WO2022030158A1 - Dispositif de conversion de rayonnement ionisant et procédé de détection de rayonnement ionisant - Google Patents

Dispositif de conversion de rayonnement ionisant et procédé de détection de rayonnement ionisant Download PDF

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Publication number
WO2022030158A1
WO2022030158A1 PCT/JP2021/025297 JP2021025297W WO2022030158A1 WO 2022030158 A1 WO2022030158 A1 WO 2022030158A1 JP 2021025297 W JP2021025297 W JP 2021025297W WO 2022030158 A1 WO2022030158 A1 WO 2022030158A1
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Prior art keywords
ionizing radiation
radiation conversion
conversion device
perovskite compound
substrate
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PCT/JP2021/025297
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English (en)
Japanese (ja)
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太佑 松井
幸広 金子
卓之 根上
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パナソニックＩｐマネジメント株式会社
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Publication of WO2022030158A1 publication Critical patent/WO2022030158A1/fr

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01T—MEASUREMENT OF NUCLEAR OR X-RADIATION
    • G01T1/00—Measuring X-radiation, gamma radiation, corpuscular radiation, or cosmic radiation
    • G01T1/16—Measuring radiation intensity
    • G01T1/24—Measuring radiation intensity with semiconductor detectors
    • 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

  • This disclosure relates to an ionizing radiation conversion device and a method for detecting ionizing radiation.
  • Non-Patent Document 1 methyl ammonium iodide is used as a perovskite compound that converts X-rays into electric charges.
  • An object of the present disclosure is to provide an ionizing radiation conversion device having high sensitivity to ionizing radiation.
  • the ionizing radiation conversion device is The substrate and the ionizing radiation conversion layer arranged on the substrate are provided.
  • the ionizing radiation conversion layer contains a perovskite compound having an average particle size of 1 ⁇ m or more and a resin material.
  • the present disclosure provides an ionizing radiation conversion device having high sensitivity to ionizing radiation.
  • FIG. 1 shows a cross-sectional view of an ionizing radiation conversion device according to one aspect of the present disclosure.
  • FIG. 2 shows a cross-sectional view of an ionizing radiation conversion device according to another aspect of the present disclosure.
  • FIG. 3 shows a cross-sectional view of the ionizing radiation conversion device according to still another aspect of the present disclosure.
  • the absorbed ionizing radiation for example, X-ray
  • the ionizing radiation has a high penetrating ability. Therefore, from the viewpoint of the absorbing ability, it is desirable that the ionizing radiation conversion layer is thick.
  • the film thickness of the ionizing radiation conversion layer be less than or equal to the carrier diffusion length.
  • the ionizing radiation conversion thin film formed on the substrate is basically polycrystal, but the polycrystal has a grain boundary, so that the carrier diffusion is compared with the single crystal.
  • the length is extremely small. Therefore, in order to extract the carriers generated in the polycrystalline film, the ionizing radiation conversion thin film needs to be a very thin film (usually 1 ⁇ m or less).
  • it is a single crystal film it is possible to take out the generated carriers even if the film thickness is increased, but in the perovskite compound, a single crystal is grown on the substrate to form a thin film due to the restrictions of the substrate and the process. That is difficult. Therefore, in the ionizing radiation conversion layer, it is difficult to achieve both a film thickness sufficient for absorbing ionizing radiation and taking out carriers without loss.
  • the substrate can be filled with a high-quality perovskite compound in an amount capable of sufficiently absorbing ionizing radiation. Therefore, the ionizing radiation conversion device of the present disclosure has high sensitivity to ionizing radiation.
  • ionizing radiation means ⁇ ray, ⁇ ray, neutron beam, proton beam, X-ray, or ⁇ ray.
  • FIG. 1 shows a cross-sectional view of the ionizing radiation conversion device 100 according to one aspect of the present disclosure.
  • the ionizing radiation conversion device 100 includes a substrate 10 and an ionizing radiation conversion layer 20 arranged on the substrate 10.
  • the ionizing radiation conversion layer 20 contains a perovskite compound having an average particle size of 1 ⁇ m or more.
  • the ionizing radiation conversion device 100 has high sensitivity to ionizing radiation. That is, the ionizing radiation conversion device 100 can efficiently convert ionizing radiation into electric charges.
  • a perovskite compound having an average particle size of 1 ⁇ m or more can efficiently absorb ionizing radiation, and the charge generated by the ionizing radiation can be efficiently transferred within the particles.
  • the ionizing radiation conversion device 100 can be used, for example, as an ionizing radiation detector, an image pickup device, a dosimeter, or a beta volta battery.
  • the ionizing radiation conversion device 100 may further include a read-out circuit that reads out the electric charge.
  • the readout circuit is electrically connected to the ionizing radiation conversion device 100.
  • the readout circuit may be located inside the substrate 10 or may be located outside the substrate 10, for example.
  • FIG. 2 shows a cross-sectional view of the ionizing radiation conversion device 200 according to another aspect of the present disclosure.
  • the ionizing radiation conversion device 200 further includes an electrode 30 in addition to the ionizing radiation conversion device 100.
  • the ionizing radiation conversion layer 20 is arranged between the substrate 10 and the electrode 30.
  • the ionizing radiation incident on the ionizing radiation conversion device 200 loses a part of the energy in the ionizing radiation conversion layer 20 to form electron-hole pairs.
  • the generated holes and electrons reach the substrate 10 and the electrode 30, respectively, and are taken out to an external circuit.
  • Ionizing radiation may be detected by detecting the charge or light generated by irradiating the perovskite compound with ionizing radiation. According to the above detection method, ionizing radiation can be detected with high sensitivity.
  • the substrate 10 may be made of glass or plastic. Alternatively, the substrate 10 may be made of a conductive material.
  • the conductive material may or may not have translucency.
  • An example of a conductive material having translucency is a metal oxide.
  • An example of the metal oxide is (I) Indium-tin composite oxide, (Ii) Antimony-doped tin oxide, (Iii) Fluorine-doped tin oxide, (Iv) zinc oxide doped with at least one element selected from the group consisting of boron, aluminum, gallium, and indium, or (v) a complex thereof.
  • non-transmissive conductive materials include platinum, gold, silver, copper, aluminum, rhodium, indium, titanium, iron, nickel, tin, zinc, or alloys containing any of these, or conductivity. It is a carbon material of.
  • the electrode 30 is made of a conductive material. Examples of conductive materials are as described above.
  • an electrode may be further provided between the substrate 10 and the ionizing radiation conversion layer 20.
  • the electrode is made of a conductive material.
  • the "perovskite compound” is a compound represented by ABX 3 or an analog thereof.
  • the compound represented by ABX 3 is, for example, BaTiO 3 , MgSiO 3 , CsPbI 3 , CsPbBr 3 or (CH 3 NH 3 ) PbI 3 .
  • the methylammonium cation that is, CH 3 NH 3+
  • MA the methylammonium cation
  • the analog of the compound represented by ABX 3 has the following structure (i) or (ii).
  • the perovskite compound may contain two or more cations and one or more monovalent anions.
  • the perovskite compound may substantially consist of two or more cations and one or more monovalent anions.
  • a perovskite compound is substantially composed of two or more cations and one or more monovalent anions" means that two or more cations are used with respect to the total amount of substance of all the elements constituting the perovskite compound. And it means that the total amount of substance of one or more monovalent anions is 90 mol% or more.
  • the perovskite compound may consist of two or more cations and one or more monovalent anions.
  • the two or more cations may contain at least one selected from the group consisting of Pb 2+ , Sn 2+ , Ge 2+ , and Bi 3+ .
  • the monovalent anion is, for example, a halogen anion or a composite anion.
  • halogen anions are fluorine anions, chlorine anions, bromine anions, or iodine anions.
  • composite anions are SCN-, NO 3- , or HCOO- .
  • the perovskite compound may be, for example, a compound represented by ABX 3 (A is a monovalent cation, B is a divalent cation, and X is a halogen anion). Since such a perovskite compound has a high ability to absorb ionizing radiation and a long carrier diffusion length, the ionizing radiation can be efficiently converted into an electric signal.
  • Examples of monovalent cations are organic cations or alkali metal cations.
  • organic cations are MA, formamidinium cations (ie NH 2 CHNH 2+ ), phenylethylammonium cations (ie C 6 H 5 C 2 H 4 NH 3 + ), or guanidinium cations (ie NH 2 CHNH 2 +). CH 6 N 3 + ).
  • alkali metal cations examples include cesium cations (ie, Cs + ) or rubidium cations (ie, Rb + ).
  • divalent metal cations are lead cations (ie, Pb 2+ ), tin cations (ie, Sn 2+ ), or germanium cations (ie, Ge 2+ ).
  • Perovskite compounds include, for example, CH 3 NH 3 PbI 3 , CH 3 CH 2 NH 3 PbI 3 , HC (NH 2 ) 2 PbI 3 , CH 3 NH 3 PbBr 3 , CH 3 NH 3 PbCl 3 , CsPbI 3 , or CsPbBr. It is 3 .
  • the ionizing radiation conversion layer 20 may have a thickness of 0.1 ⁇ m or more.
  • the ionizing radiation conversion layer 20 may have a thickness of 0.1 ⁇ m or more and 1 cm or less.
  • the ionizing radiation conversion layer 20 may have a thickness of 100 ⁇ m or more and 1 mm or less.
  • the ionizing radiation conversion layer 20 may contain 30 mol% or more of the perovskite compound.
  • the ionizing radiation conversion layer 20 may contain 80 mol% or more of the perovskite compound.
  • the ionizing radiation conversion layer 20 may be composed of only a perovskite compound.
  • the perovskite compound may be used as a scintillator.
  • the same effect can be obtained by arranging an element such as a photodiode that converts light into an electric signal between the substrate 10 and the ionizing radiation conversion layer 20 containing a perovskite compound. Is obtained.
  • the electrode 30 is not provided, and the substrate 10 may be a glass substrate or a plastic substrate.
  • the average particle size of the perovskite compound contained in the ionizing radiation conversion layer 20 may be 1 ⁇ m or more and 10 mm or less.
  • the average particle size of the perovskite compound may be 10 ⁇ m or more and 1 mm or less.
  • the particle size of the perovskite compound can be measured by a scanning electron microscope (SEM).
  • SEM scanning electron microscope
  • the particle group is observed with an electron microscope, and the directional diameter of a specific particle in the electron microscope image is measured.
  • the directional diameters of the particles of the 30 perovskite compounds are calculated, and their average value is regarded as the average particle diameter of the perovskite compound.
  • FIG. 3 shows a cross-sectional view of the ionizing radiation conversion device 300 according to still another aspect of the present disclosure.
  • the ionizing radiation conversion layer 20 may contain not only the ionizing radiation conversion material 21 containing the perovskite compound but also the resin material 22. As a result, the perovskite compound can be fixed, and the mechanical strength of the ionizing radiation conversion layer 20 is improved. In this way, the resin material 22 functions as a binder.
  • the resin material 22 may contain at least one selected from the group consisting of cellulose resin, epoxy resin, acrylic resin, polyolefin resin, polyether resin, and silicone resin.
  • the volume ratio of the resin material 22 to the perovskite compound may be 0.01% or more and 50% or less.
  • the volume ratio of the resin material to the perovskite compound may be 0.1% or more and 10% or less.
  • the substrate 10 may have a readout circuit.
  • the pixel pitch is, for example, 125 micrometers.
  • the ionizing radiation conversion layer 20 containing the perovskite compound is formed on the substrate 10.
  • a raw material is prepared so that the perovskite compound has a desired composition.
  • the solution obtained by dissolving the raw material of the perovskite compound in a solvent is heated to, for example, a predetermined temperature to precipitate particles of the perovskite compound.
  • a solution containing the obtained particles of the perovskite compound, a resin material, and a solvent is prepared.
  • the ionizing radiation conversion layer 20 is obtained by applying the prepared solution on the substrate 10 and drying it.
  • a ⁇ -butyrolactone solution containing 1 mol / L of PbI 2 and 1 mol / L of formamidinium iodide (CH (NH 2 ) 2 I) is prepared as a raw material for the perovskite compound.
  • a toluene solution containing the particles of the perovskite compound and a resin material (for example, polymethylmethacrylate) in a weight ratio of 1% is prepared.
  • the produced solution is applied onto the substrate 10 and dried to obtain the ionizing radiation conversion layer 20.
  • the electrode 30 is formed on the produced ionizing radiation conversion layer 20 by forming gold with a thickness of 100 nm, for example, by a vapor deposition method. In this way, an ionizing radiation conversion device is obtained.
  • the method for detecting ionizing radiation of the present disclosure is a method of detecting ionizing radiation using the above-mentioned ionizing radiation conversion device of the present disclosure.
  • the method for detecting ionizing radiation of the present disclosure includes, for example, a substrate 10 and an ionizing radiation conversion layer 20 arranged on the substrate 10, and the ionizing radiation conversion layer 20 is a perovskite compound having an average particle size of 1 ⁇ m or more. Use the contained ionizing radiation conversion device.
  • the charge or light generated by irradiating the perovskite compound with ionizing radiation by the ionizing radiation conversion device is detected.
  • the ionizing radiation conversion device of the present disclosure is used, for example, in an ionizing radiation detector.
  • Substrate 20 Ionizing radiation conversion layer 21 Ionizing radiation conversion material 22 Resin material 30 Electrodes 100, 200, 300 Ionizing radiation conversion device

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  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Molecular Biology (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Measurement Of Radiation (AREA)
  • Luminescent Compositions (AREA)
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Abstract

La présente invention concerne un dispositif de conversion de rayonnement ionisant comprenant un substrat et une couche de conversion de rayonnement ionisant disposée sur le substrat. La couche de conversion de rayonnement ionisant contient un composé de pérovskite présentant un diamètre moyen de particule d'au moins 1 μm et un matériau de résine.
PCT/JP2021/025297 2020-08-06 2021-07-05 Dispositif de conversion de rayonnement ionisant et procédé de détection de rayonnement ionisant WO2022030158A1 (fr)

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JP2020-134157 2020-08-06
JP2020134157A JP2023127003A (ja) 2020-08-06 2020-08-06 電離放射線変換デバイスおよび電離放射線の検出方法

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017082081A1 (fr) * 2015-11-09 2017-05-18 浜松ホトニクス株式会社 Détecteur de rayonnement et procédé de fabrication de détecteur de rayonnement
WO2020003603A1 (fr) * 2018-06-26 2020-01-02 国立大学法人京都大学 Détecteur de rayonnement et procédé de fabrication de détecteur de rayonnement

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017082081A1 (fr) * 2015-11-09 2017-05-18 浜松ホトニクス株式会社 Détecteur de rayonnement et procédé de fabrication de détecteur de rayonnement
WO2020003603A1 (fr) * 2018-06-26 2020-01-02 国立大学法人京都大学 Détecteur de rayonnement et procédé de fabrication de détecteur de rayonnement

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