In-situ polymerization perovskite X-ray detector and preparation method thereof

Abstract

The invention relates to an in-situ polymerization perovskite X-ray detector and a preparation method thereof, the structure of the detector comprises an in-situ polymerization perovskite layer, and the in-situ polymerization perovskite layer is formed by mixing a perovskite precursor, an organic solvent, a polymer monomer and an initiator. According to the invention, the perovskite wet film containing the uniformly dispersed polymer monomers is constructed, and polymerization of the polymer monomers is synchronously carried out by using the initiator in the perovskite recrystallization process to form a copolymer network, so that the perovskite thin film is stabilized. The in-situ polymerized copolymer network can be used as a bridge of perovskite halide crystals, and the film forming quality and the crack resistance ductility of the perovskite film are greatly improved. More importantly, a copolymer network chain contains a large number of functional groups which can be used as active sites to effectively passivate a defect structure in perovskite and remarkably promote migration of charges, so that the migration rate of carriers and the photoelectric conversion efficiency are greatly improved, and the output of high-stability photoelectric performance and response speed of a device is further realized.

Description

Technical Field

[0001] The present invention belongs to the field of X-ray detectors, and in particular relates to an in-situ polymerized perovskite X-ray detector and a preparation method thereof. Background Art

[0002] Metal halide perovskite X-ray detectors have become a promising direct imaging technology due to their high photoelectric conversion efficiency and low cost. However, the lattice defects and large number of grain boundaries in perovskites will accelerate the aging and degradation of the device, seriously affecting the service life of the device. In addition, due to the imaging area of ​​the detector and the strong penetration ability of X-rays, the perovskite film must have sufficient thickness (greater than 500μm) and size (greater than 10 cm*10 cm). The perovskite recrystallization process in the large-area perovskite thick film preparation technology is often accompanied by grain boundary and grain stacking, and ultimately leads to rough and uneven perovskite films and cracks. More importantly, metal halide perovskites are often accompanied by harmful heavy metal ions (such as Pb 2+ The leakage of heavy metal ions poses a threat to the environment and human health, severely limiting the widespread application of metal halide perovskite X-ray detectors. Therefore, developing a strategy for preparing highly stable perovskite thick films and significantly extending the service life of metal halide perovskite X-ray detectors remains a key technical challenge. Summary of the Invention

[0003] The purpose of the present invention is to provide an in-situ polymerized perovskite X-ray detector and a preparation method thereof. The method is simple to operate, can improve the density and mechanical strength of the perovskite film, thereby improving the film formation quality and toughness of the perovskite film, and can be used in the assembly and integration of perovskite X-ray direct imaging detectors to greatly improve the stability of the device.

[0004] To achieve the above-mentioned purpose, the technical solution adopted by the present invention is: an in-situ polymerized perovskite X-ray detector, whose structure from bottom to top is a substrate, an electron transport layer, an in-situ polymerized perovskite layer, a hole transport layer and a metal electrode layer; The in-situ polymerized perovskite layer is composed of a mixture of a perovskite precursor, an organic solvent, a polymer monomer, and an initiator; The perovskite precursor is CsPbI3, CsPbBr3, FACsPb I3 , one or more of MACsPbI3, MACsPbBrI2, FACsPbBr3, Cs2AgBiBr6, MAPbI3, MAPbBr3, and CsMAPbBr3; The polymer monomer is one of acrylamide, dopamine, polyvinyl pyrrolidone, styrene, methacrylic acid, acrylonitrile, acrylate, ketoacrylate, epoxy acrylate, hydroxyethyl acrylate, ‌4,4'-hexafluoroisopropylidene-phthalic anhydride, pyromellitic dianhydride, 4,4'-diaminodiphenyl ether, monomethoxy polyethylene glycol, and ethylene glycol dimethacrylate; The initiator is one of 2,2-azoisobutyronitrile, 2-hydroxy-2-methylpropenone, Irgacure 2925, benzophenone, acetophenone, azobisisobutyronitrile, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methylpropanone, azobisisobutylimidazoline hydrochloride, and folic acid.

[0005] Preferably, the organic solvent is one of acetonitrile, methanol, ethanol, dimethyl sulfoxide, dimethylformamide, chloroform, acetone, ethyl acetate, ether, and ethylene glycol monomethyl ether.

[0006] Preferably, the thickness of the electron transport layer is 3-20 nm; the thickness of the iodine-based perovskite film is 400-750 μm; the thickness of the hole transport layer is 3-25 nm; and the thickness of the metal electrode layer is 5-80 nm.

[0007] To achieve the above object, the present invention further provides a method for preparing the above-mentioned in-situ polymerized perovskite X-ray detector, comprising the following steps: S1: spraying an electron transport layer dispersion onto a substrate, and then performing an annealing treatment to prepare an electron transport layer; S2: Preparation of in-situ polymerized perovskite layer; S2-1: adding a perovskite precursor to an organic solvent, stirring and dissolving the mixture to obtain a perovskite precursor solution; S2-2: Adding polymer monomers and initiators to the perovskite precursor solution prepared in step S2-1, and forming a uniformly dispersed composite solution by ultrasonication and stirring; S2-3: Apply a layer of the composite stock solution prepared in step S2-2 on the electron transport layer prepared in step S1 by scraping, spraying or spin coating, and then transfer the composite stock solution to a heating table for thermal annealing and irradiation with ultraviolet light to obtain an in-situ polymerized perovskite layer; S3: coating the in-situ polymerized perovskite layer prepared in step S2 with a layer of 2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirobifluorene or C60 by blade coating, spray coating or spin coating to prepare a hole transport layer; S4: Vapor-depositing a layer of gold or silver on the hole transport layer prepared in step S3 as a metal electrode.

[0008] Preferably, in step S1, the annealing temperature is 100° C. to 120° C., the annealing time is 15 to 30 minutes, and the spraying time is 3 to 5 minutes.

[0009] Preferably, in step S2-1, the concentration of the perovskite precursor solution is 7-12 mg / mL.

[0010] Preferably, in step S2-2, the mass ratio between the polymer monomer and the perovskite precursor is (0.01-0.5): 1. Preferably, in step S2-2, the mass ratio between the initiator and the polymer monomer is (0.001-0.1): 1.

[0011] Preferably, in step S2-3, the annealing temperature of the heating stage is 100°C to 120°C, the annealing time is 1 to 3 hours, and the irradiation time of the ultraviolet lamp is 1 to 3 hours.

[0012] The technical principle of the present invention is: by constructing a perovskite wet film containing uniformly dispersed polymer monomers, an initiator is used to simultaneously polymerize the polymer monomers during the perovskite recrystallization process to form a copolymer network, thereby stabilizing the perovskite film. This in situ polymerized copolymer network can serve as a bridge for the perovskite halide crystals, significantly improving the film quality and crack resistance of the perovskite film. More importantly, the copolymer network chain contains a large number of functional groups, which can serve as active sites to effectively passivate the defect structure inside the perovskite and significantly promote the migration of charges, thereby achieving a significant increase in carrier mobility and photoelectric conversion efficiency, thereby achieving highly stable photoelectric performance and response speed output of the device.

[0013] Compared with the prior art, the present invention has the following beneficial effects: (1) The present invention constructs a perovskite wet film containing uniformly dispersed polymer monomers, and forms an in-situ polymerized perovskite thick film by simultaneously performing a perovskite recrystallization reaction and a monomer polymerization reaction. This copolymer network formed by in-situ polymerization, which is uniformly and effectively distributed inside the perovskite thick film, greatly alleviates the microstrain during the growth of the perovskite crystals, dissipates the mechanical stress inside the film, improves the mechanical strength of the film, and thus significantly improves the film quality and toughness of the perovskite film. On the other hand, the copolymer network formed by in-situ polymerization effectively fills the pores formed by the evaporation of the solution, further reduces the defects inside the thick film, and makes the perovskite thick film more dense and thick.

[0014] (2) The present invention constructs a highly stable perovskite thick film through the in-situ polymerization reaction of polymer monomers. The copolymer network formed by this in-situ polymerization is rich in a large number of highly active groups, which can react with the uncoordinated Pb 2+Ionic coordination makes the bonding strength between the copolymer network and the perovskite crystal stronger, thereby effectively passivating the defect structure inside the perovskite and significantly promoting the migration of charges, achieving higher photoelectric conversion efficiency and more sensitive response speed output.

[0015] (3) The present invention utilizes the simultaneous polymerization of monomers and precipitation of perovskite crystals. This method is rationally designed and simple to operate. The perovskite thick film is stabilized by a copolymer network that is uniformly and effectively distributed within the perovskite. The film is dense and thick, possessing excellent mechanical strength and crack resistance. More importantly, the stability of this in-situ polymerized perovskite thick film is significantly improved, resulting in outstanding results. This allows for large-scale production and can be directly used as a core component in the assembly and integration of perovskite X-ray detectors. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 A schematic structural diagram of an in-situ polymerized perovskite X-ray detector prepared according to an embodiment of the present invention; Figure 2 This is a surface SEM image of the in-situ polymerized perovskite film prepared in Example 1 of the present invention; Figure 3 This is a surface SEM image of the perovskite film prepared in Comparative Example 1 of the present invention; Figure 4 Schematic diagrams of X-ray responses of X-ray direct detectors prepared in Example 1 and Comparative Example 1 of the present invention, respectively; Figure 5 This is a surface SEM image of the in-situ polymerized perovskite film prepared in Example 2 of the present invention; Figure 6 This is a surface SEM image of the perovskite film prepared in Comparative Example 2 of the present invention; Figure 7 These are X-ray response performance diagrams of the X-ray direct detectors prepared in Example 2 of the present invention and Comparative Example 2, respectively. DETAILED DESCRIPTION

[0017] The present invention will be further described in detail below with reference to the embodiments.

[0018] The perovskite precursors in the following examples can be purchased directly from the market or prepared using methods reported in existing literature.

[0019] Example 1 An in-situ polymerized perovskite X-ray detector, such as Figure 1As shown, its structure from bottom to top is a substrate, an electron transport layer, an in situ polymerized perovskite layer, a hole transport layer and a metal electrode layer; the in situ polymerized perovskite layer is composed of a mixture of a perovskite precursor MACsPbBrI2, an organic solvent acetone, a polymer monomer ethylene glycol dimethacrylate and an initiator 2-hydroxy-2-methylpropenoate.

[0020] The method for preparing the above-mentioned in-situ polymerized perovskite X-ray detector comprises the following steps: S1: Spraying the electron transport layer dispersion tin dioxide solution (2 mg / ml) onto a conductive glass substrate for 4 minutes, followed by annealing at 100°C for 20 minutes to prepare the electron transport layer with a thickness of 3 nm. S2: Preparation of in situ polymerized perovskite films; S2-1: Add 1 g of MACsPbBrI2 to 100 mL of acetone and stir to dissolve to obtain a MACsPbBrI2 solution, a precursor of perovskite; the concentration of the perovskite precursor solution is 10 mg / mL; S2-2: Prepare a polymer monomer@perovskite precursor composite solution: Weigh 300 mg of ethylene glycol dimethacrylate polymer monomer and 5 mg of 2-hydroxy-2-methylpropenoate initiator, add them to the perovskite precursor solution prepared in step S2-1, sonicate for 30 minutes, and stir to dissolve to obtain a polymer monomer@perovskite precursor composite solution; the mass ratio of the polymer monomer to the perovskite precursor is 3:10; the mass ratio of the initiator to the polymer monomer is 1:60; S2-3: A layer of the precursor composite solution prepared in step S2-2 is coated on the electron transport layer obtained in step S1 by doctor blading, and then the precursor composite solution is transferred to a heating table and annealed at 100°C for 2 hours while being irradiated under a UV lamp, so that the perovskite recrystallization process and the polymerization reaction of the polymer monomer proceed synchronously, thereby obtaining an in situ polymerized MACsPbBrI2 perovskite composite film with a thickness of 650 μm. S3: Spray coating a layer of 2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirobifluorene (spiro-OMeTAD) as a hole transport layer on the in-situ polymerized MACsPbBrI2 perovskite composite film prepared in step S2-3, with a thickness of 15 nm. S4: a layer of Ag metal electrode is deposited on the hole transport layer prepared in step S3 by evaporation, and the thickness thereof is controlled to be 50 nm.

[0021] Comparative Example 1 This comparative example is a conventional perovskite X-ray detector, whose structure from bottom to top is substrate, electron transport layer, perovskite film, hole transport layer and metal electrode layer; The above-mentioned conventional method for preparing a perovskite X-ray detector differs from that of Example 1 in that step S2-2 is omitted, and a layer of the perovskite precursor solution in step S2-1 is directly coated on the electron transport layer prepared in step S1 by scraping, and then transferred to a vacuum drying oven and annealed at 100°C for 2h to obtain a perovskite film. The other steps remain consistent with Example 1.

[0022] The results of Example 1 and Comparative Example 1 are as follows: Figure 2 The scanning electron microscope (SEM) image of the in-situ polymerized MACsPbBrI2 perovskite composite film prepared in Example 1 is shown. Figure 3 The following is a scanning electron microscope (SEM) image of a conventional perovskite film in Comparative Example 1. Figure 2 As shown, the in-situ polymerized MACsPbBrI2 perovskite composite film in Example 1 exhibits a dense, flat and smooth surface, while the conventional perovskite in Comparative Example 1 shows a relatively loose surface with clearly observable loose pores on the surface. This fully demonstrates that the copolymer network formed by in-situ polymerization only inside the perovskite can alleviate the strain during the perovskite recrystallization process, effectively fill the pores formed by solution evaporation, reduce defects inside the film, make the perovskite thick film more dense and thick, and significantly improve the film quality and crack resistance of the perovskite film. Figure 4 The photocurrent curves of the perovskite X-ray detectors prepared in Example 1 and Comparative Example 1 under X-ray irradiation switching are shown. Figure 4 As shown, the photocurrent value of the in situ polymerized perovskite X-ray detector prepared in Example 1 is about 109 nA, which is significantly higher than the photocurrent value of the conventional detector in Comparative Example 1 (82 nA). This fully demonstrates that the copolymer network formed by in situ polymerization inside the perovskite can significantly passivate the defect structure inside the perovskite and fundamentally promote the migration of charges, thereby achieving a higher photoelectric conversion efficiency.

[0023] Example 2 An in-situ polymerized perovskite X-ray detector, such as Figure 1 As shown, its structure from bottom to top is substrate, electron transport layer, in situ polymerized perovskite layer, hole transport layer and metal electrode layer; the in situ polymerized perovskite layer is composed of a mixture of perovskite precursor FACsPbI3, organic solvent dimethylformamide, polymer monomer styrene and initiator azobisisobutyronitrile.

[0024] The method for preparing the above-mentioned in-situ polymerized perovskite X-ray detector comprises the following steps: S1: Spraying the electron transport layer dispersion titanium dioxide solution (5 mg / ml) onto a conductive glass substrate for 5 min, followed by annealing at 120°C for 40 min to prepare the electron transport layer with a thickness of 10 nm. S2: Preparation of in situ polymerized perovskite films; S2-1: Add 1.2 g of FACsPbI3 to 100 mL of dimethylformamide and stir to dissolve to obtain a perovskite precursor FACsPbI3 solution; the concentration of the perovskite precursor solution is 12 mg / mL; S2-2: Prepare a polymer monomer@perovskite precursor composite solution: Weigh 100 mg of styrene polymer monomer and 2 mg of azobisisobutyronitrile initiator and add them to the perovskite precursor solution prepared in step S2-1. After ultrasonic treatment for 30 minutes, stir and dissolve to obtain a polymer monomer@perovskite precursor composite solution; the mass ratio of the polymer monomer to the perovskite precursor is 1:12; the mass ratio of the initiator to the polymer monomer is 1:50; S2-3: Spray coating a layer of the precursor composite solution prepared in step S2-2 on the electron transport layer obtained in step S1, then transferring the layer to a heating table and annealing at 110° C. for 1.5 h while irradiating the layer under ultraviolet light, so that the perovskite recrystallization process and the polymerization reaction of the polymer monomer proceed synchronously, thereby obtaining an in-situ polymerized FACsPbI3 perovskite composite film having a thickness of 550 μm; S3: Spray coating a layer of 2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirobifluorene (spiro-OMeTAD) as a hole transport layer on the in-situ polymerized FACsPbI3 perovskite composite film prepared in step S2-3, with a thickness of 10 nm. S4: a layer of Ag metal electrode is deposited on the hole transport layer prepared in step S3 by evaporation, and the thickness thereof is controlled to be 30 nm.

[0025] Comparative Example 2 This comparative example is a conventional perovskite X-ray detector, whose structure from bottom to top is substrate, electron transport layer, perovskite film, hole transport layer and metal electrode layer; The above-mentioned conventional method for preparing a perovskite X-ray detector differs from that of Example 2 in that step S2-2 is omitted, and a layer of the perovskite precursor solution in step S2-1 is directly coated on the electron transport layer prepared in step S1 by spraying, and then transferred to a vacuum drying oven and annealed at 110°C for 1.5 hours to obtain a perovskite film. The other steps remain consistent with Example 2.

[0026] The results of Example 2 and Comparative Example 2 are as follows: Figure 5 The scanning electron microscope (SEM) image of the in-situ polymerized FACsPbI3 perovskite composite film prepared in Example 2 is shown. Figure 6 The following is a scanning electron microscope (SEM) image of a conventional perovskite film in comparative example 2. Figure 5 As shown, the surface of the in-situ polymerized FACsPbI3 perovskite composite film in Example 2 is relatively flat and smooth, while the surface of the conventional perovskite in Comparative Example 2 is significantly uneven, and the pore structure left by the evaporation of the solution can be clearly observed. This shows that the copolymer network formed by in-situ polymerization helps to improve the quality of perovskite film formation, enhance toughness, and promote the formation of dense and thick perovskite films. Figure 7 The photocurrent curves of the perovskite X-ray detectors prepared in Example 2 and Comparative Example 2 under X-ray irradiation switching are shown. Figure 7 As shown in the figure, the photocurrent value of the in situ polymerized perovskite X-ray detector prepared in this embodiment is about 110 nA, which is significantly higher than the photocurrent value of the conventional detector in Comparative Example 2 (88 nA). This fully demonstrates that the active groups on the in situ polymerized copolymer network can react with the uncoordinated Pb in the perovskite. 2+ Coordination and passivation of the defect structure inside the perovskite greatly improve the migration rate of carriers and charges, thereby achieving higher photoelectric conversion efficiency. Example 3 An in-situ polymerized perovskite X-ray detector, such as Figure 1 As shown, its structure from bottom to top is a substrate, an electron transport layer, an in situ polymerized perovskite layer, a hole transport layer and a metal electrode layer; the in situ polymerized perovskite layer is composed of a mixture of perovskite precursor CsMAPbBr3, an organic solvent dimethyl sulfoxide, a polymer monomer dopamine and an initiator Irgacure 2925.

[0027] The method for preparing the above-mentioned in-situ polymerized perovskite X-ray detector comprises the following steps: S1: Spraying the electron transport layer dispersion tin dioxide solution (5 mg / ml) onto the TFT substrate for 3 minutes, followed by annealing at 110°C for 15 minutes to prepare the electron transport layer with a thickness of 4 nm. S2: Preparation of in situ polymerized perovskite films; S2-1: Add 0.7 g of CsMAPbBr3 to 100 mL of dimethyl sulfoxide and stir to dissolve to obtain a CsMAPbBr3 perovskite precursor solution; the concentration of the perovskite precursor solution is 7 mg / mL; S2-2: Prepare a polymer monomer@perovskite precursor composite solution: Weigh 50 mg of dopamine polymer monomer and 5 mg of Irgacure 2925 and add them to the perovskite precursor solution prepared in step S2-1. After ultrasonic treatment for 30 minutes, stir and dissolve to obtain a dopamine@perovskite precursor composite solution; the mass ratio between the polymer monomer and the perovskite precursor is 1:14; the mass ratio between the initiator and the polymer monomer is 1:10.

[0028] S2-3: A layer of the precursor composite solution prepared in step S2-2 is coated on the electron transport layer obtained in step S1 by doctor blading, and then the precursor composite solution is transferred to a heating table for annealing at 100°C and irradiated under ultraviolet light for 1.5 hours to obtain a polydopamine@CsMAPbBr3 perovskite composite film with a thickness of 550 μm. S3: Spray coating a layer of 2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirobifluorene (spiro-OMeTAD) as a hole transport layer on the original polydopamine@CsMAPbBr3 perovskite composite film prepared in step S2-3, with a thickness of 12 nm. S4: A layer of Au metal electrode is deposited on the hole transport layer prepared in step S3 by evaporation, and the thickness thereof is controlled to be 30 nm.

[0029] Comparative Example 3 This comparative example is a conventional perovskite X-ray detector, whose structure from bottom to top is substrate, electron transport layer, perovskite film, hole transport layer and metal electrode layer; The above-mentioned conventional method for preparing a perovskite X-ray detector differs from that of Example 3 in that step S2-2 is omitted, and a layer of the perovskite precursor solution in step S2-1 is directly coated on the electron transport layer prepared in step S1 by scraping, and then transferred to a vacuum drying oven and annealed at 100°C for 1.5 hours to obtain a perovskite film. The other steps remain the same as those of Example 3.

[0030] The photocurrent value of the new detector in Example 3 is approximately 120 nA, which is much higher than the photocurrent value of the conventional detector in Comparative Example 3 (40 nA). This is mainly because the in-situ polymerized perovskite composite film has good film-forming properties, high toughness and crack resistance, and its chemical stability is also enhanced. The charge transfer rate of the film is greatly improved, thereby achieving a high photocurrent output value.

Claims

1. An in-situ polymerized perovskite X-ray detector, characterized in that: Its structure from bottom to top is substrate, electron transport layer, in-situ polymerized perovskite layer, hole transport layer and metal electrode layer; The in-situ polymerized perovskite layer is composed of a mixture of a perovskite precursor, an organic solvent, a polymer monomer, and an initiator; The perovskite precursor is CsPbI3, CsPbBr3, FACsPb I3 , one or more of MACsPbI3, MACsPbBrI2, FACsPbBr3, Cs2AgBiBr6, MAPbI3, MAPbBr3, and CsMAPbBr3; The polymer monomer is one of acrylamide, dopamine, polyvinyl pyrrolidone, styrene, methacrylic acid, acrylonitrile, acrylate, ketoacrylate, epoxy acrylate, hydroxyethyl acrylate, ‌4,4'-hexafluoroisopropylidene-phthalic anhydride, pyromellitic dianhydride, 4,4'-diaminodiphenyl ether, monomethoxy polyethylene glycol, and ethylene glycol dimethacrylate; The initiator is one of 2,2-azoisobutyronitrile, 2-hydroxy-2-methylpropenone, Irgacure 2925, benzophenone, acetophenone, azobisisobutyronitrile, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methylpropanone, azobisisobutylimidazoline hydrochloride, and folic acid.

2. The in-situ polymerized perovskite X-ray detector according to claim 1, characterized in that: The organic solvent is one of acetonitrile, methanol, ethanol, dimethyl sulfoxide, dimethylformamide, chloroform, acetone, ethyl acetate, ether, and ethylene glycol monomethyl ether.

3. The in-situ polymerized perovskite X-ray detector according to claim 1 or 2, characterized in that: The thickness of the electron transport layer is 3-20 nm; the thickness of the in-situ polymerized perovskite layer is 400-750 μm; The thickness of the hole transport layer is 3~25nm; the thickness of the metal electrode layer is 5~80nm.

4. The method for preparing an in-situ polymerized perovskite X-ray detector according to any one of claims 1 to 3, characterized in that: The following steps are involved: S1: spraying an electron transport layer dispersion onto a substrate, and then performing an annealing treatment to prepare an electron transport layer; S2: Preparation of in-situ polymerized perovskite layer; S2-1: adding a perovskite precursor to an organic solvent, stirring and dissolving the mixture to obtain a perovskite precursor solution; S2-2: Adding polymer monomers and initiators to the perovskite precursor solution prepared in step S2-1, and forming a uniformly dispersed composite solution by ultrasonication and stirring; S2-3: Apply a layer of the composite stock solution prepared in step S2-2 on the electron transport layer prepared in step S1 by scraping, spraying or spin coating, and then transfer the composite stock solution to a heating table for thermal annealing and irradiation with ultraviolet light to obtain an in-situ polymerized perovskite layer; S3: coating the in-situ polymerized perovskite layer prepared in step S2 with a layer of 2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirobifluorene or C60 by blade coating, spray coating or spin coating to prepare a hole transport layer; S4: Vapor-depositing a layer of gold or silver on the hole transport layer prepared in step S3 as a metal electrode.

5. The method for preparing an in-situ polymerized perovskite X-ray detector according to claim 4, characterized in that: In step S1, the annealing temperature is 100° C. to 120° C., the annealing time is 15 to 30 minutes, and the spraying time is 3 to 5 minutes.

6. The method for preparing an in-situ polymerized perovskite X-ray detector according to claim 4 or 5, characterized in that: In step S2-1, the concentration of the perovskite precursor solution is 7-12 mg / mL.

7. The method for preparing an in-situ polymerized perovskite X-ray detector according to claim 4 or 5, characterized in that: In step S2-2, the mass ratio between the polymer monomer and the perovskite precursor is (0.01-0.5):

1.

8. The method for preparing an in-situ polymerized perovskite X-ray detector according to claim 4 or 5, characterized in that: In step S2-2, the mass ratio between the initiator and the polymer monomer is (0.001-0.1):

1.

9. The method for preparing an in-situ polymerized perovskite X-ray detector according to claim 4 or 5, characterized in that: In step S2-3, the annealing temperature of the heating stage is 100°C to 120°C, the annealing time is 1 to 3 hours, and the irradiation time of the ultraviolet lamp is 1 to 3 hours.

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