayer perovskite thin film specifically includes the following steps: S100: Select a transparent substrate coated with ITO or FTO, and ultrasonically clean it sequentially with detergent, deionized water, and ethanol. After treatment in a UV ozone environment, a layer is deposited on the ITO or FTO. Charge transport layer; S200, deposited The transparent substrate of the charge transport layer is processed in an air plasma environment and then transferred to a glove box; S300, prepare a mixed solution containing long-chain organic amines and metal halide precursors, and... A two-dimensional perovskite precursor film is deposited on the charge transport layer; S400: After annealing the transparent substrate on a hot plate, thermal evaporation deposition is performed. Layers, and deposited through atomic layers on Cover with another layer layer; S500: A three-dimensional perovskite solution is prepared using mixed cations and halides as precursors and GBL or DMF / DMSO as solvent. The three-dimensional perovskite solution is then uniformly spread and spin-coated onto... A three-dimensional perovskite layer is formed on the layer; S600, Repeat step S400 again to deposit via thermal evaporation. Layers and layer; S700: Use a scraper to remove the surface perovskite layer to expose part of the ITO or FTO layer, then use thermal evaporation to deposit the metal electrode layer.

[0084] In step S100, the transparent substrate has a size of 2.5cm × 2.5cm, and it is ultrasonically cleaned with detergent, deionized water and ethanol for 32 minutes, and treated in an ozone environment with ultraviolet ozone for 15 minutes.

[0085] In step S100, a layer is deposited on ITO or FTO. The specific operation of the charge transport layer is as follows: It is equipped with 15 mg / ml of... An aqueous solution was deposited on a transparent substrate surface by spin coating at a rate of 2800 rpm. Charge transport layer.

[0086] In step S200, deposited The transparent substrate of the charge transport layer was treated in an air plasma environment for 25 minutes.

[0087] In step S300, the long-chain organic amine includes , Or a mixture of both, the metal halide precursor includes In the mixed solution, the molar ratio of long-chain organic amine to metal halide precursor is 2.5:1.

[0088] In step S300, at When a two-dimensional perovskite precursor film is deposited on the charge transport layer, it is formed by spin coating at a rate of 2200 rpm.

[0089] In step S400, when the transparent substrate is annealed on the hot plate, the annealing temperature is 105°C and the annealing time is 10 minutes.

[0090] In step S400, the The thickness of the layer is 40 nm, the The SnO2 layer on the layer is 60 nm thick.

[0091] In step S500, the mixed cations include , as well as Organic or inorganic ions, including the halide, are , The concentration of the solute in the three-dimensional perovskite solution is 2.5 mol / L.

[0092] In step S500, when spin-coating the three-dimensional perovskite layer, the three-dimensional perovskite solution used is 280uL, the total spin-coating time is set to 70s, the spin-coating speed for the first 40s is 600rpm, the spin-coating speed for the second 40s is 2800rpm, and 185uL of chlorobenzene is added as an anti-solvent 15s before the end of spin-coating.

[0093] In step S500, after spin coating is completed, the spin-coated film is placed on a hot stage and annealed in a nitrogen atmosphere at 95°C for 15 minutes. Then, the gas supply is stopped, and the hot stage is heated to 110°C for annealing for 2 hours.

[0094] In step S700, the metal electrode layer is Cu or Au, and its thickness is 110 nm.

[0095] Example 7 like Figure 2-5 As shown, this embodiment of the invention provides a multilayer perovskite thin film, prepared using one of the multilayer perovskite thin film preparation methods in Examples 1-6. It includes a transparent substrate 1, on which a carrier transport layer 2 is disposed. The carrier transport layer 2 is coated with ITO or FTO. A charge transport layer 3 is disposed on the surface of the carrier transport layer 2. A two-dimensional perovskite layer 4 is deposited on the charge transport layer 2. The surface of the charge transport layer 3 is provided with a two-dimensional perovskite layer 4, and the surface of this two-dimensional perovskite layer 4 is sequentially deposited upwards with... Protective layer 5 and Protective layer 6, A three-dimensional perovskite layer 7 is provided on the protective layer 6, and the surface of the three-dimensional perovskite layer 7 is also sequentially deposited upwards with... Protective layer 5 and Protective layer 6, A metal electrode layer 8 is provided on the surface of the protective layer 6. A notch is cut downward along one side of the three-dimensional perovskite layer 7, extending to the surface of the carrier transport layer 2. A metal electrode layer 8 is provided on the carrier transport layer 2 at the notch.

[0096] Those skilled in the art will readily understand that the above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for preparing a multilayer perovskite thin film, characterized in that, Specifically, the following steps are included: S100: Select a transparent substrate coated with ITO or FTO, and ultrasonically clean it sequentially with detergent, deionized water, and ethanol. After treatment in a UV ozone environment, a layer is deposited on the ITO or FTO. Charge transport layer; S200, deposited The transparent substrate of the charge transport layer is processed in an air plasma environment and then transferred to a glove box; S300, prepare a mixed solution containing long-chain organic amines and metal halide precursors, and... A two-dimensional perovskite precursor film is deposited on the charge transport layer; S400: After annealing the transparent substrate on a hot plate, thermal evaporation deposition is performed. Layers, and deposited through atomic layers on Cover with another layer layer; S500: A three-dimensional perovskite solution is prepared using mixed cations and halides as precursors and GBL or DMF / DMSO as solvent. The three-dimensional perovskite solution is then uniformly spread and spin-coated onto... A three-dimensional perovskite layer is formed on the layer; S600, Repeat step S400 again to deposit via thermal evaporation. Layers and layer; S700: Use a scraper to remove the surface perovskite layer to expose part of the ITO or FTO layer, then use thermal evaporation to deposit the metal electrode layer.

2. The method for preparing a multilayer perovskite thin film according to claim 1, characterized in that, In step S100, the transparent substrate has a size of 2.5cm × 2.5cm, and it is ultrasonically cleaned with detergent, deionized water and ethanol for 30-45 minutes, and treated in an ozone environment with ultraviolet ozone for 10-30 minutes.

3. The method for preparing a multilayer perovskite thin film according to claim 2, characterized in that, Deposit a layer on ITO or FTO The specific operation of the charge transport layer is as follows: equip it with 5-15 mg / ml of... An aqueous solution is deposited on a transparent substrate surface by spin coating at a rate of 1000-3000 rpm. Charge transport layer.

4. A method for preparing a multilayer perovskite thin film according to any one of claims 1-3, characterized in that, Deposited The transparent substrate of the charge transport layer is treated in an air plasma environment for 10-30 minutes.

5. A method for preparing a multilayer perovskite thin film according to any one of claims 1-3, characterized in that, The long-chain organic amines include , Or a mixture of both, the metal halide precursor includes In the mixed solution, the molar ratio of long-chain organic amine to metal halide precursor is 3:1 to 1:

1.

6. The method for preparing a multilayer perovskite thin film according to claim 5, characterized in that, In step S300, at When a two-dimensional perovskite precursor film is deposited on the charge transport layer, it is formed by spin coating at a rate of 2000-4000 rpm.

7. A method for preparing a multilayer perovskite thin film according to any one of claims 1-3, characterized in that, In step S400, when the transparent substrate is annealed on the hot plate, the annealing temperature is 100-120℃ and the annealing time is 5-10 minutes. The The thickness of the layer is 30-60 nm, the On the layer The layer thickness is 50-70nm.

8. A method for preparing a multilayer perovskite thin film according to any one of claims 1-3, characterized in that, In step S500, the mixed cations include , as well as Organic or inorganic ions, including the halide, are , ; The concentration of solute in the three-dimensional perovskite solution is 1.5-3 mol / L.

9. The method for preparing a multilayer perovskite thin film according to claim 8, characterized in that, In step S500, when spin-coating the three-dimensional perovskite layer, the three-dimensional perovskite solution used is 250-300uL, the total spin-coating time is set to 60-70s, the spin-coating speed for the first 30-40s is 500-1000rpm, the spin-coating speed for the last 30s is 2000-3000rpm, and 100-200uL of chlorobenzene is added as an anti-solvent 10-20s before the end of spin-coating; After spin coating is completed, place the spin-coated film on a hot plate and anneal it in a nitrogen atmosphere at 90-100℃ for 10-20 minutes. Then stop the gas supply and raise the temperature of the hot plate to 100-120℃ for annealing for 1-3 hours.

10. A multilayer perovskite thin film, prepared using the method for preparing a multilayer perovskite thin film as described in any one of claims 1-9, characterized in that, Includes a transparent substrate (1), on which a carrier transport layer (2) is provided, wherein the carrier transport layer (2) is coated with ITO or FTO; The surface of the charge carrier transport layer (2) is provided with a charge transport layer (3), which is a charge transport layer (3) Deposited on the carrier transport layer (2); A two-dimensional perovskite layer (4) is provided on the surface of the charge transport layer (3), and the surface of the two-dimensional perovskite layer (4) is sequentially deposited with the following materials: Protective layer (5) and Protective layer (6), A three-dimensional perovskite layer (7) is provided on the protective layer (6), and the surface of the three-dimensional perovskite layer (7) is also sequentially deposited upwards with... Protective layer (5) and Protective layer (6), The protective layer (6) has a metal electrode layer (8) on its surface; Furthermore, a notch is cut downward along one side of the three-dimensional perovskite layer (7), the notch extends to the surface of the carrier transport layer (2), and a metal electrode layer (8) is provided on the carrier transport layer (2) at the notch.

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