WO2023087453A1 - Détecteur d'image à rayons x direct et son procédé de fabrication - Google Patents

Détecteur d'image à rayons x direct et son procédé de fabrication Download PDF

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WO2023087453A1
WO2023087453A1 PCT/CN2021/138092 CN2021138092W WO2023087453A1 WO 2023087453 A1 WO2023087453 A1 WO 2023087453A1 CN 2021138092 W CN2021138092 W CN 2021138092W WO 2023087453 A1 WO2023087453 A1 WO 2023087453A1
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ray image
image detector
direct
substrate
quantum
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PCT/CN2021/138092
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Chinese (zh)
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薛冬峰
李云龙
陈慧雯
王晓明
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中国科学院深圳先进技术研究院
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01B—MEASURING LENGTH, THICKNESS OR SIMILAR LINEAR DIMENSIONS; MEASURING ANGLES; MEASURING AREAS; MEASURING IRREGULARITIES OF SURFACES OR CONTOURS
    • G01B15/00—Measuring arrangements characterised by the use of electromagnetic waves or particle radiation, e.g. by the use of microwaves, X-rays, gamma rays or electrons
    • G01B15/04—Measuring arrangements characterised by the use of electromagnetic waves or particle radiation, e.g. by the use of microwaves, X-rays, gamma rays or electrons for measuring contours or curvatures
    • G01B15/045—Measuring arrangements characterised by the use of electromagnetic waves or particle radiation, e.g. by the use of microwaves, X-rays, gamma rays or electrons for measuring contours or curvatures by measuring absorption
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01T—MEASUREMENT OF NUCLEAR OR X-RADIATION
    • G01T1/00—Measuring X-radiation, gamma radiation, corpuscular radiation, or cosmic radiation
    • G01T1/02—Dosimeters
    • G01T1/026—Semiconductor dose-rate meters
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K39/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic radiation-sensitive element covered by group H10K30/00
    • H10K39/30—Devices controlled by radiation
    • H10K39/36—Devices specially adapted for detecting X-ray radiation
    • 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 optoelectronic technology, and in particular relates to a direct X-ray image detector and a preparation method thereof.
  • the direct type X-ray image detector consists of a semiconductor active layer and a thin film transistor pixel array.
  • the working principle is that the semiconductor active layer directly converts the X-rays passing through the measured object into electrical signals, and then uses a computer to control the capacitor in the thin film transistor pixel array.
  • the switch collects electrical signals and converts the electrical signals into images.
  • the color depth of pixels in the images is determined by the intensity of the generated electrical signals. Since the measured object absorbs X-rays differently, the X-ray dose rate passing through the measured object can reflect the shape of the object, and the role of the semiconductor active layer is to convert these X-rays with different dose rates into electrical signals of different intensities , describe the shape of the object through the color depth of the pixel.
  • the aggregation speed of octahedrons in the nucleation process of two-dimensional hybrid perovskite is controlled, and the volatilization speed of solvents and additives in the film growth process is controlled at the same time.
  • this conventional method is easy to synthesize multi-n quantum well films, which is not conducive to the uniform transport of carriers to the array substrate.
  • the current research on the regulation of the vertical substrate orientation of two-dimensional hybrid perovskite is mostly used in solar cells, so the thickness of the film is about 0.5 ⁇ m, which has low absorption of high-energy X-rays and produces fewer carriers. The signal is weak, affecting the final imaging clarity.
  • the purpose of the present application is to provide a direct type X-ray image detector and its preparation method, aiming to solve the problem of low absorption coefficient of X-rays and poor imaging effect of the existing direct type X-ray image detector to a certain extent.
  • the present application provides a method for preparing a direct X-ray image detector, comprising the following steps:
  • the halide salt includes an organic ammonium halide or an alkali metal halide
  • a substrate with a pixel array distributed on its surface forming a film of the precursor gel on the surface of the pixel array of the substrate, annealing, and forming a two-dimensional hybrid perovskite quantum array film on the surface of the pixel array of the substrate layer;
  • An electrode layer is prepared on the surface of the quantum array film layer away from the substrate to obtain a direct X-ray image detector.
  • the number of carbon atoms of the long-chain organic carboxylic acid is 3-10.
  • the organic ligand is selected from at least one of n-butylamine, isobutylamine, ⁇ -phenethylamine, allylamine, and 2-thio-ethylamine.
  • the thickness of the quantum array film layer is 8-20 ⁇ m.
  • the long-chain organic carboxylic acid is selected from at least one of propionic acid, n-butyric acid, isobutyric acid and n-valeric acid.
  • the method for synthesizing the ionic liquid adopts a vacuum rotary evaporation method.
  • the step of synthesizing the ionic liquid comprises:
  • the crude product was rotary evaporated under reduced pressure at a temperature of 60-100°C, and the product was collected;
  • the product is subjected to crystallization treatment at a temperature of -30 ⁇ -10°C to obtain a crystalline product
  • the crystalline product is purified to obtain the ionic liquid.
  • 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.
  • organic ammonium halide salt is selected from: methylamine hydroiodide, 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 ) At least one of 2 Br and CH 2 (NH 3 ) 2 I.
  • the alkali metal halide is selected from at least one of CsCl, CsBr, CsI, RbCl, RbBr, and RbI.
  • the organic solvent is selected from: a mixed solvent of dimethyl sulfoxide and N,N-dimethylformamide.
  • the step of preparing the precursor gel includes: after dissolving the ionic liquid, the halogenated carbon group metal and the halide salt in an organic solvent, heat preservation at a temperature of 90-110°C for 5 ⁇ 120s, obtain the precursor gel;
  • the step of the annealing treatment includes: at a temperature of 100-150°C, after scraping the precursor gel onto the surface of the pixel array of the substrate, at a temperature of 80-150°C Under dry annealing for 5 ⁇ 20 minutes;
  • the volume ratio of the dimethyl sulfoxide to the N,N-dimethylformamide is (1-4):(1-4).
  • the present application provides a direct X-ray image detector, including: a substrate, a pixel array bonded on the surface of the substrate, a quantum array film layer vertically grown on the surface of the pixel array, and lamination The electrode layer arranged on the surface of the quantum array film layer; wherein, the quantum array film layer contains a general structural formula of A'A n-1 B n X 3n+1 and/or A' 2 A n-1 A two-dimensional hybrid perovskite of B n X 3n+1 , where A' is an organic ligand, A is an ammonium ion or an alkali metal ion, B is a carbon group metal ion, and X is a halogen ion; n is 2 ⁇ 10 .
  • the thickness of the quantum array film layer is 8-20 ⁇ m.
  • the organic ligand is selected from at least one of n-butylamine, isobutylamine, ⁇ -phenethylamine, allylamine, and 2-thio-ethylamine.
  • organic ammonium ion is selected from at least one of CH 3 NH 3 + and CH 2 (NH 3 ) 2 + .
  • the alkali metal ion is selected from at least one of Cs + and Rb + .
  • the carbon group metal ion is selected from at least one of lead and tin.
  • halide ion is selected from at least one of chlorine, bromine and iodine.
  • the material of the pixel array includes: at least one of ITO, FTO, P3HT:PCBM.
  • the material of the substrate is selected from glass.
  • the electrode layer is selected from at least one of carbon electrodes and metal electrodes.
  • the preparation method of the direct type X-ray image detector uses a long-chain organic carboxylic acid and an organic ligand to synthesize an ionic liquid, and then dissolves the ionic liquid, a halogenated carbon group metal, and a halide salt in an organic solvent, and utilizes The strong coordination between the carbonyl group and the octahedral central cation, as well as the intermolecular force between the carboxylic acid alkyl chains, reduce the driving force of [BX 6 ] octahedral aggregation, inhibit the rapid aggregation of octahedron, and improve the precursor solution Viscosity, forming a stable precursor gel.
  • the gel film layer is constructed in situ.
  • the octahedron of the two-dimensional hybrid perovskite and the interlayer organic cation self-assemble through the intermolecular force, and the pixel array is perpendicular to the Basal growth.
  • the two-dimensional hybrid perovskite crystals grow, the strong coordination between the carbonyl group in the long-chain organic acid and the octahedral central cation makes the organic solvent and carboxylic acid in the gel layer volatilize at a uniform speed, and through annealing treatment , a two-dimensional hybrid perovskite quantum array film is formed.
  • an electrode layer is prepared on the surface of the quantum array film layer away from the substrate to obtain a direct X-ray image detector.
  • a quantum well array with a single well width distribution be constructed, but also the film thickness of the quantum array film layer can be increased, thereby improving the ability of the direct type X-ray image detector to capture X-rays, and improving the absorption and conversion efficiency of the device for X-rays. Realize high-definition imaging of X-rays.
  • the two-dimensional hybrid perovskite grown vertically on the surface of the pixel array in the quantum array film layer makes the carriers in the quantum array film layer move along Directional migration along the growth direction of the quantum well suppresses lateral drift and scattering of carriers, improves carrier transfer efficiency, and avoids carrier loss.
  • the direct X-ray image detector prepared by the above method can not only construct a quantum well array with a single well width distribution, so that the carriers can be evenly transported to the array substrate, which is to realize high-definition imaging of the X-ray direct detector; Increase the film thickness of the quantum array film layer, thereby improving the ability of the direct type X-ray image detector to capture X-rays, thereby further improving the absorption and conversion efficiency of the device for X-rays. Therefore, the direct X-ray image detector provided by the present application has pixel confinement characteristics, can directly absorb and convert X-rays into charge carriers, has high absorption and conversion efficiency of X-rays, and has high detection sensitivity.
  • FIG. 1 is a schematic flow chart of a method for preparing a direct X-ray image detector provided in an embodiment of the present application
  • Fig. 2 is a schematic structural diagram of a direct X-ray image detector provided in an embodiment of the present application
  • FIG. 3 is a graph showing the functional relationship between the photocurrent density and the X-ray dose rate of the direct X-ray image detectors provided in Examples 1-3 and Comparative 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, where a, b, 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 specifying the quantity 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 a method for preparing a direct X-ray image detector, including the following steps:
  • the halide salt includes an organic ammonium halide or an alkali metal halide
  • the general structural formula of the two-dimensional hybrid perovskite in the quantum array film layer prepared in the embodiment of the present application is A'A n-1 B n X 3n+1 and/or A' 2 A n-1 B n X 3n+ 1.
  • the carbon group metal ion at the B position and the halogen ion at the X position form a [BX 6 ] octahedron through coordination, and the cations such as ammonium ions or alkali metal ions at the A position are distributed in the gaps generated by the octahedral common top connection, and the coordination
  • the number is 12, and the organic ligand at the A' position is bonded to the anion on the edge of the octahedron through electrostatic attraction, forming an organic spacer layer.
  • the [BX 6 ] octahedral layer forms a natural quantum well, where n represents the well width of the quantum well, that is, the number of octahedral layers, preferably 2-10.
  • the quantum array film layer can absorb X-rays and directly convert them into electrical signals. It is evenly transmitted to the substrate formed with the pixel array, and then the electrical signal is converted into an image, and high-definition images with different color shades are formed according to the intensity of the electrical signal.
  • the preparation method of the direct X-ray image detector uses long-chain organic carboxylic acid and organic ligand to synthesize ionic liquid, and then dissolves ionic liquid, halide carbon group metal and halide salt in organic solvent , using the strong coordination between the carbonyl group and the octahedral central cation, and the intermolecular force between the carboxylic acid alkyl chains, to reduce the driving force of [BX 6 ] octahedral aggregation, inhibit the rapid aggregation of octahedron, and improve the precursor
  • the viscosity of the precursor solution forms a stable precursor gel.
  • the gel film layer is constructed in situ.
  • the octahedron of the two-dimensional hybrid perovskite and the interlayer organic cation self-assemble through the intermolecular force, and the pixel array is perpendicular to the Basal growth.
  • the two-dimensional hybrid perovskite crystals grow, the strong coordination between the carbonyl group in the long-chain organic acid and the octahedral central cation makes the organic solvent and carboxylic acid in the gel layer volatilize at a uniform speed, and through annealing treatment , a two-dimensional hybrid perovskite quantum array film is formed.
  • an electrode layer is prepared on the surface of the quantum array film layer away from the substrate to obtain a direct X-ray image detector.
  • the preparation method of the direct-type X-ray image detector in the embodiment of the present application introduces long-chain organic carboxylic acid, reduces the aggregation rate of [BX 6 ] octahedron, and increases the viscosity of the precursor solution, which not only can construct a quantum well array with a wide distribution of single wells , and can increase the film thickness of the quantum array film layer, thereby improving the ability of the direct type X-ray image detector to capture X-rays, and improving the absorption and conversion efficiency of the device for X-rays. Realize high-definition imaging of X-rays.
  • the long-chain organic carboxylic acid and the organic ligand are synthesized into an ionic liquid, and the high viscosity, boiling point and solubility of the ionic liquid, as well as the recrystallization purification of the ionic liquid, improve the product purity and reduce the The influence of raw material impurities on the crystallization product improves the crystallization efficiency and purity of the subsequent two-dimensional hybrid perovskite.
  • the long-chain organic carboxylic acid has 3 to 10 carbon atoms, and the organic carboxylic acid with the length of carbon atoms can not only better adjust the driving force of [BX 6 ] octahedral aggregation , and have better intermolecular forces, which can effectively adjust the aggregation rate of octahedra and the viscosity of the precursor solution, thereby regulating the crystallization rate and growth method of the two-dimensional hybrid perovskite, ensuring that the two-dimensional hybrid perovskite Uniform growth along the direction perpendicular to the substrate to construct a quantum well array with a single well width distribution.
  • the number of carbon atoms in the long-chain organic carboxylic acid may be 3, 4, 5, 6, 7, 8, 9, 10, etc.
  • the long-chain organic carboxylic acid is selected from at least one of propionic acid, n-butyric acid, isobutyric acid, and n-valeric acid. Further preferably, the long-chain organic carboxylic acid is selected from at least one of propionic acid, n-butyric acid and isobutyric acid.
  • the organic ligand is selected from: at least one of n-butylamine, isobutylamine, ⁇ -phenethylamine, allylamine, and 2-thio-ethylamine; these organic ligands pass through The electrostatic attraction bonds with the anions at the edge of the octahedron to form an organic spacer layer.
  • the dielectric constant of the spacer layer is mismatched with the octahedral sheet, the [BX 6 ] octahedral layer forms a natural quantum well.
  • the method for synthesizing the ionic liquid adopts a reduced-pressure rotary evaporation method.
  • the step of synthesizing an ionic liquid comprises:
  • the mixing treatment time is 1 to 3 hours.
  • An acid-base reaction occurs between an organic carboxylic acid and an organic ligand, such as: R-COOH+R-NH 2 ⁇ R-COONH 3 -R, the reaction is an exothermic reaction, and the temperature of the examples in this application is 0°C ⁇ 5°C
  • the mixed treatment can reduce the heat of the reaction system and remove impurities whose freezing point is higher than that of the ice-water bath.
  • the product is subjected to crystallization treatment under the condition of crystallization below the freezing point at a temperature of -30 ⁇ -10°C to obtain a crystalline product.
  • the preferred crystallization time is 1-3 hours.
  • the purification step includes: washing the crystallized product three times with diethyl ether, dichloromethane, cyclohexane, petroleum ether, etc., re-dissolving with solvents such as ethanol, acetone, tetrahydrofuran, dichloromethane, etc., adding diethyl ether, dichloromethane, etc.
  • solvents such as ethanol, acetone, tetrahydrofuran, and dichloromethane again
  • the step of preparing the precursor gel includes: after dissolving the ionic liquid, the halide carbon group metal and the halide salt in the organic solvent, the temperature is kept at 90-110°C for 5 ⁇ 120s, preferably 10-30s, to concentrate the solution to a gel state with higher viscosity.
  • the strong coordination between the carbonyl group and the octahedral central cation and the intermolecular force between the carboxylic acid alkyl chains are used to reduce the driving force for [BX 6 ] octahedral aggregation , to suppress the rapid aggregation of octahedra while increasing the viscosity of the precursor solution to form a stable precursor gel.
  • 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 halide or alkali metal halide introduces carbon group metals such as lead and tin into the lattice of two-dimensional hybrid perovskite.
  • the absorption efficiency of carbon group metals such as lead and tin on X-rays is high, which can significantly improve X-ray absorption efficiency of two-dimensional hybrid perovskite.
  • the organic ammonium halide salt 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 At least one of 2 (NH 3 ) 2 I; these organic ammonium halide salts can form perovskite materials through self-assembly with halogenated carbon group metals, and CH 3 NH 3 + , CH 2 (NH 3 ) Organic ammonium ions such as 2 + can effectively improve the thermal stability 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 perovskite materials through self-assembly with carbon group metal halides, calcium
  • alkali metal ions such as Cs + , Rb + into titanium materials can effectively improve the thermal stability of perovskite materials.
  • the organic solvent is selected from: a mixed solvent of dimethyl sulfoxide and N,N-dimethylformamide. Further, in the organic solvent, the volume ratio of dimethyl sulfoxide and N,N-dimethylformamide is (1 ⁇ 4):(1 ⁇ 4). In some specific embodiments, the volume ratio of dimethyl sulfoxide and N,N-dimethylformamide can be 4:1, 3:2, 2:3, 1:4, etc., preferably 2:3 or 1 :4.
  • the mixed organic solvent used in the examples of this application not only has a good dissolving effect on the raw material components, but also facilitates the contact reaction between the components; it is also beneficial to control the growth rate and orientation of the two-dimensional hybrid perovskite, and to optimize the Crystalline quality.
  • the nucleation rate suppression effect of hybrid perovskite crystals is poor. Therefore, using a mixed solvent of dimethyl sulfoxide and N,N-dimethylformamide, the ratio of the two affects the volatilization rate of the system solvent, thereby affecting the orientation of the film layer.
  • the annealing step includes: scraping the precursor gel onto the surface of the pixel array of the substrate at a temperature of 100-150°C; Annealing under low conditions for 5-20 minutes.
  • the precursor gel is scraped onto a substrate with a pixel array formed at a temperature of 100-150°C.
  • the thickness of the array film layer improves the absorption efficiency of the device for X-rays; on the other hand, the hot substrate is conducive to the growth of the two-dimensional hybrid perovskite along the direction perpendicular to the substrate, forming a quantum well with a vertical substrate orientation.
  • annealing is carried out at a temperature of 80-150°C for 5-20 minutes.
  • the two-dimensional hybrid perovskite is further self-assembled, and the crystal form of the perovskite is more ordered. Improve the purity and integrity of the two-dimensional hybrid perovskite to make its performance more stable, so as to obtain the quantum array film layer of the two-dimensional hybrid perovskite vertically grown on the surface of the pixel array.
  • the annealing rate is too slow or the annealing temperature is too low, the optimization effect on the crystal form and purity of the two-dimensional hybrid perovskite is not good, which is not conducive to improving the stability of the two-dimensional hybrid perovskite; if the annealing heating rate is too high Fast or the temperature is too high, the material is easy to decompose.
  • the thickness of the quantum array film layer is 8-20 ⁇ m, which improves the ability of the direct-type X-ray image detector to capture X-rays, and improves the device's ability to capture X-rays. absorption conversion efficiency.
  • the thickness of the quantum array film layer includes but is not limited to 8-10 ⁇ m, 10-12 ⁇ m, 12-15 ⁇ m, 15-18 ⁇ m, 18-20 ⁇ m, etc.
  • the step of cleaning the substrate formed with the pixel array is also included: the substrate formed with the pixel array is successively washed in an ultrasonic cleaner with solvents such as deionized water, acetone, ethanol and isopropanol, using Dry with nitrogen flow, and clean in an ultraviolet ozone cleaning machine for 0-20 min, preferably 10-15 min. Next, place the substrate formed with the pixel array on a film coating machine and preheat to 80-150°C, preferably 100-120°C.
  • solvents such as deionized water, acetone, ethanol and isopropanol
  • the electrode layer prepared on the surface of the quantum array film layer away from the substrate may be a carbon electrode or a metal electrode.
  • the preparation of the carbon electrode includes the steps of: coating the carbon paste on the surface of the quantum array film by scraping, and then curing at 80-120°C for 5-45 minutes, preferably at 90-110°C , cured for 20-30 min to form a carbon electrode layer.
  • the metal electrode can be prepared by vacuum evaporation or sputtering, and the electrode layer can be made of Al, Ag, Au, Cu and other metal materials.
  • the second aspect of the embodiment of the present application provides a direct X-ray image detector prepared in the above embodiment, including: a substrate, a pixel array bonded to the surface of the substrate, and a quantum sensor vertically grown on the surface of the pixel array.
  • the quantum array film layer contains a general structural formula of A'A n-1 B n X 3n+1 and/or A' 2 A n-1 B n X 3n+1 two-dimensional hybrid perovskite, where A' is an organic ligand, A is an ammonium ion or an alkali metal ion, B is a carbon group metal ion, and X is a halogen ion; n is 2 ⁇ 10.
  • the direct X-ray image detector prepared by the method of the above embodiment provided in the second aspect of the embodiment of the present application includes a laminated substrate-pixel array-quantum array film layer-electrode layer, and the structure in the quantum array film layer A two-dimensional hybrid perovskite with the general formula A'A n-1 B n X 3n+1 and/or A' 2 A n-1 B n X 3n+1 , the carbon group metal ion at the B site and the X site
  • the halide ions form the [BX 6 ] octahedron through coordination, and cations such as ammonium ions or alkali metal ions at the A site are distributed in the gaps generated by the octahedral common top connection.
  • the coordination number is 12, and the organic ligand at the A' Gravity bonds to the anions at the edges of the octahedrons, forming an organic spacer layer.
  • the [BX 6 ] octahedral layer forms a natural quantum well, where n represents the well width of the quantum well, that is, the number of octahedral layers.
  • the quantum well structure has a confinement effect on the carriers.
  • the two-dimensional hybrid perovskite grown vertically on the surface of the pixel array in the quantum array film layer of the embodiment of the present application allows the carriers in the quantum array film layer to move along the direction of the quantum well.
  • the direct X-ray image detector prepared by the method of the above embodiment can not only construct a quantum well array with a single well width distribution, but also allow carriers to be uniformly transported to the array substrate, which is to realize high-definition imaging of the X-ray direct detector; Moreover, the film thickness of the quantum array film layer can be increased, thereby improving the ability of the direct type X-ray image detector to capture X-rays, thereby further improving the absorption and conversion efficiency of the device for X-rays. Therefore, the direct X-ray image detector provided by the embodiment of the present application has pixel confinement characteristics, can directly absorb and convert X-rays into charge carriers, has high X-ray absorption conversion efficiency, and high detection sensitivity.
  • the thickness of the quantum array film layer is 8-20 ⁇ m, which improves the ability of the direct-type X-ray image detector to capture X-rays, and improves the device's ability to capture X-rays. absorption conversion efficiency.
  • the thickness of the quantum array film layer includes but is not limited to 8-10 ⁇ m, 10-12 ⁇ m, 12-15 ⁇ m, 15-18 ⁇ m, 18-20 ⁇ m, etc.
  • the organic ligand is selected from: at least one of n-butylamine, isobutylamine, ⁇ -phenethylamine, allylamine, and 2-thio-ethylamine; these organic ligands pass through The electrostatic attraction bonds with the anions at the edge of the octahedron to form an organic spacer layer.
  • the dielectric constant of the spacer layer is mismatched with the octahedral sheet, the [BX 6 ] octahedral layer forms a natural quantum well, two-dimensional hybridization
  • n represents the well width of the quantum well, that is, the number of octahedral layers.
  • the organic ammonium ion is selected from at least one of: CH 3 NH 3 + , CH 2 (NH 3 ) 2 + ; these organic ammonium ions can effectively improve the thermal stability of the two-dimensional hybrid perovskite performance.
  • the alkali metal ions are selected from at least one of Cs + and Rb + ; these alkali metal ions can effectively improve the thermal stability of the two-dimensional hybrid perovskite.
  • the carbon group metal ion is selected from: at least one of lead and tin; these carbon group metals have high absorption efficiency for X-rays, and can significantly improve the absorption efficiency of two-dimensional hybrid perovskites for X-rays .
  • the halide ion is selected from at least one of chlorine, bromine, and iodine.
  • Halogen ions form [BX 6 ] regular octahedra with carbon group metal elements in the form of 6 coordination, and eight [BX 6 ] regular octahedrons form a cage in the form of common vertex connection, and A is ammonium ion or alkali metal ion occupying the cage
  • the center plays a supporting role in the perovskite structure and forms 12 coordination with halogen.
  • the organic ligands at the A' site are bonded to the anions at the edge of the octahedron through electrostatic attraction, forming an organic spacer layer.
  • the materials of the pixel array include: indium tin oxide (ITO), fluorine-doped SnO 2 conductive glass (FTO), poly-3-hexylthiophene and fullerene derivative [6,6]-phenyl - At least one of the blends of C61-isomethyl butyrate (P3HT:PCBM).
  • the material of the substrate is selected from glass.
  • the electrode layer is selected from at least one of carbon electrodes and metal electrodes.
  • metal materials such as Al, Ag, Au, and Cu may be used for the electrode layer.
  • a kind of direct type X -ray image detector, its preparation comprises the steps:
  • step 1 ionic liquid, methylamine hydroiodide (MAI) and lead iodide (PbI 2 ) in a mixed solvent of dimethyl sulfoxide and N,N-dimethylformamide (volume ratio of 1 :4), raise the temperature of the obtained solution to 100°C, set the constant temperature time for 30 s, lower the temperature to room temperature, and concentrate the solution to a high-viscosity gel to obtain a precursor gel;
  • the reaction equation is: , that is, ionic liquid, Methylamine hydroiodide (MAI), lead iodide (PbI 2 ) react by the ratio of the amount of substance of 2:(n+1):n, wherein n is 10, and the concentration of lead iodide in solvent is 3 mol/L, the total solvent volume is 0.5 ml.
  • the indium tin oxide pixel substrate (10 ⁇ 10 ⁇ m indium tin oxide pixel dot substrate distributed on the glass substrate)
  • the carbon paste was coated on the surface of the film by scraping.
  • the amount of carbon paste was 80 ⁇ L, and then cured at 110°C for 30 min to form a carbon electrode and prepare a direct X-ray image detector.
  • a direct type X -ray image detector the difference between it and Embodiment 1 is that in step 1, n-butylamine is replaced by phenethylamine.
  • a direct X-ray image detector the difference from Embodiment 1 is that in step 1, lead iodide is replaced by lead bromide.
  • a direct type X -ray image detector the difference from Embodiment 1 is: in step 1, propionic acid is replaced by acetic acid. In step 3, the precursor gel is deposited on the indium tin oxide pixel substrate by spin coating, and annealed to form a quantum array film with pixel confinement.
  • the two-dimensional hybrid calcium The thickness of the titanite quantum array thin film is about 0.5 ⁇ m.
  • the photocurrent density of the film layer of the direct X-ray image detector prepared in Examples 1 to 3 and Comparative Example 1 was measured under different dose rates of X-ray irradiation. Change, and calculate the X-ray sensitivity according to the fitting line, that is, the slope of the line, and the average energy of X-ray is about 20 keV. The test results are shown in Figure 3, where the abscissa is the dose rate, and the ordinate is the photocurrent density.
  • the ionic liquid prepared from long-chain carboxylic acid as raw material is used as the precursor of perovskite in the process of direct type X-ray image detector in Examples 1 to 3 of the present application, and the method by scraping Compared with Comparative Example 1, which did not use long-chain carboxylic acid, the prepared direct X-ray image detector exhibited higher X-ray sensitivity, indicating that the long-chain carboxylic acid-type ionic liquid is conducive to the construction of thicker quantum arrays
  • the film layer is beneficial to improve the sensitivity of the direct type X-ray image detector, thereby improving the imaging clarity of the X-ray.

Abstract

Détecteur d'image à rayons X direct et son procédé de fabrication. Le procédé de fabrication du détecteur d'image à rayons X direct comprend les étapes suivantes : la synthèse d'un acide carboxylique organique à longue chaîne et d'un ligand organique dans un liquide ionique ; la dissolution du liquide ionique, d'un métal halocarbure et d'un sel d'halogénure dans un solvant organique pour obtenir un gel précurseur ; la formation d'un film sur la surface d'un réseau de pixels d'un substrat à l'aide du gel précurseur, et le recuit, pour former une couche de film de réseau quantique de pérovskite hybride bidimensionnelle sur la surface du réseau de pixels du substrat ; et la préparation d'une couche d'électrode pour obtenir un détecteur d'image à rayons X direct. Selon le procédé de fabrication du détecteur d'image à rayons X direct, un acide carboxylique organique à longue chaîne est introduit, le taux d'agrégation octaédrique [BX6] est réduit, la viscosité de la solution de précurseur est améliorée, un réseau de puits quantiques ayant une distribution de largeur de puits unique est construit, l'épaisseur de formation de film de la couche de film de réseau quantique est augmentée, l'efficacité de conversion et d'absorption de rayons X du dispositif est améliorée, et une imagerie haute définition de rayons X est obtenue.
PCT/CN2021/138092 2021-11-19 2021-12-14 Détecteur d'image à rayons x direct et son procédé de fabrication WO2023087453A1 (fr)

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