WO2023010744A1 - X光活性材料及其制备方法和应用 - Google Patents

X光活性材料及其制备方法和应用 Download PDF

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WO2023010744A1
WO2023010744A1 PCT/CN2021/137705 CN2021137705W WO2023010744A1 WO 2023010744 A1 WO2023010744 A1 WO 2023010744A1 CN 2021137705 W CN2021137705 W CN 2021137705W WO 2023010744 A1 WO2023010744 A1 WO 2023010744A1
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ray
active material
perovskite
ray active
carbon group
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French (fr)
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薛冬峰
李云龙
王晓明
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Shenzhen Institute of Advanced Technology of CAS
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Shenzhen Institute of Advanced Technology of CAS
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the application belongs to the field of photoelectric technology, and in particular relates to an X-ray active material and a preparation method thereof, a preparation method of a perovskite X-ray active layer, and an X-ray detector.
  • An X-ray detector is a device that converts X-ray energy into electrical signals that can be recorded.
  • X-ray detectors have been used more and more in small security inspection equipment, industrial parts inspection, large container inspection, medical treatment and other fields.
  • X-ray detectors are mostly used as indirect conversion X-ray detectors using scintillators, which are usually composed of scintillators, detector chips, and substrates; the working principle is that X photons enter the scintillator and are converted into visible light The output enters the detector chip, and then the photoelectric conversion is performed by the detector chip to form an electrical signal, which is transmitted to the subsequent signal processing chip through the wires on the chip and the substrate to form the final image.
  • direct conversion X-ray detectors can directly convert X-ray absorption into charge carriers, and have the advantages of small radiation dose, high spatial resolution, large contrast range, and simple device structure. There are broader application prospects in terms of application.
  • the core of the direct conversion X-ray flat panel image detector is the X-ray active layer, which is a material that directly converts X-ray absorption into charge carriers.
  • the X-ray active layer is a material that directly converts X-ray absorption into charge carriers.
  • X-ray active layer is a material that directly converts X-ray absorption into charge carriers.
  • a-Se:As arsenic-doped amorphous selenium material
  • devices based on this material have harsh fabrication conditions and extremely low detection efficiency for high-energy X-rays. Therefore, finding alternative materials is of great significance for the development of next-generation X-ray image detectors.
  • Halide perovskite materials are considered to be the most likely next-generation materials to replace a-Se:As due to their excellent X-ray absorption properties, high carrier mobility, and long carrier lifetime.
  • the perovskite X-ray active layer prepared by the current technology is mostly perovskite single crystal based on nucleation and growth in solution. This method can conveniently obtain high-quality and certain thickness perovskite materials, but this process method is not suitable for The preparation of the functional layer in the later stage brings restrictions, and the cost is high, the speed is slow, and the area is small, so it is not suitable for large-scale industrial production.
  • the purpose of this application is to provide an X-ray active material and its preparation method, as well as an X-ray detector, which aims to solve the problem that there are few types of X-ray active materials that can directly convert X-rays into electrical signals.
  • the present application provides an X-ray active material
  • the X-ray active material is a halide perovskite material, and its general chemical formula is: AYZ 3 ; wherein, A includes alkali metal ions or organic ammonium ions, and Y Including carbon group metal elements, Z includes at least one halogen.
  • the A includes Cs + or Cs + and Rb + .
  • the organic ammonium ion includes: at least one of CH 3 NH 3 + and CH 2 (NH 3 ) 2 + .
  • the Y includes: at least one of lead and tin.
  • halogen includes: at least one of chlorine, bromine and iodine.
  • the general chemical formula of the X-ray active material is: APbZ 1 x Z 2 3-x ; wherein, Z 1 and Z 2 are selected from different halogens, 0.5 ⁇ x ⁇ 1.5.
  • the general chemical formula of the X-ray active material is: APbBr x I 3-x .
  • the present application provides a method for preparing an X-ray active material, comprising the following steps:
  • the organic ammonium halide or the alkali metal halide and the carbon group metal halide are mixed and reacted with the first organic solvent, vacuum dried and annealed to obtain the perovskite type X-ray active material.
  • the ratio of the molar weight of organic ammonium ions or alkali metal ions, the molar weight of carbon group metal ions to the molar weight of halogen is 1:1:3.
  • vacuum drying temperature is 20-40°C.
  • the conditions of the annealing treatment include: increasing the temperature from 20-40°C to 110-130°C at a rate of 5-10°C/h.
  • organic ammonium halide is selected from: CH 3 NH 3 Cl, CH 3 NH 3 Br, CH 3 NH 3 I, CH 2 (NH 3 ) 2 Cl, CH 2 (NH 3 ) 2 Br, CH 2 ( at least one of NH 3 ) 2 I.
  • the alkali metal halide is selected from at least one of CsCl, CsBr, CsI, RbCl, RbBr, and RbI.
  • the halogenated carbon group metal is selected from at least one of lead chloride, lead bromide, lead iodide, tin chloride, tin bromide, and tin iodide.
  • the first organic solvent is selected from at least one of chlorobenzene, toluene, and N-methylpyrrolidone.
  • the present application provides a method for preparing a perovskite X-ray active layer, comprising the following steps:
  • the mixed slurry is deposited on a substrate, annealed after vacuum drying, and a perovskite X-ray active layer is formed on the substrate.
  • the mass ratio of the X-ray active material, the conductive polymer binder and the second organic solvent is (90-110):1:(10-20).
  • the step of mixing the X-ray active material, the conductive polymer binder and the second organic solvent includes: mixing the raw material components of the X-ray active material with the conductive polymer binder and the The second organic solvent is mixed.
  • the conductive polymer binder is selected from at least one of polythiophene and poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine].
  • the second solvent is selected from at least one of chlorobenzene, toluene, and N-methylpyrrolidone.
  • vacuum drying temperature is 20-40°C.
  • the conditions of the annealing treatment include: increasing the temperature from 20-40°C to 110-130°C at a rate of 5-10°C/h.
  • the perovskite X-ray active layer has a thickness of 100-1000 ⁇ m.
  • the raw material components of the X-ray active material include: organic ammonium halides or alkali metal halides and carbon group metal halides.
  • the present application provides an X-ray detector, which includes the above-mentioned X-ray active material, or the perovskite X-ray active layer prepared by the above method.
  • the X-ray active material provided in the first aspect of the present application is a halide perovskite material with the general chemical formula: AYZ 3 , where A includes alkali metal ions or organic ammonium ions, Y includes carbon group metal elements, and Z includes at least one A halogen, the Z position forms a regular octahedron with the Y-position carbon group metal element in the form of 6 coordination, and eight [YZ 6 ] 4- octahedrons form a cage in the form of common vertex connections, and the A position occupies the center of the cage. To the supporting role of the perovskite structure, it forms a 12-coordination with the Z site.
  • the Y-position carbon group metal element has a large atomic number and high absorption efficiency for X-rays, which is far greater than that of selenium and other elements.
  • the X-ray perovskite active material provided by this application significantly improves the X-ray absorption and conversion efficiency of the active material through the synergistic effect of alkali metal ions or organic ammonium ions in AYZ 3 and carbon group metal elements such as halogen and lead.
  • the X-ray active material has the characteristics of high charge carrier mobility, long charge carrier diffusion length, and very good bulk defect tolerance, so that it has better application prospects.
  • the organic ammonium halide or the alkali metal halide and the carbon group metal halide are mixed with the first organic solvent under an inert atmosphere , so that each raw material component is fully contacted and reacted, self-assembled to generate the primary product of perovskite X-ray active material, and then the solvent component in the reaction system is removed by drying treatment, and then annealing treatment is carried out to make the X-ray active material further Self-assembly makes the perovskite crystal form more orderly, improves the purity and integrity of the X-ray active material, and makes its performance more stable, thereby obtaining the perovskite X-ray active material.
  • the preparation method of the X-ray active material of the present application has low equipment requirements, simple and efficient process, and low cost, and is suitable for large-scale industrial production and application
  • the X-ray active material, the conductive polymer binder and the second organic solvent are mixed under an inert atmosphere Uniform, then deposit the mixed slurry on the substrate, remove the excess solvent in the slurry by vacuum drying, and then perform annealing treatment to solidify the slurry and make the X-ray active material further self-assemble to improve the X-ray activity in the active layer
  • the order, structural integrity, purity, performance stability and other characteristics of the material perovskite crystal form in order to prevent the raw material from absorbing water and deliquescence and being oxidized.
  • the preparation method of the perovskite X-ray active layer of the present application has a simple process and low equipment requirements.
  • the deposition of the mixed slurry on the substrate can quickly prepare perovskite X-ray active layers of different thicknesses in a large area, and the preparation is flexible and efficient, and
  • the prepared perovskite X-ray active layer has good bonding stability with the substrate, high conversion efficiency for X-ray absorption, superior photoelectric performance, and wide application range.
  • the X-ray detector provided in the fourth aspect of the present application contains the above-mentioned X-ray active material or perovskite X-ray active layer.
  • the X-ray detector receives X-ray radiation
  • the X-ray activity in the perovskite X-ray active layer The material first absorbs photons to generate electron and hole pairs, and then these electron and hole pairs are converted into free carriers under the action of an external electric field, migrate to the electrodes, and are finally collected by their respective electrodes.
  • the X-ray detector of the present application can directly convert X-ray absorption into charge carriers, has high conversion efficiency of X-ray absorption, also has high efficiency for high-energy X-ray detection, and has good photoelectric stability.
  • Figures 1 to 2 are schematic structural views of the X-ray active materials provided in the examples of the present application.
  • Fig. 3 is that embodiment 1 of the present application and comparative example 1 provide the I-t test figure of X-ray detector under the X-ray irradiation of different time;
  • Fig. 4 is an I-V test diagram of an X-ray detector made of the X-ray active material provided in Example 1 of the present application.
  • the term "and/or” describes the association relationship of associated objects, indicating that there may be three relationships, for example, A and/or B may mean: A exists alone, A and B exist simultaneously, and B exists alone Condition. Among them, A and B can be singular or plural.
  • the character "/" generally indicates that the contextual objects are an "or" relationship.
  • At least one means one or more, and “multiple” means two or more.
  • At least one of the following” or similar expressions refer to any combination of these items, including any combination of single or plural items.
  • at least one (one) of a, b or c or “at least one (one) of a, b and c” can mean: a, b, c, a-b (that is, a and b), a-c, b-c, or a-b-c, wherein a, b, and c can be single or multiple.
  • sequence numbers of the above-mentioned processes do not mean the order of execution, and some or all steps may be executed in parallel or sequentially, and the execution order of each process shall be based on its functions and The internal logic is determined and should not constitute any limitation to the implementation process of the embodiment of the present application.
  • the weight of the relevant components mentioned in the description of the embodiments of the present application can not only refer to the specific content of each component, but also represent the proportional relationship between the weights of the various components.
  • the scaling up or down of the content of the fraction is within the scope disclosed in the description of the embodiments of the present application.
  • the mass in the description of the embodiments of the present application may be ⁇ g, mg, g, kg and other well-known mass units in the chemical industry.
  • first and second are only used for descriptive purposes to distinguish objects such as substances from each other, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of indicated technical features.
  • first XX can also be called the second XX
  • second XX can also be called the first XX.
  • a feature defined as “first” and “second” may explicitly or implicitly include one or more of these features.
  • the first aspect of the embodiment of the present application provides an X-ray active material
  • the X-ray active material is a halide perovskite material, and its general chemical formula is: AYZ 3 ; wherein, A includes a base Metal ions or organic ammonium ions, Y includes carbon group metal elements, and Z includes at least one halogen.
  • the X-ray active material provided in the first aspect of the embodiment of the present application is a halide perovskite material with a general chemical formula: AYZ 3 , where A includes alkali metal ions or organic ammonium ions, Y includes carbon group metal elements, and Z includes At least one halogen, the Z position forms a regular octahedron with the Y-position carbon group metal element in the form of 6 coordination, and eight [YZ 6 ] 4- octahedrons form a cage in the form of a common vertex connection, and the A position occupies the cage The center acts as a support for the perovskite structure and forms a 12-coordination with the Z site.
  • the Y-position carbon group metal element has a large atomic number and high absorption efficiency for X-rays, which is far greater than that of selenium and other elements.
  • the X-ray perovskite active material provided in the examples of this application significantly improves the X-ray absorption and conversion of the active material through the synergistic effect of alkali metal ions or organic ammonium ions in AYZ 3 and carbon group metal elements such as halogen and lead.
  • the crystal structure formed by AYZ 3 is connected by common vertices to form a carrier path, which is conducive to the migration and transmission of carriers, so that X-ray active materials have high charge carrier mobility and long charge carrier diffusion. Length, and very good bulk defect tolerance and other characteristics, so that it has better application prospects.
  • the A-site ions of the X-ray active material in the embodiment of the present application mainly serve to provide lattice occupation and three-dimensional perovskite structure support, and can also affect the solubility, stability and other physical properties of the perovskite material.
  • A includes Cs + or Cs + and Rb + , and these alkali metal ions at the A site can effectively improve the thermal stability of the X-ray active material.
  • the organic ammonium ions include: at least one of CH 3 NH 3 + , CH 2 (NH 3 ) 2 + ; these organic ammonium ions at the A position can improve the film-forming performance of the X-ray active material.
  • Y includes at least one of lead and tin.
  • halogen includes at least one of chlorine, bromine, and iodine.
  • these Z-position halogens can form a regular octahedral structure with the Y-position, and the octahedrons share vertices to form a carrier path, so that the formed perovskite X-ray active materials have high charge carrier mobility, long electron Carrier diffusion length; on the other hand, the top of the valence band in the energy band structure of perovskite X-ray active materials mainly comes from the contribution of bonding coupling between the 6s orbital of the carbon group metal element and the outer p orbital at the Z site.
  • the general chemical formula of the X-ray active material is: APbZ 1 x Z 2 3-x ; wherein Z 1 and Z 2 are selected from different halogens, 0.5 ⁇ x ⁇ 1.5.
  • the Z site of the X-ray active material in the embodiment of the present application contains two different halogens at the same time. The introduction of two kinds of halogens into the perovskite lattice can better adjust the photoelectric properties of the perovskite X-ray active material, making the active material It has better X-ray absorption conversion properties.
  • the self-assembly of the perovskite crystal form in the X-ray active material can be promoted, and the quality of the active material can be improved.
  • the embodiment of the present application is preferably 0.5 ⁇ x ⁇ 1.5.
  • the value range of x enables two different halogens to have a better synergistic effect, and achieves a balanced optimization of the band gap, carrier mobility, and X-ray sensitivity of the X active material. .
  • the general chemical formula of the X-ray active material is: APbBr x I 3-x , 0.5 ⁇ x ⁇ 1.5.
  • the embodiment of the present application introduces bromine element into the crystal lattice of the X-ray active material, which can effectively regulate the photoelectricity of the active material, so that the active material has better X-ray absorption conversion properties, and the introduction of an appropriate amount of bromine can further promote the perovskite Self-assembly of X-ray active materials, thereby improving the preparation efficiency of active materials.
  • the synergistic effect of bromine and iodine elements improves the X-ray absorption conversion efficiency of the active material, and at the same time facilitates the synthesis and preparation of the perovskite material, thereby improving the quality of the perovskite material.
  • the general chemical formula of the X-ray active material is: APbBr x I 3-x , 0.85 ⁇ x ⁇ 1.05 in the X-ray active material, bromine and iodine have better synergistic effects in this ratio range
  • the role can realize the optimization of the balance between the band gap, charge carrier mobility and X-ray sensitivity of X-ray active materials.
  • the general chemical formula of the X-ray active material is: APbBr x I 3-x , 0.85 ⁇ x ⁇ 1.05 in the X-ray active material, A includes Cs + , Cs + and Rb + , CH 3 NH 3 + and at least one of CH 2 (NH 3 ) 2 + .
  • the X-ray active materials in the examples of this application can be prepared by the methods in the following examples.
  • the second aspect of the embodiment of the present application provides a method for preparing an X-ray active material, comprising the following steps:
  • the organic ammonium halide or the alkali metal halide and the carbon group metal halide are mixed and reacted with the first organic solvent, then vacuum-dried and annealed to obtain a perovskite-type X-ray active material.
  • the organic ammonium halide or the alkali metal halide and the carbon group metal halide are mixed with the first organic solvent.
  • each raw material component is fully contacted and reacted, self-assembled to generate the primary product of perovskite-type X-active material, and then the solvent component in the reaction system is removed by drying treatment, and then annealing treatment is performed to make the X-ray activity through thermal disturbance
  • the material is further self-assembled to make the perovskite crystal form more orderly, improve the purity and complete structure of the X-ray active material, and make its performance more stable, thereby obtaining the perovskite X-ray active material.
  • the preparation method of the X-ray active material in the embodiment of the present application has low equipment requirements, simple and efficient process, and low cost, and is suitable for industrialized large-scale production and application.
  • the ratio of the molar amount of the organic ammonium ion or the alkali metal ion, the molar amount of the carbon group metal ion to the molar amount of the halogen is 1:1:3; the ratio of the molar amount is effective The stability of the perovskite crystal form of the X-ray active material is ensured.
  • the vacuum drying temperature is 20-40°C.
  • each raw material component undergoes preliminary self-assembly during the mixing process to form a perovskite crystal form, and then at a temperature of Vacuum drying at room temperature of 20-40° C. to remove the solvent in the mixed slurry to obtain a dry primary product. If the drying temperature is too high, the material will easily decompose.
  • the annealing conditions include: increasing the temperature from 20-40°C to 110-130°C at a rate of 5-10°C/h.
  • the temperature of the dried perovskite-type X-ray active material is raised from 20-40°C to 110-130°C at a rate of 5-10°C/h for gradient annealing.
  • the thermal disturbance in the X-ray active material further self-assembles, makes the perovskite crystal form more orderly, improves the purity and complete structure of the X-ray active material, and makes its performance more stable, thus obtaining perovskite X-ray active material.
  • the annealing rate is too slow or the annealing temperature is too low, the optimization effect on the X-ray active material perovskite crystal form and purity is not good, which is not conducive to improving the stability of the X-ray active material; if the annealing temperature rise rate is too fast Or the temperature is too high, then the material is easy to decompose.
  • the organic ammonium halide is selected from the group consisting of: CH 3 NH 3 Cl, CH 3 NH 3 Br, CH 3 NH 3 I, CH 2 (NH 3 ) 2 Cl, CH 2 (NH 3 ) 2 Br, CH 2 At least one of (NH 3 ) 2 I; these organic ammonium halides can form perovskite materials with the general chemical formula AYZ 3 after self-assembly with halogenated carbon group metals, where A includes CH 3 NH 3 + , CH At least one of 2 (NH 3 ) 2 + , Y includes carbon group metal elements, Z includes at least one halogen, CH 3 NH 3 + , CH 2 (NH 3 ) 2 + introduced at the A site of the perovskite material Such organic ammonium salts can effectively improve the film-forming performance of perovskite materials.
  • the alkali metal halide is selected from at least one of: CsCl, CsBr, CsI, RbCl, RbBr, and RbI; these alkali metal halides can form a chemical formula of AYZ after self-assembly with a carbon group metal halide A perovskite material, wherein A includes at least one of Cs + and Rb + , Y includes a carbon group metal element, Z includes at least one halogen, Cs + or Cs + introduced into the A site of the perovskite material and Alkali metal ions such as Rb + can effectively improve the thermal stability of perovskite materials.
  • the carbon group metal halide is selected from at least one of lead chloride, lead bromide, lead iodide, tin chloride, tin bromide, and tin iodide; these carbon group metal halides can be combined with organic Self-assembly of ammonium halides or alkali metal halides introduces carbon group metals such as lead and tin into the perovskite lattice of X-ray active materials.
  • the first organic solvent is selected from at least one of chlorobenzene, toluene, and N-methylpyrrolidone, and these organic solvents can uniformly and stably disperse organic ammonium halides, alkali metal halides, and carbon group metal halides. In the solvent, it is beneficial for each raw material component to contact and react with each other.
  • the third aspect of the embodiment of the present application provides a method for preparing a perovskite X-ray active layer, comprising the following steps:
  • the preparation method of the perovskite X-ray active layer provided in the third aspect of the embodiment of the present application, in order to prevent the raw material from absorbing water and deliquescence and being oxidized, the X-ray active material, the conductive polymer binder and the second organic The solvent is mixed evenly, and then the mixed slurry is deposited on the substrate, and the excess solvent in the slurry is removed by vacuum drying, and then annealed, so that the slurry is solidified and formed, and the X-ray active material is further self-assembled to improve the active layer.
  • the preparation method of the perovskite X-ray active layer in the embodiment of this application has a simple process and low equipment requirements.
  • the deposition of the mixed slurry on the substrate can quickly prepare perovskite X-ray active layers of different thicknesses in a large area, and the preparation is flexible and efficient.
  • the prepared perovskite X-ray active layer has good bonding stability with the substrate, high conversion efficiency for X-ray absorption, superior photoelectric performance, and wide application range.
  • the mass ratio of the X-ray active material, the conductive polymer binder and the second organic solvent is (90-110):1:(10-20)
  • the mass ratio of each raw material component in the mixed slurry not only ensures the viscosity of the mixed slurry, but also facilitates the deposition and formation of the mixed slurry on the surface of the substrate, and has good bonding stability with the substrate; it also ensures that the prepared Perovskite X-ray active layer absorbs and converts X-rays, and charge carrier transfer efficiency.
  • the conductive polymer binder not only plays the role of adjusting the viscosity of the slurry, but also plays the role of a hole transport path, and synergistically improves the charge transport efficiency of the perovskite active layer. If the content of the X-ray active material is too low, the absorption conversion efficiency of the X-ray perovskite X-ray active layer is reduced.
  • the mass ratio of the X-ray active material, the conductive polymer binder and the second organic solvent is 100:1:20.
  • the step of mixing the X-ray active material, the conductive polymer binder and the second organic solvent includes: mixing the raw material components of the X-ray active material with the conductive polymer binder and the second organic solvent mix.
  • the raw material components of the X-ray active material can be directly mixed with the conductive polymer binder and the second organic solvent, and the X-ray active material can be generated in situ during the curing and molding process of the perovskite X-ray active layer , improve the stability of the combination of active materials and binders, deposition, etc., so that the performance of the formed perovskite X-ray active layer is better.
  • the raw material components of the X-ray active material include: organic ammonium halides or alkali metal halides and carbon group metal halides, and the raw materials of these X-ray active materials can self-assemble under the condition of the second organic solvent to form perovskite X active material in mineral crystal form.
  • the conductive polymer binder is selected from: polythiophene (P3HT), poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA) At least one; these conductive polymer binders have excellent hole mobility, have a good energy level matching effect with perovskite-type X-ray active materials, are conducive to exciton splitting, and adhere to perovskite X-ray active materials. Strong compatibility, which can improve the bonding stability between the perovskite X-ray active layer and the substrate.
  • P3HT polythiophene
  • PTAA poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine]
  • the second organic solvent is selected from at least one of chlorobenzene, toluene, and N-methylpyrrolidone.
  • These organic solvents are effective for X-ray active materials such as organic ammonium halides, alkali metal halides, and carbon group metals
  • X-ray active materials such as organic ammonium halides, alkali metal halides, and carbon group metals
  • Raw material components, as well as X-ray active materials, conductive polymer binders and other materials have a good dispersion effect, so that each component is uniformly and stably dispersed in the solvent, which is conducive to the mutual contact and reaction of each component.
  • the manner of depositing the mixed slurry on the substrate may be scraping, coating, etc., and the substrate may be glass with indium tin oxide ITO.
  • the size of the substrate can be (1-3 inches) ⁇ (1-3 inches).
  • the mixed slurry in the embodiment of the present application is deposited on the substrate by scraping, etc., and can be used in a larger area. More uniform film-forming areas are obtained on the substrate, and large-scale and rapid preparation of perovskite X-ray active layers of different thicknesses is achieved, which is flexible and efficient.
  • the vacuum drying temperature is 20-40°C.
  • the solvent in the mixed slurry is removed by vacuum drying, and the material is solidified and shaped. If the drying temperature is too high, it is easy to cause cracks in the deposited mixed slurry layer, which will destroy the stability of the perovskite X-ray active layer.
  • the annealing conditions include: increasing the temperature from 20-40°C to 110-130°C at a rate of 5-10°C/h.
  • annealing the dried deposition layer can not only further remove the solvent components in the deposition layer, but also further self-assemble the perovskite X-ray active material through thermal disturbance, and improve the order of the perovskite crystal form. Properties such as sex, structural integrity, purity, and performance stability, thereby improving the optoelectronic performance of the perovskite X-ray active layer.
  • the annealing rate is too slow or the annealing temperature is too low, the optimization effect on the perovskite crystal form and purity in the perovskite X-ray active layer is not good, which is not conducive to improving the optoelectronic properties and stability of the perovskite X-ray active layer. properties; if the annealing heating rate is too fast or the temperature is too high, it is easy to cause cracks in the perovskite X-ray active layer and destroy the stability of the perovskite X-ray active layer.
  • the perovskite X-ray active layer has a thickness of 100-1000 ⁇ m.
  • the preparation method of the perovskite X-ray active layer in the embodiment of the present application can quickly prepare perovskite X-ray active layers with different thicknesses in a large area, and the preparation is flexible and efficient, so that the perovskite X-ray active layer can be adapted to devices of different systems , to improve its application flexibility.
  • the mixed slurry is deposited on the substrate at 200 ⁇ L/(1 inch ⁇ 3 inches), and the slurry is deposited under this condition to obtain a suitable film thickness and good film uniformity, And the mixed slurry has better contact performance with substrates such as ITO.
  • the fourth aspect of the embodiment of the present application provides an X-ray detector, the X-ray detector includes the above-mentioned X-ray active material, or the perovskite X-ray active layer prepared by the above method.
  • the X-ray detector provided in the fourth aspect of the embodiment of the present application contains the above-mentioned X-ray active material or perovskite X-ray active layer.
  • X in the perovskite X-ray active layer Photoactive materials first absorb photons to generate electrons and hole pairs, and then these electrons and hole pairs are converted into free carriers under the action of an external electric field, migrate to the electrodes, and are finally collected by their respective electrodes.
  • the X-ray detector of the embodiment of the present application can directly convert X-ray absorption into charge carriers, has high conversion efficiency of X-ray absorption, and also has high efficiency for high-energy X-ray detection, and has good photoelectric stability.
  • a perovskite-based X-ray detector the preparation of which comprises the steps of:
  • the perovskite dye was coated on the ITO substrate by adjusting the width of the gap between the scraper and the substrate and the scraping rate; the obtained dye layer was vacuum-dried at room temperature to remove the solvent, and the Gradient annealing was performed on the perovskite layer from room temperature to 120°C at a rate of /h to obtain a perovskite X-ray active layer of CH 3 NH 3 PbI 3 with a thickness of 500 ⁇ m;
  • the evaporation rate is Under the condition of evaporation time of 1500s, Au was vacuum-deposited on the surface of perovskite X-ray active layer to form Au metal back electrode, and a perovskite-based X-ray detector with ITO/CH 3 NH 3 PbI 3 /Au structure was obtained .
  • a perovskite-based X-ray detector the preparation of which comprises the steps of:
  • the perovskite dye was coated on the ITO substrate by adjusting the width of the gap between the scraper and the substrate and the scraping rate; the obtained dye layer was vacuum-dried at room temperature to remove the solvent, and the Gradient annealing was performed on the perovskite layer from room temperature to 120°C at a rate of /h to obtain a perovskite X-ray active layer of CH 2 (NH 3 ) 2 PbI 3 with a thickness of 500 ⁇ m;
  • the evaporation rate is Under the condition of evaporation time of 1500s, Au was vacuum-deposited on the surface of the perovskite X-ray active layer to form an Au metal back electrode, and a perovskite-based X-ray with ITO/CH 2 (NH 3 ) 2 PbI 3 /Au structure was obtained. light detector.
  • a perovskite-based X-ray detector the preparation of which comprises the steps of:
  • the perovskite dye was coated on the ITO substrate by adjusting the width of the gap between the scraper and the substrate and the scraping rate; the obtained dye layer was vacuum-dried at room temperature to remove the solvent, and the Gradient annealing was performed on the perovskite layer from room temperature to 120°C at a rate of /h to obtain a perovskite X-ray active layer of CsPbI 3 with a thickness of 500 ⁇ m;
  • the evaporation rate is Under the condition that the evaporation time is 1500s, Au is vacuum evaporated on the surface of perovskite X-ray active layer to form Au metal back electrode, and a perovskite-based X-ray detector with ITO/CsPbI 3 /Au structure is obtained.
  • a perovskite-based X-ray detector the preparation of which comprises the steps of:
  • the perovskite dye was coated on the ITO substrate by adjusting the width of the gap between the scraper and the substrate and the scraping rate; the obtained dye layer was vacuum-dried at room temperature to remove the solvent, and the Gradient annealing was performed on the perovskite layer from room temperature to 120°C at a rate of /h to obtain a perovskite X-ray active layer of CH 3 NH 3 PbBrI 2 with a thickness of 500 ⁇ m;
  • the evaporation rate is Under the condition that the evaporation time is 1500s, Au is vacuum-deposited on the surface of perovskite X-ray active layer to form Au metal back electrode, and a perovskite-based X-ray detector with ITO/CH 3 NH 3 PbBrI 2 /Au structure is obtained .
  • a perovskite-based X-ray detector the preparation of which comprises the steps of:
  • the perovskite dye was coated on the ITO substrate by adjusting the width of the gap between the scraper and the substrate and the scraping rate; the obtained dye layer was vacuum-dried at room temperature to remove the solvent, and the Gradient annealing was performed on the perovskite layer from room temperature to 120°C at a rate of /h to obtain a perovskite X-ray active layer of CsPbBr 3 with a thickness of 500 ⁇ m;
  • the evaporation rate is Under the condition that the evaporation time is 1500s, Au is vacuum evaporated on the surface of perovskite X-ray active layer to form Au metal back electrode, and a perovskite-based X-ray detector with ITO/CsPbBr 3 /Au structure is obtained.
  • the perovskite-based X-ray detectors provided in Examples 1 to 5 and Comparative Example 1 were subjected to photocurrent tests, that is, I-t tests, to obtain X-ray detectors at different times.
  • the perovskite-based X-ray detectors prepared from the perovskite X-ray active layer in Examples 1 to 5 of the present application respectively contain CH 3 NH 3 PbI 3 , CH 2 (NH 3 ) 2 PbI 3 , CsPbI 3 , CH 3 NH 3 PbBrI 2 , CsPbBr 3 and other X-ray active materials make X-ray detectors exhibit higher X-ray sensitivity and more High mobility lifetime product value, lower bias requirement.
  • the X-ray perovskite active material of the embodiment of the present application significantly improves the X-ray absorption and conversion efficiency of the active material through the synergistic effect of alkali metal ions or organic ammonium ions and carbon group metal elements such as halogens and lead, and at the same time improves It improves its carrier transfer efficiency and material stability, making it have better application prospects.

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Abstract

本申请属于光电技术领域，尤其涉及一种X光活性材料及其制备方法，以及一种钙钛矿X光活性层的制备方法，一种X光探测器。其中，X光活性材料为卤化物钙钛矿材料，其化学通式为：AYZ 3；其中，A包括碱金属离子或者有机铵离子，Y包括碳族金属元素，Z包括至少一种卤素。本申请X光活性材料，通过碱金属离子或者有机铵离子与卤素、铅等碳族金属元素等的协同作用，显著提高了活性材料的X光吸收及转化效率，同时提高了其载流子迁移效率以及材料的稳定性，使其有更好的应用前景。

Description

X光活性材料及其制备方法和应用 技术领域
本申请属于光电技术领域，尤其涉及一种X光活性材料及其制备方法，以及一种钙钛矿X光活性层的制备方法，一种X光探测器。
背景技术
X光探测器(X-ray detector)是一种将X射线能量转换为可供记录的电信号的装置。近年来，随着X光探测器的大规模推广和使用，X光探测器在小型安检设备、工业零件检测、大型集装箱检测、医疗等领域的运用越来越多。
目前，X光探测器应用较多的是采用闪烁体的间接转化X光探测器，通常由闪烁体，探测器芯片，以及基板组合而成；工作原理是X光子入射进入闪烁体，转换为可见光输出，进入探测器芯片，再由探测器芯片进行光电转换，形成电信号，并通过芯片与基板上的导线传输至后续的信号处理芯片，从而形成最终的图像。与之相比，直接转化X光探测器可直接将X光吸收转化为电荷载流子，具有所需辐射剂量小、空间分辨率高、对比度范围大以及器件结构简单等优势，在高端医疗影像应用方面有更广阔的应用前景。直接转化X光平板影像探测器的核心是X光活性层，它是一种直接将X光吸收转化成电荷载流子的材料。目前，性能优越的X光活性材料可选择种类少，砷掺杂的无定型硒材料(a-Se:As)作为X光活性层是主流方法。但是，基于该材料的器件一方面制备条件苛刻，另一方面对高能量X光探测效率极低。因此，寻找可替代材料对发展下一代X光影像探测器意义重大。
卤化物钙钛矿材料由于具有优秀的X光吸收性质、高的载流子迁移率以及长的载流子寿命，因此被视为最有可能替代a-Se:As的下一代材料。当前技术制备钙钛矿X光活性层多为基于溶液中成核生长的钙钛矿单晶，这种方法可以比较方便的获得高质量和一定厚度的钙钛矿材料，但是这种工艺方法对后期功 能层制备带来限制，且成本高、速率慢、面积小，因此不适合大规模工业生产。同时，在目前的技术中，钙钛矿单晶多数是基于双金属电极，与基于导电氧化铟锡(ITO)的TFT等阵列基底结合效果差，严重制约钙钛矿基直接转化X光探测器影像应用前景。
发明内容
本申请的目的在于提供一种X光活性材料及其制备方法，以及一种X光探测器，旨在一定程度上解决现有可直接将X光转化成电信号的X光活性材料种类少，对高能量X光探测效率低的问题。
为实现上述申请目的，本申请采用的技术方案如下：
第一方面，本申请提供一种X光活性材料，所述X光活性材料为卤化物钙钛矿材料，其化学通式为：AYZ 3；其中，A包括碱金属离子或者有机铵离子，Y包括碳族金属元素，Z包括至少一种卤素。
进一步地，所述A包括Cs +或者Cs +和Rb +。
进一步地，所述有机铵离子包括：CH 3NH 3 +、CH 2(NH 3) 2 +中的至少一种。
进一步地，所述Y包括：铅、锡中的至少一种。
进一步地，所述卤素包括：氯、溴、碘中的至少一种。
进一步地，所述X光活性材料的化学通式为：APbZ 1 xZ 2 3-x；其中，Z 1和Z 2分别选自不同的卤素，0.5≤x≤1.5。
进一步地，所述X光活性材料的化学通式为：APbBr xI 3-x。
进一步地，所述X光活性材料中0.85≤x≤1.05。
第二方面，本申请提供一种X光活性材料的制备方法，包括以下步骤：
在惰性气氛下，将有机卤化铵或者卤化碱金属和卤化碳族金属与第一有机溶剂进行混合反应后，真空干燥并退火处理，得到钙钛矿型X光活性材料。
进一步地，所述X光活性材料中，有机铵离子或者碱金属离子的摩尔量、碳族金属离子的摩尔量与卤素的摩尔量之比为1:1:3。
进一步地，所述真空干燥的温度为20～40℃。
进一步地，所述退火处理的条件包括：以5～10℃/h的速率将温度从20～40℃升温至110～130℃。
进一步地，所述有机卤化铵选自：CH 3NH 3Cl、CH 3NH 3Br、CH 3NH 3I、CH 2(NH 3) 2Cl、CH 2(NH 3) 2Br、CH 2(NH 3) 2I中的至少一种。
进一步地，所述卤化碱金属选自：CsCl、CsBr、CsI、RbCl、RbBr、RbI中的至少一种。
进一步地，所述卤化碳族金属选自：氯化铅、溴化铅、碘化铅、氯化锡、溴化锡、碘化锡中的至少一种。
进一步地，所述第一有机溶剂选自：氯苯、甲苯、N-甲基吡咯烷酮中的至少一种。
第三方面，本申请提供一种钙钛矿X光活性层的制备方法，包括以下步骤：
在惰性气氛下，将X光活性材料、导电高分子粘合剂与第二有机溶剂混合，得到混合浆料；
将所述混合浆料沉积在衬底上，真空干燥后进行退火处理，在所述衬底上形成钙钛矿X光活性层。
进一步地，所述混合浆料中，所述X光活性材料、所述导电高分子粘合剂和所述第二有机溶剂的质量比为(90～110):1：(10～20)。
进一步地，所述将X光活性材料、导电高分子粘合剂与第二有机溶剂混合的步骤包括：将所述X光活性材料的原料组分与所述导电高分子粘合剂和所述第二有机溶剂进行混合。
进一步地，，所述导电高分子粘合剂选自：聚噻吩、聚[双(4-苯基)(2,4,6-三甲基苯基)胺]中的至少一种。
进一步地，所述第二有溶剂选自：氯苯、甲苯、N-甲基吡咯烷酮中的至少一种。
进一步地，所述真空干燥的温度为20～40℃。
进一步地，所述退火处理的条件包括：以5～10℃/h的速率将温度从20～40℃升温至110～130℃。
进一步地，所述钙钛矿X光活性层的厚度100-1000μm。
进一步地，所述X光活性材料的原料组分包括：有机卤化铵或者卤化碱金属和卤化碳族金属。
第四方面，本申请提供一种X光探测器，所述X光探测器包括上述的X光活性材料，或者上述方法制备的钙钛矿X光活性层。
本申请第一方面提供的X光活性材料为卤化物钙钛矿材料，化学通式为：AYZ 3，其中，A包括碱金属离子或者有机铵离子，Y包括碳族金属元素，Z包括至少一种卤素，Z位以6配位的形式与Y位碳族金属元素形成正八面体，八个[YZ 6] 4-正八面体以共顶点连接的形式组成一个笼子，A位占据该笼子的中心起到钙钛矿结构支撑作用，与Z位形成12配位。并且，Y位碳族金属元素，原子序数大，对X光的吸收效率高，远远大于硒等元素。本申请提供的X光钙钛矿活性材料，通过AYZ 3中碱金属离子或者有机铵离子与卤素、铅等碳族金属元素等的协同作用，显著提高了活性材料的X光吸收及转化效率，同时使X光活性材料拥有高电荷载流子迁移率，长电荷载流子扩散长度，以及非常好的体相缺陷容忍度等特性，使其有更好的应用前景。
本申请第二方面提供的X光活性材料的制备方法，为防止原料吸水潮解以及被氧化，在惰性气氛下，将有机卤化铵或者卤化碱金属和卤化碳族金属与第一有机溶剂进行混合处理，使各原料组分充分接触反应，进行自组装生成钙钛矿型X活性材料的初产物，然后通过干燥处理去除反应体系中溶剂成分，再进行退火处理，通过热扰动使X光活性材料进一步自组装，使钙钛矿晶型更加有序化，提高X光活性材料的纯度、结构完整，使其性能更稳定，从而得到钙钛矿型X光活性材料。本申请X光活性材料的制备方法，对设备要求低，工艺简单高效，成本低，适用于工业化大规模生产和应用。
本申请第三方面提供的钙钛矿X光活性层的制备方法，为防止原料吸水潮 解以及被氧化，在惰性气氛下，将X光活性材料、导电高分子粘合剂与第二有机溶剂混合均匀，然后将混合浆料沉积在衬底上，通过真空干燥去除浆料中多余溶剂，再进行退火处理，使浆料固化成型的同时使X光活性材料进一步自组装，提高活性层中X活性材料钙钛矿晶型的有序性，结构完整性，纯度，性能稳定性等特性。本申请钙钛矿X光活性层的制备方法，工艺简单，对设备要求低，混合浆料在衬底上沉积可以大面积快速制备不同厚度的钙钛矿X光活性层，制备灵活高效，且制备的钙钛矿X光活性层与衬底结合稳定性好，对X光吸收转化效率高，光电性能优越，适应范围广。
本申请第四方面提供的X光探测器，由于包含有上述X光活性材料或者钙钛矿X光活性层，X光探测器接受X光辐射时，钙钛矿X光活性层中X光活性材料首先吸收光子产生电子和空穴对，然后这些电子和空穴对在外电场的作用下转换为自由载流子向电极迁移，最后被各自的电极收集。本申请X光探测器能够直接将X光吸收转化成电荷载流子，X光吸收转化效率高，对高能量X光探测同样具有较高的效率，且光电稳定性好。
附图说明
为了更清楚地说明本申请实施例中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本申请的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1～2是本申请实施例提供的X光活性材料的结构示意图；
图3是本申请实施例1和对比例1提供X光探测器在不同时间的X光辐照下的I-t测试图；
图4是本申请实施例1提供的X光活性材料制备的X光探测器的I-V测试图。
具体实施方式
为了使本申请要解决的技术问题、技术方案及有益效果更加清楚明白，以下结合实施例，对本申请进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本申请，并不用于限定本申请。
本申请中，术语“和/或”，描述关联对象的关联关系，表示可以存在三种关系，例如，A和/或B，可以表示：单独存在A，同时存在A和B，单独存在B的情况。其中A，B可以是单数或者复数。字符“/”一般表示前后关联对象是一种“或”的关系。
本申请中，“至少一个”是指一个或者多个，“多个”是指两个或两个以上。“以下至少一项(个)”或其类似表达，是指的这些项中的任意组合，包括单项(个)或复数项(个)的任意组合。例如，“a，b或c中的至少一项(个)”，或，“a，b和c中的至少一项(个)”，均可以表示：a，b，c，a-b(即a和b)，a-c，b-c，或a-b-c，其中a，b，c分别可以是单个，也可以是多个。
应理解，在本申请的各种实施例中，上述各过程的序号的大小并不意味着执行顺序的先后，部分或全部步骤可以并行执行或先后执行，各过程的执行顺序应以其功能和内在逻辑确定，而不应对本申请实施例的实施过程构成任何限定。
在本申请实施例中使用的术语是仅仅出于描述特定实施例的目的，而非旨在限制本申请。在本申请实施例和所附权利要求书中所使用的单数形式的“一种”和“该”也旨在包括多数形式，除非上下文清楚地表示其他含义。
本申请实施例说明书中所提到的相关成分的重量不仅仅可以指代各组分的具体含量，也可以表示各组分间重量的比例关系，因此，只要是按照本申请实施例说明书相关组分的含量按比例放大或缩小均在本申请实施例说明书公开的范围之内。具体地，本申请实施例说明书中的质量可以是μg、mg、g、kg等化工领域公知的质量单位。
术语“第一”、“第二”仅用于描述目的，用来将目的如物质彼此区分开，而 不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量。例如，在不脱离本申请实施例范围的情况下，第一XX也可以被称为第二XX，类似地，第二XX也可以被称为第一XX。由此，限定有“第一”、“第二”的特征可以明示或者隐含地包括一个或者更多个该特征。
如附图1和2所示，本申请实施例第一方面提供一种X光活性材料，X光活性材料为卤化物钙钛矿材料，其化学通式为：AYZ 3；其中，A包括碱金属离子或者有机铵离子，Y包括碳族金属元素，Z包括至少一种卤素。
本申请实施例第一方面提供的X光活性材料为卤化物钙钛矿材料，化学通式为：AYZ 3，其中，A包括碱金属离子或者有机铵离子，Y包括碳族金属元素，Z包括至少一种卤素，Z位以6配位的形式与Y位碳族金属元素形成正八面体，八个[YZ 6] 4-正八面体以共顶点连接的形式组成一个笼子，A位占据该笼子的中心起到钙钛矿结构支撑作用，与Z位形成12配位。并且，Y位碳族金属元素，原子序数大，对X光的吸收效率高，远远大于硒等元素。本申请实施例提供的X光钙钛矿活性材料，通过AYZ 3中碱金属离子或者有机铵离子与卤素、铅等碳族金属元素等的协同作用，显著提高了活性材料的X光吸收及转化效率，同时AYZ 3形成的以共顶点连接的晶体构型形成载流子通路，有利于载流子的迁移传输，使X光活性材料拥有高电荷载流子迁移率，长电荷载流子扩散长度，以及非常好的体相缺陷容忍度等特性，使其有更好的应用前景。
本申请实施例X光活性材料的A位离子主要起到提供格位占据和三维钙钛矿结构支撑的作用，同时也能影响钙钛矿材料的溶解度、稳定性等物理性质。在一些实施例中，A包括Cs +或者Cs +和Rb +，A位的这些碱金属离子可有效提高X光活性材料的热稳定性。在另一些实施例中，有机铵离子包括：CH 3NH 3 +、CH 2(NH 3) 2 +中的至少一种；A位的这些有机铵离子可提高X光活性材料的成膜性能。
在一些实施例中，Y包括：铅、锡中的至少一种。本申请实施例X光活性材料中Y位包括铅、锡中的至少一种碳族金属元素，根据物质对X光吸收系数 的关系Z 4/E 3(Z为原子序数，E为X光能量)可知，在同样的X光能量段，铅(Z＝82)、锡(Z＝50)对X光的吸收远远大于硒(Z＝34)，因而这些碳族金属元素对X光的吸收效率高，远远大于硒等元素，可显著提高X光活性材料对X光的吸收效率；另一方面，这些碳族金属元素的6s轨道与Z位的外层p轨道可成键耦合，贡献于钙钛矿X光活性材料的能带结构中价带顶，而碳族金属元素的6p轨道，贡献于钙钛矿能带结构中导带底。
在一些实施例中，卤素包括：氯、溴、碘中的至少一种。一方面，这些Z位卤素均可与Y位形成正八面体结构，八面体共顶点连接形成载流子通路，使得所形成的钙钛矿X光活性材料拥有高电荷载流子迁移率、长电荷载流子扩散长度；另一方面，钙钛矿X光活性材料的能带结构中价带顶主要来源于碳族金属元素的6s轨道与Z位的外层p轨道成键耦合贡献。
在一些实施例中，X光活性材料的化学通式为：APbZ 1 xZ 2 3-x；其中，Z 1和Z 2分别选自不同的卤素，0.5≤x≤1.5。本申请实施例X光活性材料的Z位同时含有两种不同的卤素，在钙钛矿晶格中同时引入两种卤素可更好地调节钙钛矿X光活性材料的光电性能，使活性材料具有更好地X光吸收转化性质。并且，通过两种卤素的协同作用，可促进X光活性材料中钙钛矿晶型自组装，提高活性材料的品质。本申请实施例优选0.5≤x≤1.5，x的该取值范围使两种不同的卤素有更好地协同作用，实现对X活性材料带隙、载流子迁移率、X光灵敏度的平衡优化。另外，Y位选自铅，铅有更大的原子序数(原子序数Z＝82)，对X光有更高的吸收效率；同时拥有更高的电荷载流子迁移率、长电荷载流子扩散长度以及非常好的体相缺陷容忍度等特性。
在一些实施例中，X光活性材料的化学通式为：APbBr xI 3-x，0.5≤x≤1.5。本申请实施例在X光活性材料的晶格中引入溴元素，可有效调控活性材料的光电性，使活性材料具有更好地X光吸收转化性质，而且引入适量的溴可进一步促进钙钛矿X光活性材料的自组装，从而提高了活性材料的制备效率。通过溴和碘元素的协同作用提高活性材料对X光吸收转化效率，同时有利于钙钛矿材料 的合成制备，从而提高钙钛矿材料的品质。
在一些优选实施例中，X光活性材料的化学通式为：APbBr xI 3-x，X光活性材料中0.85≤x≤1.05，溴和碘在该配比区间有更好地协同增效作用，可实现X光活性材料带隙、电荷载流子迁移率与X光灵敏度的平衡最佳化。
在一些具体实施例中，X光活性材料的化学通式为：APbBr xI 3-x，X光活性材料中0.85≤x≤1.05，A包括Cs +、Cs +和Rb +、CH 3NH 3 +、CH 2(NH 3) 2 +中的至少一种。
本申请实施例X光活性材料可通过以下实施例方法制备。
本申请实施例第二方面提供一种X光活性材料的制备方法，包括以下步骤：
S10.在惰性气氛下，将有机卤化铵或者卤化碱金属和卤化碳族金属与第一有机溶剂进行混合反应后，真空干燥并退火处理，得到钙钛矿型X光活性材料。
本申请实施例第二方面提供的X光活性材料的制备方法，为防止原料吸水潮解以及被氧化，在惰性气氛下，将有机卤化铵或者卤化碱金属和卤化碳族金属与第一有机溶剂进行混合处理，使各原料组分充分接触反应，进行自组装生成钙钛矿型X活性材料的初产物，然后通过干燥处理去除反应体系中溶剂成分，再进行退火处理，通过热扰动使X光活性材料进一步自组装，使钙钛矿晶型更加有序化，提高X光活性材料的纯度、结构完整，使其性能更稳定，从而得到钙钛矿型X光活性材料。本申请实施例X光活性材料的制备方法，对设备要求低，工艺简单高效，成本低，适用于工业化大规模生产和应用。
在一些实施例中，X光活性材料中，有机铵离子或者碱金属离子的摩尔量、碳族金属离子的摩尔量与卤素的摩尔量之比为1:1:3；该摩尔量之比有效确保了X光活性材料的钙钛矿晶型的稳定性。
在一些实施例中，真空干燥的温度为20～40℃。本申请实施例有机卤化铵或者卤化碱金属和卤化碳族金属与第一有机溶剂进行混合反应后，各原料组分在混合过程中进行初步自组装，形成钙钛矿晶型，然后在温度为20～40℃的室温条件下真空干燥，去除混合浆料中溶剂，得到干燥的初产物。若干燥温度过 高，材料容易分解。
在一些实施例中，退火处理的条件包括：以5～10℃/h的速率将温度从20～40℃升温至110～130℃。本申请实施例将干燥后的钙钛矿型X光活性材料的初产物以5～10℃/h的速率将温度从20～40℃升温至110～130℃进行梯度退火处理，通过退火处理过程中的热扰动，使X光活性材料进一步自组装，使钙钛矿晶型更加有序化，提高X光活性材料的纯度、结构完整，使其性能更稳定，从而得到钙钛矿型X光活性材料。其中，若退火速率过慢或者退火温度过低，则对X光活性材料钙钛矿晶型、纯度等的优化效果不佳，不利于提高X光活性材料的稳定性；若退火升温速率过快或者温度过高，则材料容易分解。
在一些实施例中，有机卤化铵选自：CH 3NH 3Cl、CH 3NH 3Br、CH 3NH 3I、CH 2(NH 3) 2Cl、CH 2(NH 3) 2Br、CH 2(NH 3) 2I中的至少一种；这些有机卤化铵通过与卤化碳族金属自组装后可形成化学通式为AYZ 3的钙钛矿材料，其中，A包括CH 3NH 3 +、CH 2(NH 3) 2 +中的至少一种，Y包括碳族金属元素，Z包括至少一种卤素，钙钛矿材料的A位引入的CH 3NH 3 +、CH 2(NH 3) 2 +等有机铵盐可有效提高钙钛矿材料的成膜性能。
在一些实施例中，卤化碱金属选自：CsCl、CsBr、CsI、RbCl、RbBr、RbI中的至少一种；这些卤化碱金属通过与卤化碳族金属自组装后可形成化学通式为AYZ 3的钙钛矿材料，其中，A包括Cs +、Rb +中的至少一种，Y包括碳族金属元素，Z包括至少一种卤素，钙钛矿材料的A位引入的Cs +或者Cs +和Rb +等碱金属离子可有效提高钙钛矿材料的热稳定性能。
在一些实施例中，卤化碳族金属选自：氯化铅、溴化铅、碘化铅、氯化锡、溴化锡、碘化锡中的至少一种；这些卤化碳族金属可与有机卤化铵或者卤化碱金属自组装，将铅、锡等碳族金属引入到X光活性材料的钙钛矿晶格中，铅(Z＝82)、锡(Z＝50)等碳族金属对X光的吸收远远大于硒(Z＝34)，可显著提高X光活性材料对X光的吸收效率；另一方面，这些碳族金属元素的6s轨道与Z位的外层p轨道可成键耦合，贡献于钙钛矿X光活性材料的能带结构 中价带顶，而碳族金属元素的6p轨道，贡献于钙钛矿能带结构中导带底。
在一些实施例中，第一有机溶剂选自：氯苯、甲苯、N-甲基吡咯烷酮中的至少一种，这些有机溶剂使有机卤化铵、卤化碱金属、卤化碳族金属均匀稳定地分散在溶剂中，有利于各原料组分相互接触反应。
本申请实施例第三方面提供一种钙钛矿X光活性层的制备方法，包括以下步骤：
S20.在惰性气氛下，将X光活性材料、导电高分子粘合剂与第二有机溶剂混合，得到混合浆料；
S30.将混合浆料沉积在衬底上，真空干燥后进行退火处理，在衬底上形成钙钛矿X光活性层。
本申请实施例第三方面提供的钙钛矿X光活性层的制备方法，为防止原料吸水潮解以及被氧化，在惰性气氛下，将X光活性材料、导电高分子粘合剂与第二有机溶剂混合均匀，然后将混合浆料沉积在衬底上，通过真空干燥去除浆料中多余溶剂，再进行退火处理，使浆料固化成型的同时使X光活性材料进一步自组装，提高活性层中X活性材料钙钛矿晶型的有序性，结构完整性，纯度，性能稳定性等特性。本申请实施例钙钛矿X光活性层的制备方法，工艺简单，对设备要求低，混合浆料在衬底上沉积可以大面积快速制备不同厚度的钙钛矿X光活性层，制备灵活高效，且制备的钙钛矿X光活性层与衬底结合稳定性好，对X光吸收转化效率高，光电性能优越，适应范围广。
在一些实施例中，上述步骤S20中，混合浆料中，X光活性材料、导电高分子粘合剂和第二有机溶剂的质量比为(90～110):1：(10～20)，混合浆料中各原料组分的该质量配比，既确保了混合浆料的粘稠度，有利于混合浆料在衬底表面沉积成型，与衬底结合稳定性好；又确保了制备的钙钛矿X光活性层对X光的吸收转化效率，以及电荷载流子迁移效率。其中，导电高分子粘合剂既起到调整浆料粘度的作用，同时能起到空穴传输路径的作用，协同提高钙钛矿活性层的电荷传输效率。若X光活性材料含量过低，则降低了钙钛矿X光活性层 对X光的吸收转化效率。若导电高分子粘合剂含量过低，则混合浆料粘稠度太低，流动性太大，不利于混合浆料在衬底表面沉积稳定；若导电高分子粘合剂含量过高，则混合浆料粘稠度太高，则不利于浆料均匀的沉积在衬底表面，且不利于保持活性层高的载流子迁移效率。若第二有机溶剂含量过低或过高，同样会影响混合浆料的粘稠度，不利于浆料沉积成型。在一些具体实施例中，混合浆料中，X光活性材料、导电高分子粘合剂和第二有机溶剂的质量比为100:1:20。
在一些实施例中，将X光活性材料、导电高分子粘合剂与第二有机溶剂混合的步骤包括：将X光活性材料的原料组分与导电高分子粘合剂和第二有机溶剂进行混合。本申请实施例可直接将X光活性材料的原料组分与导电高分子粘合剂和第二有机溶剂进行混合处理，在钙钛矿X光活性层固化成型的过程中原位生成X光活性材料，提高活性材料与粘合剂、沉积等的结合稳定性，使形成的钙钛矿X光活性层性能更好。
在一些实施例中，X光活性材料的原料组分包括：有机卤化铵或者卤化碱金属和卤化碳族金属，这些X光活性材料的原料在第二有机溶剂条件下可进行自组装形成钙钛矿晶型的X活性材料。
在一些实施例中，导电高分子粘合剂选自：聚噻吩(P3HT)、聚[双(4-苯基)(2,4,6-三甲基苯基)胺](PTAA)中的至少一种；这些导电高分子粘合剂具有优秀的空穴迁移率，与钙钛矿型X光活性材料能级匹配效果好，利于激子拆分，且与钙钛矿X光活性材料粘合性强，可提高钙钛矿X光活性层与衬底的结合稳定性。
在一些实施例中，第二有溶剂选自：氯苯、甲苯、N-甲基吡咯烷酮中的至少一种，这些有机溶剂对有机卤化铵、卤化碱金属、卤化碳族金属等X光活性材料原料组分，以及X光活性材料、导电高分子粘合剂等材料有较好的分散作用，使各组分均匀稳定地分散在溶剂中，有利于各组分相互接触反应。
在一些实施例中，上述步骤S30中，将混合浆料沉积在衬底上的方式可以 是刮涂、涂布等方式，衬底可以是带有铟锡氧化物ITO的玻璃。在一些实施例中，衬底的尺寸可以是(1-3英寸)×(1-3英寸)，本申请实施例混合浆料通过刮涂等形式沉积在衬底上，可以在较大面积的衬底上得到更多的均匀成膜区域，实现大面积快速制备不同厚度的钙钛矿X光活性层，制备灵活高效。
在一些实施例中，真空干燥的温度为20～40℃。本申请实施例将X光活性材料、导电高分子粘合剂与第二有机溶剂的混合浆料沉积在衬底后，通过真空干燥除去混合浆料中溶剂，使材料固化成型。若干燥温度过高，则容易导致沉积的混合浆料层出现裂缝，破坏钙钛矿X光活性层的稳定性。
在一些实施例中，退火处理的条件包括：以5～10℃/h的速率将温度从20～40℃升温至110～130℃。本申请实施例对干燥后的沉积层进行退火处理，既能够进一步去除沉积层中溶剂成分，又能够通过热扰动使钙钛矿X光活性材料进一步自组装，提高钙钛矿晶型的有序性，结构完整性，纯度，性能稳定性等特性，从而提高钙钛矿X光活性层的光电性能。若退火速率过慢或者退火温度过低，则对钙钛矿X光活性层中钙钛矿晶型、纯度等的优化效果不佳，不利于提高钙钛矿X光活性层的光电性及稳定性；若退火升温速率过快或者温度过高，则容易导致钙钛矿X光活性层出现裂缝，破坏了钙钛矿X光活性层的稳定性。
在一些实施例中，钙钛矿X光活性层的厚度100-1000μm。本申请实施例钙钛矿X光活性层的制备方法，可以大面积快速制备不同厚度的钙钛矿X光活性层，制备灵活高效，使钙钛矿X光活性层适应于不同体系的器件中，提高其应用灵活性。
在一些实施例中，按200μL/(1英寸×3英寸)，将混合浆料沉积在衬底上，在此条件下沉积浆料，可获得合适的成膜厚度和良好的成膜均匀度，且混合浆料与ITO等衬底接触性能更好。
本申请实施例第四方面提供一种X光探测器，X光探测器包括上述的X光活性材料，或者上述方法制备的钙钛矿X光活性层。
本申请实施例第四方面提供的X光探测器，由于包含有上述X光活性材料 或者钙钛矿X光活性层，X光探测器接受X光辐射时，钙钛矿X光活性层中X光活性材料首先吸收光子产生电子和空穴对，然后这些电子和空穴对在外电场的作用下转换为自由载流子向电极迁移，最后被各自的电极收集。本申请实施例X光探测器能够直接将X光吸收转化成电荷载流子，X光吸收转化效率高，对高能量X光探测同样具有较高的效率，且光电稳定性好。
为使本申请上述实施细节和操作能清楚地被本领域技术人员理解，以及本申请实施例X活性材料及其制备方法、钙钛矿X光活性层的制备方法、X光探测器的进步性能显著的体现，以下通过多个实施例来举例说明上述技术方案。
实施例1
一种钙钛矿基X光探测器，其制备包括步骤：
1、在氩气(或者氮气)惰性气氛下，将CH 3NH 3I和PbI 2按照1:1的质量比例进行混合后，加入P3HT作为导电高分子粘合剂，加入氯苯和NMP溶剂，其中，CH 3NH 3I和PbI 2的总质量与P3HT和溶剂的质量比为100:1:20，然后充分搅拌形成高粘度的黑色钙钛矿染料；
2、采用刮涂的技术，通过调节刮刀与基底的缝隙宽度以及刮涂速率，将钙钛矿染料涂覆在ITO基底上；所获得的染料层在室温下真空干燥去除溶剂后，以5℃/h的速率从室温升温至120℃对钙钛矿层进行梯度退火处理，获得CH 3NH 3PbI 3的钙钛矿X光活性层，厚度为500μm；
3、在真空度为10 -6mbar，蒸镀速率为
Figure PCTCN2021137705-appb-000001
蒸镀时间为1500s的条件下，在钙钛矿X光活性层表面真空蒸镀Au，形成Au金属背电极，得到ITO/CH 3NH 3PbI 3/Au结构的钙钛矿基X光探测器。
实施例2
一种钙钛矿基X光探测器，其制备包括步骤：
1、在氩气(或者氮气)惰性气氛下，将CH 2(NH 3) 2I和PbI 2按照1:1的质量比例进行混合后，加入P3HT作为导电高分子粘合剂，加入氯苯和NMP溶剂， 其中，CH 2(NH 3) 2I和PbI 2的总质量与P3HT和溶剂的质量比为100:1:20，然后充分搅拌形成高粘度的黑色钙钛矿染料；
2、采用刮涂的技术，通过调节刮刀与基底的缝隙宽度以及刮涂速率，将钙钛矿染料涂覆在ITO基底上；所获得的染料层在室温下真空干燥去除溶剂后，以5℃/h的速率从室温升温至120℃对钙钛矿层进行梯度退火处理，获得CH 2(NH 3) 2PbI 3的钙钛矿X光活性层，厚度为500μm；
3、在真空度为10 -6mbar，蒸镀速率为
Figure PCTCN2021137705-appb-000002
蒸镀时间为1500s的条件下，在钙钛矿X光活性层表面真空蒸镀Au，形成Au金属背电极，得到ITO/CH 2(NH 3) 2PbI 3/Au结构的钙钛矿基X光探测器。
实施例3
一种钙钛矿基X光探测器，其制备包括步骤：
1、在氩气(或者氮气)惰性气氛下，将CsI和PbI 2按照1:1的质量比例进行混合后，加入P3HT作为导电高分子粘合剂，加入氯苯和NMP溶剂，其中，CsI和PbI 2的总质量与P3HT和溶剂的质量比为100:1:20，然后充分搅拌形成高粘度的橙红色钙钛矿染料；
2、采用刮涂的技术，通过调节刮刀与基底的缝隙宽度以及刮涂速率，将钙钛矿染料涂覆在ITO基底上；所获得的染料层在室温下真空干燥去除溶剂后，以5℃/h的速率从室温升温至120℃对钙钛矿层进行梯度退火处理，获得CsPbI 3的钙钛矿X光活性层，厚度为500μm；
3、在真空度为10 -6mbar，蒸镀速率为
Figure PCTCN2021137705-appb-000003
蒸镀时间为1500s的条件下，在钙钛矿X光活性层表面真空蒸镀Au，形成Au金属背电极，得到ITO/CsPbI 3/Au结构的钙钛矿基X光探测器。
实施例4
一种钙钛矿基X光探测器，其制备包括步骤：
1、在氩气(或者氮气)惰性气氛下，将CH 3NH 3Br和PbI 2按照1:1的质量比例进行混合后，加入P3HT作为导电高分子粘合剂，加入氯苯和NMP溶剂， 其中，CH 3NH 3Br和PbI 2的总质量与P3HT和溶剂的质量比为100:1:20，然后充分搅拌形成高粘度的棕黑色钙钛矿染料；
2、采用刮涂的技术，通过调节刮刀与基底的缝隙宽度以及刮涂速率，将钙钛矿染料涂覆在ITO基底上；所获得的染料层在室温下真空干燥去除溶剂后，以5℃/h的速率从室温升温至120℃对钙钛矿层进行梯度退火处理，获得CH 3NH 3PbBrI 2的钙钛矿X光活性层，厚度为500μm；
3、在真空度为10 -6mbar，蒸镀速率为
Figure PCTCN2021137705-appb-000004
蒸镀时间为1500s的条件下，在钙钛矿X光活性层表面真空蒸镀Au，形成Au金属背电极，得到ITO/CH 3NH 3PbBrI 2/Au结构的钙钛矿基X光探测器。
实施例5
一种钙钛矿基X光探测器，其制备包括步骤：
1、在氩气(或者氮气)惰性气氛下，将CsBr和PbBr 2按照1:1的质量比例进行混合后，加入P3HT作为导电高分子粘合剂，加入氯苯和NMP溶剂，其中，CsBr和PbBr 2的总质量与P3HT和溶剂的质量比为100:1:20，然后充分搅拌形成高粘度的橙红色钙钛矿染料；
2、采用刮涂的技术，通过调节刮刀与基底的缝隙宽度以及刮涂速率，将钙钛矿染料涂覆在ITO基底上；所获得的染料层在室温下真空干燥去除溶剂后，以5℃/h的速率从室温升温至120℃对钙钛矿层进行梯度退火处理，获得CsPbBr 3的钙钛矿X光活性层，厚度为500μm；
3、在真空度为10 -6mbar，蒸镀速率为
Figure PCTCN2021137705-appb-000005
蒸镀时间为1500s的条件下，在钙钛矿X光活性层表面真空蒸镀Au，形成Au金属背电极，得到ITO/CsPbBr 3/Au结构的钙钛矿基X光探测器。
对比例1
以Canada Analogic公司的无定型硒基X光探测器作为对比例1。
进一步的，为了验证本申请实施例的进步性，对实施例1～5和对比例1分 别提供的钙钛矿基X光探测器，进行光电流测试，即I-t测试，获得不同时间下的X光响应电量，从而获得材料的X光灵敏度(S，Sensitivity)，实施例1和对比例1的测试图如附图3所示，其中，●为实施例1，▲为对比例1，横坐标为时间，纵坐标为电流；然后，进行I-V测试，获得不同偏压下的X光响应电量，根据经典的Hecht方程拟合，获得材料的迁移率寿命乘积值(μt，μt product)，实施例1的测试图如附图4所示，其中，holes measured孔测量，electrons measured电子测量，fitted line拟合线，横坐标为电压，纵坐标为电流，测试结果如下表1所示：
表1
Figure PCTCN2021137705-appb-000006
由上述测试结果可知，相对于对比例1无定型硒基X光探测器，本申请实施例1～5由钙钛矿X光活性层制备的钙钛矿基X光探测器中分别包含有CH 3NH 3PbI 3、CH 2(NH 3) 2PbI 3、CsPbI 3、CH 3NH 3PbBrI 2、CsPbBr 3等X光活性材料，使X光探测器表现出更高的X光灵敏度，以及更高的迁移率寿命乘积值，更低的偏压需求。说明本申请实施例X光钙钛矿活性材料，通过碱金属离子或者有机铵离子与卤素、铅等碳族金属元素等的协同作用，显著提高了活性材料的X光吸收及转化效率，同时提高了其载流子迁移效率以及材料的稳定性，使其有更好的应用前景。
以上所述仅为本申请的较佳实施例而已，并不用以限制本申请，凡在本申请的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本申请的保护范围之内。

Claims (10)

  1. 一种X光活性材料，其特征在于，所述X光活性材料为卤化物钙钛矿材料，其化学通式为：AYZ 3；其中，A包括碱金属离子或者有机铵离子，Y包括碳族金属元素，Z包括至少一种卤素。
  2. 如权利要求1所述的X光活性材料，其特征在于，所述A包括Cs +或者Cs +和Rb +；
    和/或，所述有机铵离子包括：CH 3NH 3 +、CH 2(NH 3) 2 +中的至少一种；
    和/或，所述Y包括：铅、锡中的至少一种；
    和/或，所述卤素包括：氯、溴、碘中的至少一种。
  3. 如权利要求2所述的X光活性材料，其特征在于，所述X光活性材料的化学通式为：APbZ 1 xZ 2 3-x；其中，Z 1和Z 2分别选自不同的卤素，0.5≤x≤1.5。
  4. 如权利要求3所述的X光活性材料，其特征在于，所述X光活性材料的化学通式为：APbBr xI 3-x；
    和/或，所述X光活性材料中0.85≤x≤1.05。
  5. 一种X光活性材料的制备方法，其特征在于，包括以下步骤：
    在惰性气氛下，将有机卤化铵或者卤化碱金属和卤化碳族金属与第一有机溶剂进行混合反应后，真空干燥并退火处理，得到钙钛矿型X光活性材料。
  6. 如权利要求5所述的X光活性材料的制备方法，其特征在于，所述X光活性材料中，有机铵离子或者碱金属离子的摩尔量、碳族金属离子的摩尔量与卤素的摩尔量之比为1:1:3；
    和/或，所述真空干燥的温度为20～40℃；
    和/或，所述退火处理的条件包括：以5～10℃/h的速率将温度从20～40℃升温至110～130℃；
    和/或，所述有机卤化铵选自：CH 3NH 3Cl、CH 3NH 3Br、CH 3NH 3I、CH 2(NH 3) 2Cl、CH 2(NH 3) 2Br、CH 2(NH 3) 2I中的至少一种；
    和/或，所述卤化碱金属选自：CsCl、CsBr、CsI、RbCl、RbBr、RbI中的至少一种；
    和/或，所述卤化碳族金属选自：氯化铅、溴化铅、碘化铅、氯化锡、溴化锡、碘化锡中的至少一种；
    和/或，所述第一有机溶剂选自：氯苯、甲苯、N-甲基吡咯烷酮中的至少一种。
  7. 一种钙钛矿X光活性层的制备方法，其特征在于，包括以下步骤：
    在惰性气氛下，将X光活性材料、导电高分子粘合剂与第二有机溶剂混合，得到混合浆料；
    将所述混合浆料沉积在衬底上，真空干燥后进行退火处理，在所述衬底上形成钙钛矿X光活性层。
  8. 如权利要求7所述的钙钛矿X光活性层的制备方法，其特征在于，所述混合浆料中，所述X光活性材料、所述导电高分子粘合剂和所述第二有机溶剂的质量比为(90～110)；1：(10～20)；
    和/或，所述将X光活性材料、导电高分子粘合剂与第二有机溶剂混合的步骤包括：将所述X光活性材料的原料组分与所述导电高分子粘合剂和所述第二有机溶剂进行混合；
    和/或，所述导电高分子粘合剂选自：聚噻吩、聚[双(4-苯基)(2,4,6-三甲基苯基)胺]中的至少一种；
    和/或，所述第二有机溶剂选自：氯苯、甲苯、N-甲基吡咯烷酮中的至少一种。
  9. 如权利要求8所述的钙钛矿X光活性层的制备方法，其特征在于，所述真空干燥的温度为20～40℃；
    和/或，所述退火处理的条件包括：以5～10℃/h的速率将温度从20～40℃升温至110～130℃；
    和/或，所述钙钛矿X光活性层的厚度100-1000μm；
    和/或，所述X光活性材料的原料组分包括：有机卤化铵或者卤化碱金属和卤化碳族金属。
  10. 一种X光探测器，其特征在于，所述X光探测器包括如权利要求1～4任一项所述的X光活性材料，或者如权利要求5～6任一项所述方法制备的X光活性材料，或者如权利要求7～9任一项所述方法制备的钙钛矿X光活性层。
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