CN113823741A - X-ray active material and preparation method and application thereof - Google Patents
X-ray active material and preparation method and application thereof Download PDFInfo
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- CN113823741A CN113823741A CN202110897199.2A CN202110897199A CN113823741A CN 113823741 A CN113823741 A CN 113823741A CN 202110897199 A CN202110897199 A CN 202110897199A CN 113823741 A CN113823741 A CN 113823741A
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- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 claims description 3
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- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 claims description 3
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- LTSUHJWLSNQKIP-UHFFFAOYSA-J tin(iv) bromide Chemical compound Br[Sn](Br)(Br)Br LTSUHJWLSNQKIP-UHFFFAOYSA-J 0.000 claims description 3
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- QPBYLOWPSRZOFX-UHFFFAOYSA-J tin(iv) iodide Chemical compound I[Sn](I)(I)I QPBYLOWPSRZOFX-UHFFFAOYSA-J 0.000 claims description 3
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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
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- 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
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- 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
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- 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
Abstract
The application belongs to the technical field of photoelectricity, and particularly 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. Wherein, the X-ray active material is a halide perovskite material, and the chemical general formula is as follows: AYZ3(ii) a Wherein A comprises an alkali metal ion or an organic ammonium ion, Y comprises a carbon group metal element, and Z comprises at least one halogen. According to the X-ray active material, the synergistic effect of alkali metal ions or organic ammonium ions and carbon group metal elements such as halogen and lead is utilized, the X-ray absorption and conversion efficiency of the active material is remarkably improved, and the carrier migration efficiency and the material stability are improved, so that the X-ray active material has a better application prospect.
Description
Technical Field
The application belongs to the technical field of photoelectricity, and particularly 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.
Background
An X-ray detector (X-ray detector) is a device that converts X-ray energy into electrical signals that can be recorded. In recent years, with the large-scale popularization and use of X-ray detectors, the X-ray detectors are increasingly used in the fields of small security inspection equipment, industrial part inspection, large container inspection, medical treatment and the like.
At present, X-ray detectors are mostly applied to indirect conversion X-ray detectors using scintillators, and are generally formed by combining scintillators, detector chips and substrates; the working principle is that X photons enter a scintillator and are converted into visible light to be output, the visible light enters a detector chip, the detector chip performs photoelectric conversion to form an electric signal, and the electric signal is transmitted to a subsequent signal processing chip through the chip and a lead on a substrate, so that a final image is formed. Compared with the prior art, the direct conversion X-ray detector can directly convert X-ray absorption into charge carriers, has the advantages of small required radiation dose, high spatial resolution, large contrast range, simple device structure and the like, and has wider application prospect in the aspect of high-end medical image application. The core of the direct conversion X-ray flat panel image detector is an X-ray active layer which is a material directly converting X-ray absorption into charge carriers. At present, the X-ray active material with excellent performance can select a few kinds of amorphous selenium materials (a-Se: As) doped with arsenic As an X-ray active layer, which is the mainstream method. However, the device based on the material has harsh preparation conditions on one hand and extremely low detection efficiency on high-energy X-ray on the other hand. Therefore, finding alternative materials is of great significance for the development of the next generation of X-ray image detectors.
Halide perovskite materials are considered As the next generation materials most likely 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 prior art is mostly based on perovskite single crystals nucleated and grown in a solution, the method can conveniently obtain the perovskite material with high quality and certain thickness, but the process method brings limitations to the later functional layer preparation, and has high cost, low speed and small area, so the method is not suitable for large-scale industrial production. Meanwhile, in the prior art, most of perovskite single crystals are based on bimetallic electrodes, and the perovskite single crystals are poor in combination effect with array substrates such as Thin Film Transistors (TFT) based on conductive Indium Tin Oxide (ITO), so that the application prospect of directly converting images of an X-ray detector by a perovskite substrate is severely limited.
Disclosure of Invention
The application aims to provide an X-ray active material, a preparation method thereof and an X-ray detector, and aims to solve the problems that the existing X-ray active material capable of directly converting X-ray into an electric signal is few in types and low in detection efficiency of high-energy X-ray to a certain extent.
In order to achieve the purpose of the application, the technical scheme adopted by the application is as follows:
in a first aspect, the present application provides an X-photoactive material that is a halide perovskite material having the general chemical formula: AYZ3(ii) a Wherein A comprises an alkali metal ion or an organic ammonium ion, Y comprises a carbon group metal element, and Z comprises at least one halogen.
Further, said A comprises Cs+Or Cs+And Rb+。
Further, the organic ammonium ions include: CH (CH)3NH3 +、CH2(NH3)2 +At least one of (1).
Further, the Y comprises: at least one of lead and tin.
Further, the halogen includes: at least one of chlorine, bromine and iodine.
Further, the chemical formula of the X photoactive material is as follows: APbZ1 xZ2 3-x(ii) a Wherein Z is1And Z2Are respectively selected from different halogens, x is more than or equal to 0.5 and less than or equal to 1.5.
Further, the chemical formula of the X photoactive material is as follows: APbBrxI3-x。
Furthermore, X in the X photoactive material is more than or equal to 0.85 and less than or equal to 1.05.
In a second aspect, the present application provides a method of preparing an X-ray active material comprising the steps of:
under inert atmosphere, organic ammonium halide or alkali halide and carbon halide group metal are mixed with a first organic solvent for reaction, and then vacuum drying and annealing treatment are carried out to obtain the perovskite type X photoactive material.
Further, in the X photoactive material, the ratio of the molar amount of the organic ammonium ion or the alkali metal ion to the molar amount of the carbon group metal ion to the molar amount of the halogen is 1:1: 3.
Further, the temperature of the vacuum drying is 20-40 ℃.
Further, the conditions of the annealing treatment include: heating the temperature from 20-40 ℃ to 110-130 ℃ at a rate of 5-10 ℃/h.
Further, the organic ammonium halide is selected from: CH (CH)3NH3Cl、CH3NH3Br、CH3NH3I、CH2(NH3)2Cl、CH2(NH3)2Br、CH2(NH3)2At least one of I.
Further, the alkali halide is selected from: at least one of CsCl, CsBr, CsI, RbCl, RbBr and RbI.
Further, the halocarbon group metal is selected from: at least one of lead chloride, lead bromide, lead iodide, tin chloride, tin bromide and tin iodide.
Further, the first organic solvent is selected from: at least one of chlorobenzene, toluene and N-methyl pyrrolidone.
In a third aspect, the present application provides a method of preparing a perovskite X photoactive layer, comprising the steps of:
mixing the X-ray active material, the conductive polymer adhesive and a second organic solvent in an inert atmosphere to obtain mixed slurry;
and depositing the mixed slurry on a substrate, carrying out vacuum drying and annealing treatment, and forming a perovskite X photoactive layer on the substrate.
Further, in the mixed slurry, the mass ratio of the X photoactive material to the conductive polymer binder to the second organic solvent is (90-110): 1: (10-20).
Further, the step of mixing the X photoactive material, the conductive polymer binder, and the second organic solvent includes: mixing the raw material components of the X photoactive material with the conductive polymeric binder and the second organic solvent.
Further, the conductive polymer binder is selected from: at least one of polythiophene and poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine ].
Further, the second organic solvent is selected from: at least one of chlorobenzene, toluene and N-methyl pyrrolidone.
Further, the temperature of the vacuum drying is 20-40 ℃.
Further, the conditions of the annealing treatment include: heating the temperature from 20-40 ℃ to 110-130 ℃ at a rate of 5-10 ℃/h.
Further, the thickness of the perovskite X photoactive layer is 100-1000 μm.
Further, the raw material components of the X photoactive material comprise: an organic ammonium halide or an alkali metal halide and a carbon group metal halide.
In a fourth aspect, the present application provides an X-ray detector comprising an X-ray active material as described above, or a perovskite X-ray active layer prepared by the above method.
The X-ray active material provided by the first aspect of the present application is a halide perovskite material having the general chemical formula: AYZ3Wherein A comprises an alkali metal ion or an organic ammonium ion, Y comprises a carbon group metal element, Z comprises at least one halogen, the Z site forms a regular octahedron with the carbon group metal element at the Y site in a 6-coordinated manner, and eight [ YZ ] s6]4-The regular octahedrons form a cage in a mode of being connected with a common vertex, the A site occupies the center of the cage to play a supporting role of a perovskite structure, and 12 coordination is formed between the A site and the Z site. And the Y-position carbon group metal element has large atomic number and high absorption efficiency on X-ray, and is far larger than elements such as selenium and the like. The X-ray perovskite active material provided by the application is prepared by AYZ3The synergistic effect of medium alkali metal ion or organic ammonium ion and carbon group metal elements such as halogen and lead can obviously raise X-ray absorption and conversion efficiency of active material, and at the same time make X-ray active material possess high charge carrier mobility, long charge carrier diffusion length and very good propertyThe bulk phase defect tolerance and the like, so that the method has better application prospect.
In order to prevent the raw materials from absorbing water, deliquescing and being oxidized, the preparation method of the X-ray active material provided by the second aspect of the application comprises the steps of mixing organic ammonium halide or alkali halide and carbon halide with a first organic solvent in an inert atmosphere to enable all raw material components to fully contact and react, carrying out self-assembly to generate an initial product of the perovskite X-ray active material, then removing solvent components in a reaction system through drying treatment, carrying out annealing treatment, further carrying out self-assembly on the X-ray active material through thermal disturbance, enabling the perovskite crystal form to be more ordered, improving the purity and the structure of the X-ray active material to be complete, enabling the performance of the X-ray active material to be more stable, and further obtaining the perovskite X-ray active material. The preparation method of the X-ray active material has the advantages of low requirement on equipment, simple and efficient process and low cost, and is suitable for industrial large-scale production and application.
In order to prevent the raw materials from absorbing water, deliquescing and being oxidized, the preparation method of the perovskite X photoactive layer provided by the third aspect of the application uniformly mixes the X photoactive material, the conductive polymer adhesive and the second organic solvent in an inert atmosphere, then deposits the mixed slurry on the substrate, removes redundant solvent in the slurry through vacuum drying, and then carries out annealing treatment, so that the X photoactive material is further self-assembled while the slurry is solidified and formed, and the characteristics of the ordering, structural integrity, purity, performance stability and the like of the perovskite crystal form of the X active material in the active layer are improved. The preparation method of the perovskite X photoactive layer has the advantages of simple process and low requirement on equipment, the perovskite X photoactive layers with different thicknesses can be rapidly prepared in a large area by depositing the mixed slurry on the substrate, the preparation is flexible and efficient, the prepared perovskite X photoactive layer is good in combination stability with the substrate, the absorption and conversion efficiency of X light is high, the photoelectric property is excellent, and the application range is wide.
According to the X-ray detector provided by the fourth aspect of the present application, because the X-ray active material or the perovskite X-ray active layer is included, when the X-ray detector receives X-ray radiation, the X-ray active material in the perovskite X-ray active layer firstly absorbs photons to generate electron and hole pairs, and then the electron and hole pairs are converted into free carriers under the action of an external electric field to migrate to the electrodes and finally are collected by the respective electrodes. The X-ray detector can directly absorb and convert X-rays into charge carriers, the X-ray absorption and conversion efficiency is high, high efficiency is achieved for high-energy X-ray detection, and the photoelectric stability is good.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIGS. 1-2 are schematic structural diagrams of X-ray active materials provided in embodiments of the present disclosure;
FIG. 3 is an I-t test chart of the X-ray detector provided in example 1 and comparative example 1 of the present application under different times of X-ray irradiation;
FIG. 4 is an I-V test chart of an X-ray detector made of the X-ray active material provided in example 1 of the present application.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present application more clearly apparent, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.
In this application, the term "and/or" describes an association relationship of associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
In the present application, "at least one" means one or more, "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one (one) of a, b, or c," or "at least one (one) of a, b, and c," may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, and c may be single or plural, respectively.
It should be understood that, in various embodiments of the present application, the sequence numbers of the above-mentioned processes do not mean the execution sequence, some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its function and inherent logic, and should not constitute any limitation to the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the examples of this application and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weight of the related components mentioned in the description of the embodiments of the present application may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present application as long as it is scaled up or down according to the description of the embodiments of the present application. Specifically, the mass in the description of the embodiments of the present application may be in units of mass known in the chemical industry, such as μ g, mg, g, and kg.
The terms "first" and "second" are used for descriptive purposes only and are used for distinguishing purposes such as substances from one another, and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of embodiments of the present application. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature.
As shown in FIGS. 1 and 2, in a first aspect, embodiments of the present application provide an X-ray active material, X-ray activeThe material is a halide perovskite material, and the chemical general formula of the material is as follows: AYZ3(ii) a Wherein A comprises an alkali metal ion or an organic ammonium ion, Y comprises a carbon group metal element, and Z comprises at least one halogen.
The X-ray active material provided by the first aspect of the embodiments of the present application is a halide perovskite material, and has a chemical general formula: AYZ3Wherein A comprises an alkali metal ion or an organic ammonium ion, Y comprises a carbon group metal element, Z comprises at least one halogen, the Z site forms a regular octahedron with the carbon group metal element at the Y site in a 6-coordinated manner, and eight [ YZ ] s6]4-The regular octahedrons form a cage in a mode of being connected with a common vertex, the A site occupies the center of the cage to play a supporting role of a perovskite structure, and 12 coordination is formed between the A site and the Z site. And the Y-position carbon group metal element has large atomic number and high absorption efficiency on X-ray, and is far larger than elements such as selenium and the like. The X-ray perovskite active material provided by the embodiment of the application is prepared by AYZ3The synergistic effect of medium alkali metal ion or organic ammonium ion and carbon group metal elements such as halogen and lead can obviously raise X-ray absorption and conversion efficiency of active material, and at the same time AYZ3The formed crystal configuration connected by the common vertex forms a carrier passage, which is beneficial to the migration and transmission of carriers, so that the X-ray active material has the characteristics of high charge carrier mobility, long charge carrier diffusion length, very good bulk phase defect tolerance and the like, and has better application prospect.
The A site ions of the X-ray active material in the embodiment of the application mainly play a role in providing lattice site occupation and three-dimensional perovskite structure support, and can influence the physical properties of the perovskite material, such as solubility, stability and the like. In some embodiments, a comprises Cs+Or Cs+And Rb+These alkali metal ions at the a-site are effective in improving the thermal stability of the X photoactive material. In other embodiments, the organic ammonium ions include: CH (CH)3NH3 +、CH2(NH3)2 +At least one of; these organic ammonium ions at the A site can enhance the film forming properties of the X photoactive material.
In some embodiments, Y comprises: lead and tinAt least one of (1). In the X-ray active material of the embodiment of the application, the Y position comprises at least one carbon group metal element in lead and tin, and the Z position is in accordance with the relation of the substance to the X-ray absorption coefficient4/E3(Z is an atomic number, and E is X-ray energy), it is known that lead (Z82) and tin (Z50) absorb X-rays much more than selenium (Z34) in the same X-ray energy range, and therefore these carbon group metal elements have high absorption efficiency for X-rays and much more than elements such as selenium, and the absorption efficiency of X-rays by an X-ray active material can be significantly improved; on the other hand, the 6s orbital of these carbon group metal elements may be bond-coupled to the outer p orbital of the Z-site, contributing to the valence band top in the band structure of the perovskite X photoactive material, while the 6p orbital of the carbon group metal element contributes to the conduction band bottom in the perovskite band structure.
In some embodiments, the halogen comprises: at least one of chlorine, bromine and iodine. On one hand, the Z-site halogens and the Y site form a regular octahedron structure, and the common vertexes of the octahedrons are connected to form a carrier passage, so that the formed perovskite X photoactive material has high charge carrier mobility and long charge carrier diffusion length; on the other hand, the energy band structure of the perovskite X photoactive material has the valence band top mainly derived from the 6s orbital bond coupling contribution of the carbon group metal element and the outer p orbital bond coupling contribution of the Z position.
In some embodiments, the X photoactive material has the chemical formula: APbZ1 xZ2 3-x(ii) a Wherein Z is1And Z2Are respectively selected from different halogens, x is more than or equal to 0.5 and less than or equal to 1.5. The Z site of the X-ray active material in the embodiment of the application contains two different halogens at the same time, and the photoelectric property of the perovskite X-ray active material can be better adjusted by introducing the two halogens into the perovskite lattice at the same time, so that the active material has better X-ray absorption conversion property. And the self-assembly of the perovskite crystal form in the X-ray active material can be promoted through the synergistic effect of the two halogens, so that the quality of the active material is improved. In the embodiment of the application, X is preferably more than or equal to 0.5 and less than or equal to 1.5, and the value range of X enables two different halogens to have better synergistic effect, so that the balance optimization of the band gap, the carrier mobility and the X-ray sensitivity of the X-active material is realized. In addition, the Y position is selected from lead, which has a larger atomic number (original)Sub-number Z82), higher absorption efficiency for X-rays; meanwhile, the material has the characteristics of higher charge carrier mobility, long charge carrier diffusion length, very good bulk defect tolerance and the like.
In some embodiments, the X photoactive material has the chemical formula: APbBrxI3-xX is more than or equal to 0.5 and less than or equal to 1.5. According to the embodiment of the application, bromine is introduced into crystal lattices of the X-ray active material, so that the photoelectric property of the active material can be effectively regulated and controlled, the active material has better X-ray absorption conversion property, and the self-assembly of the perovskite X-ray active material can be further promoted by introducing a proper amount of bromine, so that the preparation efficiency of the active material is improved. The X-ray absorption conversion efficiency of the active material is improved through the synergistic effect of bromine and iodine elements, and meanwhile, the synthesis preparation of the perovskite material is facilitated, so that the quality of the perovskite material is improved.
In some preferred embodiments, the X photoactive material has the chemical formula: APbBrxI3-xX is more than or equal to 0.85 and less than or equal to 1.05 in the X-ray active material, bromine and iodine have better synergistic effect in the proportioning interval, and the balance optimization of the band gap, the charge carrier mobility and the X-ray sensitivity of the X-ray active material can be realized.
In some embodiments, the X photoactive material has the chemical formula: APbBrxI3-xX is more than or equal to 0.85 and less than or equal to 1.05 in the X photoactive material, and A comprises Cs+、Cs+And Rb+、CH3NH3 +、CH2(NH3)2 +At least one of (1).
Example X photoactive materials of the present application can be prepared by the following example methods.
In a second aspect, embodiments of the present application provide a method for preparing an X-ray active material, comprising the steps of:
s10, under an inert atmosphere, mixing organic ammonium halide or alkali halide metal and carbon halide group metal with a first organic solvent for reaction, and then carrying out vacuum drying and annealing treatment to obtain the perovskite type X-ray active material.
In order to prevent the raw materials from absorbing water, deliquescing and being oxidized, the method for preparing the X-ray active material provided by the second aspect of the embodiment of the application performs mixing treatment on the organic ammonium halide or the alkali halide and the carbon halide group metal and the first organic solvent under the inert atmosphere to enable the raw material components to fully contact and react, performs self-assembly to generate an initial product of the perovskite X-ray active material, removes solvent components in a reaction system through drying treatment, performs annealing treatment, further performs self-assembly on the X-ray active material through thermal disturbance to enable the perovskite crystal form to be more ordered, improves the purity and the structure of the X-ray active material, and enables the performance of the X-ray active material to be more stable, thereby obtaining the perovskite X-ray active material. The preparation method of the X-ray active material in the embodiment of the application has the advantages of low requirement on equipment, simple and efficient process and low cost, and is suitable for industrial large-scale production and application.
In some embodiments, the ratio of the molar amount of organic ammonium ions or alkali metal ions, the molar amount of carbon group metal ions, and the molar amount of halogen in the X photoactive material is 1:1: 3; the molar ratio is effective to ensure the stability of the perovskite crystal form of the X photoactive material.
In some embodiments, the temperature of the vacuum drying is 20-40 ℃. After the organic ammonium halide or the alkali halide and the carbon halide group metal are mixed with the first organic solvent for reaction, the raw material components are subjected to preliminary self-assembly in the mixing process to form a perovskite crystal form, and then the perovskite crystal form is subjected to vacuum drying at the room temperature of 20-40 ℃, the solvent in the mixed slurry is removed, and a dried primary product is obtained. Some drying temperatures are too high, and the material is easily decomposed.
In some embodiments, the conditions of the annealing process include: heating the temperature from 20-40 ℃ to 110-130 ℃ at a rate of 5-10 ℃/h. According to the embodiment of the application, the temperature of an initial product of the dried perovskite X-ray active material is increased from 20-40 ℃ to 110-130 ℃ at the speed of 5-10 ℃/h for gradient annealing treatment, the X-ray active material is further self-assembled through thermal disturbance in the annealing treatment process, the perovskite crystal form is more ordered, the purity and the structure of the X-ray active material are improved, the performance of the X-ray active material is more stable, and therefore the perovskite X-ray active material is obtained. If the annealing rate is too slow or the annealing temperature is too low, the optimization effect on the perovskite crystal form, the purity and the like of the X photoactive material is not good, and the stability of the X photoactive material is not improved; if the annealing temperature rise rate is too fast or the temperature is too high, the material is easily decomposed.
In some embodiments, the organic ammonium halide is selected from: CH (CH)3NH3Cl、CH3NH3Br、CH3NH3I、CH2(NH3)2Cl、CH2(NH3)2Br、CH2(NH3)2At least one of I; the organic ammonium halides can form a chemical general formula of AYZ after self-assembly with carbon halide group metal3Wherein A comprises CH3NH3 +、CH2(NH3)2 +Y comprises a carbon group metal element, Z comprises at least one halogen, CH introduced at the a-site of the perovskite material3NH3 +、CH2(NH3)2 +And the organic ammonium salt can effectively improve the film forming property of the perovskite material.
In some embodiments, the alkali halide is selected from: at least one of CsCl, CsBr, CsI, RbCl, RbBr and RbI; the alkali halide metal can form a chemical formula of AYZ after self-assembly with the halocarbon group metal3Wherein A comprises Cs+、Rb+Y comprises a carbon group metal element, Z comprises at least one halogen, Cs introduced at the a-site of the perovskite material+Or Cs+And Rb+The alkali metal ions can effectively improve the thermal stability of the perovskite material.
In some embodiments, the halocarbon group metal is selected from: at least one of lead chloride, lead bromide, lead iodide, tin chloride, tin bromide and tin iodide; the carbon group metal halide can be self-assembled with organic ammonium halide or alkali metal halide, the carbon group metal such as lead, tin and the like is introduced into the perovskite lattice of the X-ray active material, the absorption of the carbon group metal such as lead (Z-82), tin (Z-50) and the like to X-ray is far greater than that of selenium (Z-34), and the absorption efficiency of the X-ray active material to the X-ray can be obviously improved; on the other hand, the 6s orbital of these carbon group metal elements may be bond-coupled to the outer p orbital of the Z-site, contributing to the valence band top in the band structure of the perovskite X photoactive material, while the 6p orbital of the carbon group metal element contributes to the conduction band bottom in the perovskite band structure.
In some embodiments, the first organic solvent is selected from: at least one of chlorobenzene, toluene and N-methyl pyrrolidone, wherein the organic solvent uniformly and stably disperses organic ammonium halide, alkali metal halide and carbon group metal halide in the solvent, thereby facilitating the mutual contact reaction of the raw material components.
A third aspect of embodiments of the present application provides a method of preparing a perovskite X photoactive layer, comprising the steps of:
s20, mixing the X-ray active material, the conductive polymer adhesive and a second organic solvent in an inert atmosphere to obtain mixed slurry;
and S30, depositing the mixed slurry on a substrate, carrying out annealing treatment after vacuum drying, and forming a perovskite X optical active layer on the substrate.
In order to prevent the raw materials from absorbing water, deliquescing and being oxidized, the method provided by the third aspect of the embodiment of the application uniformly mixes the X photoactive material, the conductive polymer binder and the second organic solvent in an inert atmosphere, deposits the mixed slurry on the substrate, removes redundant solvents in the slurry through vacuum drying, and then carries out annealing treatment, so that the X photoactive material is further self-assembled while the slurry is cured and molded, and the characteristics of the ordering, structural integrity, purity, performance stability and the like of the perovskite crystal form of the X active material in the active layer are improved. The preparation method of the perovskite X photoactive layer in the embodiment of the application has the advantages of simple process and low requirement on equipment, the perovskite X photoactive layers with different thicknesses can be rapidly prepared in a large area by depositing the mixed slurry on the substrate, the preparation is flexible and efficient, the prepared perovskite X photoactive layer is good in combination stability with the substrate, the X-ray absorption conversion efficiency is high, the photoelectric property is excellent, and the application range is wide.
In some embodiments, in the step S20, the mass ratio of the X photoactive material, the conductive polymer binder and the second organic solvent in the mixed slurry is (90-110): 1: (10-20), the mass ratio of each raw material component in the mixed slurry ensures the viscosity of the mixed slurry, is beneficial to deposition forming of the mixed slurry on the surface of the substrate, and has good combination stability with the substrate; and the absorption conversion efficiency of the prepared perovskite X-ray active layer on X-ray and the charge carrier migration efficiency are ensured. The conductive polymer adhesive not only has the function of adjusting the viscosity of the slurry, but also has the function of a hole transmission path, and the charge transmission efficiency of the perovskite active layer is synergistically improved. If the content of the X-ray active material is too low, the absorption conversion efficiency of the perovskite X-ray active layer on X-ray is reduced. If the content of the conductive high-molecular adhesive is too low, the viscosity of the mixed slurry is too low, the fluidity is too high, and the mixed slurry is not favorable for the deposition stability of the mixed slurry on the surface of the substrate; if the content of the conductive polymer adhesive is too high, the viscosity of the mixed slurry is too high, which is not beneficial to the uniform deposition of the slurry on the surface of the substrate and is not beneficial to maintaining the high carrier migration efficiency of the active layer. If the content of the second organic solvent is too low or too high, the viscosity of the mixed slurry is also affected, and the slurry is not favorable for deposition and forming. In some embodiments, the mass ratio of the X photoactive material, the conductive polymeric binder, and the second organic solvent in the mixed slurry is 100:1: 20.
In some embodiments, the step of mixing the X photoactive material, the conductive polymeric binder, and the second organic solvent comprises: the raw material components of the X-ray active material are mixed with a conductive polymeric binder and a second organic solvent. According to the embodiment of the application, the raw material components of the X-ray active material can be directly mixed with the conductive polymer adhesive and the second organic solvent, the X-ray active material is generated in situ in the process of curing and forming the perovskite X-ray active layer, the combination stability of the active material, the adhesive, the deposition and the like is improved, and the formed perovskite X-ray active layer has better performance.
In some embodiments, the starting components of the X photoactive material comprise: organic ammonium halide or alkali metal halide and carbon group metal halide, and the raw materials of the X active materials can be self-assembled to form the X active material in the perovskite crystal form under the condition of a second organic solvent.
In some embodiments, the conductive polymeric binder is selected from: at least one of polythiophene (P3HT), poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine ] (PTAA); the conductive polymer adhesive has excellent hole mobility, has good energy level matching effect with the perovskite X-ray active material, is beneficial to exciton resolution, has strong adhesion with the perovskite X-ray active material, and can improve the combination stability of the perovskite X-ray active layer and the substrate.
In some embodiments, the second organic solvent is selected from: at least one of chlorobenzene, toluene and N-methyl pyrrolidone, and the organic solvents have good dispersion effect on X photoactive material raw material components such as organic ammonium halide, alkali metal halide, carbon halide group metal and the like, and materials such as X photoactive materials, conductive polymer binders and the like, so that the components are uniformly and stably dispersed in the solvents, and mutual contact reaction of the components is facilitated.
In some embodiments, the mixed slurry is deposited on the substrate in step S30 by knife coating, or the like, and the substrate may be glass with ITO. In some embodiments, the size of the substrate can be (1-3 inches) × (1-3 inches), and the mixed slurry in the embodiments of the present application is deposited on the substrate in a blade coating manner or the like, so that more uniform film forming areas can be obtained on a larger area of the substrate, the perovskite X photoactive layers with different thicknesses can be rapidly prepared in a large area, and the preparation is flexible and efficient.
In some embodiments, the temperature of the vacuum drying is 20-40 ℃. In the embodiment of the application, after the mixed slurry of the X-ray active material, the conductive polymer adhesive and the second organic solvent is deposited on the substrate, the solvent in the mixed slurry is removed through vacuum drying, so that the material is cured and molded. If the drying temperature is too high, cracks are likely to occur in the deposited mixed slurry layer, and the stability of the perovskite X photoactive layer is impaired.
In some embodiments, the conditions of the annealing process include: heating the temperature from 20-40 ℃ to 110-130 ℃ at a rate of 5-10 ℃/h. The embodiment of the application anneals the sedimentary deposit after the drying and handles, can enough further get rid of solvent composition in the sedimentary deposit, can make perovskite X optical activity material further self-assembling through thermal disturbance again, improves the orderliness of perovskite crystal form, structural integrity, purity, characteristics such as stability of performance to improve the photoelectric properties of perovskite X optical activity layer. If the annealing rate is too slow or the annealing temperature is too low, the optimization effect on the perovskite crystal form, the purity and the like in the perovskite X photoactive layer is not good, and the photoelectric property and the stability of the perovskite X photoactive layer are not improved; if the annealing temperature rise rate is too fast or the temperature is too high, the perovskite X photoactive layer is easy to crack, and the stability of the perovskite X photoactive layer is damaged.
In some embodiments, the thickness of the perovskite X photoactive layer is 100-. According to the preparation method of the perovskite X photoactive layer, the perovskite X photoactive layers with different thicknesses can be prepared rapidly in a large area, the preparation is flexible and efficient, the perovskite X photoactive layer is suitable for devices of different systems, and the application flexibility of the perovskite X photoactive layer is improved.
In some embodiments, the mixed slurry is deposited on a substrate at 200 μ L/(1 inch × 3 inch), and the slurry is deposited under such conditions, so that a suitable film formation thickness and a good film formation uniformity can be obtained, and the mixed slurry has a better contact property with the substrate such as ITO.
In a fourth aspect, embodiments of the present application provide an X-ray detector comprising an X-ray active material as described above, or a perovskite X-ray active layer prepared by the above method.
In the X-ray detector provided by the fourth aspect of the embodiments of the present application, because the X-ray active material or the perovskite X-ray active layer is included, when the X-ray detector receives X-ray radiation, the X-ray active material in the perovskite X-ray active layer first absorbs photons to generate electron and hole pairs, and then the electron and hole pairs are converted into free carriers under the action of an external electric field to migrate to the electrodes and finally be collected by the respective electrodes. The X-ray detector can directly absorb and convert X-rays into charge carriers, is high in X-ray absorption and conversion efficiency, has high efficiency on high-energy X-ray detection, and is good in photoelectric stability.
In order to clearly understand the details and operations of the above-mentioned embodiments of the present application by those skilled in the art, and to obviously show the advanced performance of the active material X and the preparation method thereof, the preparation method of the perovskite X photoactive layer, and the X-ray detector in the examples of the present application, the above-mentioned technical solutions are illustrated by a plurality of examples below.
Example 1
A perovskite-based X-ray detector is prepared by the following steps:
1. under the inert atmosphere of argon (or nitrogen), CH is added3NH3I and PbI2Mixing according to the mass ratio of 1:1, adding P3HT as conductive polymer adhesive, and adding chlorobenzene and NMP solvent, wherein CH3NH3I and PbI2The mass ratio of the total mass of the perovskite compound to the P3HT to the solvent is 100:1:20, and then the perovskite dye with high viscosity is formed by fully stirring;
2. coating the perovskite dye on the ITO substrate by adopting a blade coating technology and adjusting the width of a gap between a scraper and the substrate and the blade coating rate; vacuum drying the obtained dye layer at room temperature to remove the solvent, and heating the dye layer from the room temperature to 120 ℃ at the speed of 5 ℃/h to perform gradient annealing treatment on the perovskite layer to obtain CH3NH3PbI3The thickness of the perovskite X photoactive layer is 500 mu m;
3. at a vacuum degree of 10-6mbar, evaporation rate of
Under the condition that the evaporation time is 1500s, carrying out vacuum evaporation on Au on the surface of the perovskite X optical active layer to form an Au metal back electrode, thus obtaining ITO/CH3NH3PbI3Perovskite base X-ray detector of/Au structure.
Example 2
A perovskite-based X-ray detector is prepared by the following steps:
1. under the inert atmosphere of argon (or nitrogen), CH is added2(NH3)2I and PbI2Mixing according to the mass ratio of 1:1, adding P3HT as conductive polymer adhesive, and adding chlorobenzene and NMP solvent, wherein CH2(NH3)2I and PbI2The mass ratio of the total mass of the perovskite compound to the P3HT to the solvent is 100:1:20, and then the perovskite dye with high viscosity is formed by fully stirring;
2. coating the perovskite dye on the ITO substrate by adopting a blade coating technology and adjusting the width of a gap between a scraper and the substrate and the blade coating rate; vacuum drying the obtained dye layer at room temperature to remove the solvent, and heating the dye layer from the room temperature to 120 ℃ at the speed of 5 ℃/h to perform gradient annealing treatment on the perovskite layer to obtain CH2(NH3)2PbI3The thickness of the perovskite X photoactive layer is 500 mu m;
3. at a vacuum degree of 10-6mbar, evaporation rate of
Under the condition that the evaporation time is 1500s, carrying out vacuum evaporation on Au on the surface of the perovskite X optical active layer to form an Au metal back electrode, thus obtaining ITO/CH2(NH3)2PbI3Perovskite base X-ray detector of/Au structure.
Example 3
A perovskite-based X-ray detector is prepared by the following steps:
1. under the inert atmosphere of argon (or nitrogen), CsI and PbI are added2Mixing according to the mass ratio of 1:1, adding P3HT as conductive polymer adhesive, and adding chlorobenzene and NMP solvent, wherein CsI and PbI2The mass ratio of the total mass of the dye to the P3HT and the solvent is 100:1:20, and then the dye is fully stirred to form the orange red perovskite dye with high viscosity;
2. coating the perovskite dye on the ITO substrate by adopting a blade coating technology and adjusting the width of a gap between a scraper and the substrate and the blade coating rate; after the obtained dye layer is dried in vacuum at room temperature to remove the solvent, the temperature is raised from the room temperature to 120 ℃ at the speed of 5 ℃/h to carry out gradient annealing treatment on the perovskite layer, and CsPbI is obtained3The thickness of the perovskite X photoactive layer is 500 mu m;
3. at a vacuum degree of 10-6mbar, evaporation rate of
Under the condition that the vapor deposition time is 1500s, carrying out vacuum vapor deposition on Au on the surface of the perovskite X optical active layer to form an Au metal back electrode, thus obtaining ITO/CsPbI3Perovskite base X-ray detector of/Au structure.
Example 4
A perovskite-based X-ray detector is prepared by the following steps:
1. under the inert atmosphere of argon (or nitrogen), CH is added3NH3Br and PbI2Mixing according to the mass ratio of 1:1, adding P3HT as conductive polymer adhesive, and adding chlorobenzene and NMP solvent, wherein CH3NH3Br and PbI2The mass ratio of the total mass of the perovskite to the P3HT to the solvent is 100:1:20, and then the mixture is fully stirred to form a high-viscosity brown black perovskite dye;
2. coating the perovskite dye on the ITO substrate by adopting a blade coating technology and adjusting the width of a gap between a scraper and the substrate and the blade coating rate; vacuum drying the obtained dye layer at room temperature to remove the solvent, and heating the dye layer from the room temperature to 120 ℃ at the speed of 5 ℃/h to perform gradient annealing treatment on the perovskite layer to obtain CH3NH3PbBrI2The thickness of the perovskite X photoactive layer is 500 mu m;
3. at a vacuum degree of 10-6mbar, evaporation rate of
Under the condition that the evaporation time is 1500s, carrying out vacuum evaporation on Au on the surface of the perovskite X optical active layer to form an Au metal back electrode, thus obtaining ITO/CH3NH3PbBrI2Perovskite base X-ray detector of/Au structure.
Example 5
A perovskite-based X-ray detector is prepared by the following steps:
1. under the inert atmosphere of argon (or nitrogen), CsBr and PbBr are added2Mixing according to the mass ratio of 1:1, adding P3HT as conductive polymer adhesive, and adding chlorobenzene and NMP solvent, wherein CsBr and PbBr2The mass ratio of the total mass of the dye to the P3HT and the solvent is 100:1:20, and then the dye is fully stirred to form the orange red perovskite dye with high viscosity;
2. coating the perovskite dye on the ITO substrate by adopting a blade coating technology and adjusting the width of a gap between a scraper and the substrate and the blade coating rate; after the obtained dye layer is dried in vacuum at room temperature to remove the solvent, the temperature is raised from the room temperature to 120 ℃ at the speed of 5 ℃/h to carry out gradient annealing treatment on the perovskite layer, and CsPbBr is obtained3The thickness of the perovskite X photoactive layer is 500 mu m;
3. at a vacuum degree of 10-6mbar, evaporation rate of
Under the condition that the evaporation time is 1500s, carrying out vacuum evaporation on Au on the surface of the perovskite X optical active layer to form an Au metal back electrode, thus obtaining ITO/CsPbBr3Perovskite base X-ray detector of/Au structure.
Comparative example 1
An amorphous selenium-based X-ray detector from Canada analog was used as comparative example 1.
Further, in order to verify the improvement of the embodiment of the present application, the perovskite-based X-ray detector provided in each of examples 1 to 5 and comparative example 1 was subjected to a photocurrent test, i.e., an I-t test, to obtain X-ray response electric quantity at different times, so as to obtain X-ray Sensitivity (S, Sensitivity) of the material, and the test graphs of example 1 and comparative example 1 are shown in fig. 3, wherein ● is example 1, a value is comparative example 1, the abscissa is time, and the ordinate is current; then, an I-V test is performed to obtain X-ray response electric quantities under different biases, and mobility lifetime product values (μ t, μ tproduct) of the material are obtained by fitting according to the classic Hecht equation, and the test chart of example 1 is shown in fig. 4, in which holes are measured, electrons are measured, and fixed line fit line, the abscissa is voltage, the ordinate is current, and the test results are shown in the following table 1:
TABLE 1
From the test results, compared with the amorphous selenium-based X-ray detector in comparative example 1, the perovskite-based X-ray detectors prepared from the perovskite X-ray active layers in examples 1 to 5 of the present application respectively include CH3NH3PbI3、CH2(NH3)2PbI3、CsPbI3、CH3NH3PbBrI2、CsPbBr3The X-ray active material enables the X-ray detector to show higher X-ray sensitivity, higher mobility life product value and lower bias voltage requirement. The X-ray perovskite active material of the embodiment of the application is demonstrated to significantly improve the X-ray absorption and conversion efficiency of the active material, and simultaneously improve the carrier transport efficiency and the material stability through the synergistic effect of the alkali metal ions or organic ammonium ions and the carbon group metal elements such as halogen and lead, so that the X-ray perovskite active material has a better application prospect.
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. An X-ray active material, wherein the X-ray active material is a halide perovskite material having the general chemical formula: AYZ3(ii) a Wherein A comprises an alkali metal ion or an organic ammonium ion, Y comprises a carbon group metal element, and Z comprises at least one halogen.
2. The X photoactive material of claim 1 wherein a comprises Cs+Or Cs+And Rb+；
And/or, the organic ammonium ions comprise: CH (CH)3NH3 +、CH2(NH3)2 +At least one of;
and/or, said Y comprises: at least one of lead and tin;
and/or, the halogen comprises: at least one of chlorine, bromine and iodine.
3. The X photoactive material of claim 2, wherein the X photoactive material has the chemical formula: APbZ1 xZ2 3-x(ii) a Wherein Z is1And Z2Are respectively selected from different halogens, x is more than or equal to 0.5 and less than or equal to 1.5.
4. The X photoactive material of claim 3, wherein the X photoactive material has a chemical formula: APbBrxI3-x；
And/or X is more than or equal to 0.85 and less than or equal to 1.05 in the X photoactive material.
5. A preparation method of an X-ray active material is characterized by comprising the following steps:
under inert atmosphere, organic ammonium halide or alkali halide and carbon halide group metal are mixed with a first organic solvent for reaction, and then vacuum drying and annealing treatment are carried out to obtain the perovskite type X photoactive material.
6. The method for preparing an X-ray active material according to claim 5, wherein the ratio of the molar amount of organic ammonium ions or alkali metal ions, the molar amount of carbon group metal ions and the molar amount of halogen in the X-ray active material is 1:1: 3;
and/or the temperature of the vacuum drying is 20-40 ℃;
and/or the annealing treatment conditions comprise: heating the temperature from 20-40 ℃ to 110-130 ℃ at a speed of 5-10 ℃/h;
and/or, the organic ammonium halide is selected from: CH (CH)3NH3Cl、CH3NH3Br、CH3NH3I、CH2(NH3)2Cl、CH2(NH3)2Br、CH2(NH3)2At least one of I;
and/or, the alkali halide is selected from: at least one of CsCl, CsBr, CsI, RbCl, RbBr and RbI;
and/or, the halocarbon group metal is selected from: at least one of lead chloride, lead bromide, lead iodide, tin chloride, tin bromide and tin iodide;
and/or, the first organic solvent is selected from: at least one of chlorobenzene, toluene and N-methyl pyrrolidone.
7. A preparation method of a perovskite X photoactive layer is characterized by comprising the following steps:
mixing the X-ray active material, the conductive polymer adhesive and a second organic solvent in an inert atmosphere to obtain mixed slurry;
and depositing the mixed slurry on a substrate, carrying out vacuum drying and annealing treatment, and forming a perovskite X photoactive layer on the substrate.
8. The method for preparing the perovskite X photoactive layer according to claim 7, wherein the mass ratio of the X photoactive material, the conductive polymer binder and the second organic solvent in the mixed slurry is (90 to 110); 1: (10-20);
and/or the step of mixing the X photoactive material, the conductive polymeric binder, and the second organic solvent comprises: mixing the raw material components of the X photoactive material with the conductive polymeric binder and the second organic solvent;
and/or, the conductive polymer binder is selected from: at least one of polythiophene and poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine ];
and/or, the second organic solvent is selected from: at least one of chlorobenzene, toluene and N-methyl pyrrolidone.
9. The method for preparing the perovskite X photoactive layer according to claim 8, wherein the temperature of vacuum drying is 20 to 40 ℃;
and/or the annealing treatment conditions comprise: heating the temperature from 20-40 ℃ to 110-130 ℃ at a speed of 5-10 ℃/h;
and/or the thickness of the perovskite X photoactive layer is 100-1000 μm;
and/or, the raw material components of the X photoactive material comprise: an organic ammonium halide or an alkali metal halide and a carbon group metal halide.
10. An X-ray detector comprising an X-ray active material according to any one of claims 1 to 4, or an X-ray active material prepared by a process according to any one of claims 5 to 6, or a perovskite X-ray active layer prepared by a process according to any one of claims 7 to 9.
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| CN111463350A (en) * | 2020-04-20 | 2020-07-28 | 浙江大学 | X-ray detector based on perovskite quantum dots and preparation method thereof |
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| CN107342365A (en) * | 2017-06-26 | 2017-11-10 | 长江大学 | A kind of perovskite photodetector and preparation method thereof |
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