WO2022030156A1 - Ionizing radiation conversion device, method for detecting ionizing radiation, and method for producing ionizing radiation conversion device - Google Patents

Ionizing radiation conversion device, method for detecting ionizing radiation, and method for producing ionizing radiation conversion device Download PDF

Info

Publication number
WO2022030156A1
WO2022030156A1 PCT/JP2021/025295 JP2021025295W WO2022030156A1 WO 2022030156 A1 WO2022030156 A1 WO 2022030156A1 JP 2021025295 W JP2021025295 W JP 2021025295W WO 2022030156 A1 WO2022030156 A1 WO 2022030156A1
Authority
WO
WIPO (PCT)
Prior art keywords
ionizing radiation
radiation conversion
substrate
conversion layer
conversion device
Prior art date
Application number
PCT/JP2021/025295
Other languages
French (fr)
Japanese (ja)
Inventor
太佑 松井
幸広 金子
卓之 根上
Original Assignee
パナソニックＩｐマネジメント株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by パナソニックＩｐマネジメント株式会社 filed Critical パナソニックＩｐマネジメント株式会社
Priority to JP2022541164A priority Critical patent/JPWO2022030156A1/ja
Publication of WO2022030156A1 publication Critical patent/WO2022030156A1/en

Links

Images

Classifications

    • 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

Definitions

  • the present disclosure relates to an ionizing radiation conversion device, a method for detecting ionizing radiation, and a method for manufacturing an ionizing radiation conversion device.
  • 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 A first laminated body including a first substrate and a first ionizing radiation conversion layer arranged on the first substrate, and a second including a second substrate and a second ionizing radiation conversion layer arranged on the second substrate.
  • the first ionizing radiation conversion layer contains a first perovskite compound and contains.
  • the second ionizing radiation conversion layer contains a second perovskite compound and contains.
  • the first ionizing radiation conversion layer is arranged between the first substrate and the second substrate.
  • the present disclosure provides an ionizing radiation conversion device having high sensitivity to ionizing radiation.
  • FIG. 1 shows a cross-sectional view of the ionizing radiation conversion device according to the first embodiment.
  • FIG. 2 shows a cross-sectional view of another ionizing radiation conversion device according to the first embodiment.
  • FIG. 3 shows a cross-sectional view of an ionizing radiation conversion device in which the first laminated body and the second laminated body are connected in parallel with each other.
  • FIG. 4 shows a cross-sectional view of an ionizing radiation conversion device consisting of a single laminate.
  • FIG. 5 shows a cross-sectional view of the ionizing radiation conversion device according to the second embodiment.
  • 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 carrier diffusion length of the polycrystalline perovskite compound is several hundred nm to several ⁇ m, and the carrier diffusion length of the single crystal perobskite compound is about several ⁇ m. If the film thickness is equal to or less than the carrier diffusion length, there is a problem that the ionizing radiation conversion layer cannot sufficiently absorb the ionizing radiation.
  • the ionizing radiation conversion layer is used as a sensor, it is possible to apply an external voltage to take out the carrier, but if the film thickness of the ionizing radiation conversion layer is large, the external voltage required for taking out the carrier becomes large. .. As a result, there arises a problem that the S / N ratio decreases due to the increase in dark current.
  • the ionizing radiation conversion device of the present disclosure by stacking a plurality of laminated devices having a thin film ionizing radiation conversion layer that facilitates carrier extraction, the ionizing radiation is sufficiently absorbed and the generated carriers are efficiently extracted. Is possible.
  • 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 the first embodiment.
  • the ionizing radiation conversion device 100 includes a first laminated body 10 and a second laminated body 20.
  • the second laminated body 20 is arranged on the first laminated body 10.
  • the first laminated body 10 has a first substrate 11 and a first ionizing radiation conversion layer 12 arranged on the first substrate 11.
  • the second laminated body 20 has a second substrate 21 and a second ionizing radiation conversion layer 22 arranged on the second substrate 21.
  • the first ionizing radiation conversion layer 12 is arranged between the first substrate 11 and the second substrate 21.
  • 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.
  • 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 first board 11 or may be located outside the first board 11, for example.
  • FIG. 2 shows a cross-sectional view of the ionizing radiation conversion device 200 according to the first embodiment.
  • the first laminated body 10 may further include a first electrode 13.
  • the first ionizing radiation conversion layer 12 is arranged between the first substrate 11 and the first electrode 13.
  • the second laminated body 20 may further include a second electrode 23.
  • the second ionizing radiation conversion layer 22 is arranged between the second substrate 21 and the second electrode 23.
  • the ionizing radiation incident on the ionizing radiation conversion device 200 loses a part of the energy in the first ionizing radiation conversion layer 12 and the second ionizing radiation conversion layer 22 to form electron hole pairs.
  • the holes and electrons generated in the first ionizing radiation conversion layer 12 reach the first substrate 11 and the first electrode 13, respectively, and are taken out to an external circuit.
  • the holes and electrons generated in the second ionizing radiation conversion layer 22 reach the second substrate 21 and the second electrode 23, respectively, and are taken out to an external circuit.
  • the first substrate 11 and the second substrate 21 may be made of glass or plastic. Alternatively, the first substrate 11 and the second substrate 21 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.
  • Both the first electrode 13 and the second electrode 23 are made of a conductive material. Examples of conductive materials are as described above.
  • At least one selected from the group consisting of the first substrate 11, the first electrode 13, the second substrate 21, and the second electrode 23 may be made of a material having no translucency. As a result, the resistance value of the electrode can be suppressed to a low level, and the performance of the ionizing radiation conversion device is improved.
  • an electrode may be further provided between the first substrate 11 and the first ionizing radiation conversion layer 12.
  • the electrode is made of a conductive material.
  • an electrode may be further provided between the second substrate 21 and the second ionizing radiation conversion layer 22.
  • the electrode is made of a conductive material.
  • the first laminated body 10 When the ionizing radiation conversion device 200 is connected to an external circuit, the first laminated body 10 may be connected in series with the second laminated body 20 or may be connected in parallel.
  • the first laminated body 10 does not have to be in contact with the second laminated body 20.
  • Another layer may be arranged between the first laminated body 10 and the second laminated body 20.
  • An example of another layer may be an insulating layer.
  • the insulating layer is composed of an insulating material.
  • the insulating material may be an organic insulating material or an inorganic insulating material. Examples of organic insulating materials are epoxy resins, silicone resins, or polyimides. Examples of inorganic insulating materials are silicon oxide, silicon nitride, silicon nitride, hafnium oxide, aluminum oxide, and tantalum oxide.
  • the insulating layer may be made of glass or plastic.
  • FIG. 3 shows a cross-sectional view of an ionizing radiation conversion device 200 in which the first laminated body 10 and the second laminated body 20 are electrically connected in parallel with each other.
  • the first laminated body 10 is electrically connected in parallel with the second laminated body 20 by the lead wire 14.
  • the parallel connection increases the current value taken out to the external circuit, so that the performance of the ionizing radiation conversion device 200 is improved.
  • FIG. 4 shows a cross-sectional view of an ionizing radiation conversion device 300 made of a single laminated body. As an example of a single laminated body, the first laminated body 10 is shown.
  • the ionizing radiation conversion layer can be made thinner as compared with the ionizing radiation conversion device 300. As a result, the distance that the generated carriers move to the electrodes is shortened, so that the carrier loss is small and the carriers can be efficiently taken out to the external circuit.
  • Ionizing radiation may be detected by detecting the electric charge generated by irradiating the first perovskite compound and the second perovskite compound with ionizing radiation. According to the above detection method, ionizing radiation can be detected with high sensitivity.
  • 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 first perovskite compound and the second perovskite compound may independently contain two or more kinds of cations and one or more kinds of 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 examples include lead cations (ie, Pb 2+ ), tin cations (ie, Sn 2+ ), or germanium cations (ie, Ge 2+ ).
  • the divalent metal cation may be Pb 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 difference between the band gap of the first perovskite compound and the band gap of the second perovskite compound may be 0.1 eV or less.
  • the first perovskite compound may be the same as the second perovskite compound.
  • Each of the first ionizing radiation conversion layer 12 and the second ionizing radiation conversion layer 22 may have a thickness of 0.1 ⁇ m or more. Each of the first ionizing radiation conversion layer 12 and the second ionizing radiation conversion layer 22 may have a thickness of 0.1 ⁇ m or more and 1 cm or less. Each of the first ionizing radiation conversion layer 12 and the second ionizing radiation conversion layer 22 may have a thickness of 100 ⁇ m or more and 1 mm or less.
  • the first ionizing radiation conversion layer 12 may have a thickness different from that of the second ionizing radiation conversion layer 22.
  • the first ionizing radiation conversion layer 12 may contain 30 mol% or more of the first perovskite compound.
  • the first ionizing radiation conversion layer 12 may contain 80 mol% or more of the first perovskite compound.
  • the first ionizing radiation conversion layer 12 may be composed of only the first perovskite compound.
  • the second ionizing radiation conversion layer 22 may contain 30 mol% or more of the second perovskite compound.
  • the second ionizing radiation conversion layer 22 may contain 80 mol% or more of the second perovskite compound.
  • the second ionizing radiation conversion layer 22 may be composed of only the second perovskite compound.
  • the perovskite compound may be used as a scintillator.
  • the same can be achieved by arranging an element such as a photodiode that converts light into an electric signal between the first ionizing radiation conversion layer 12 containing the perovskite compound and the first substrate 11. The effect of is obtained.
  • the first electrode 11 is not provided, and the first substrate 11 may be a glass substrate or a plastic substrate.
  • FIG. 5 shows a cross-sectional view of the ionizing radiation conversion device 400 according to the second embodiment.
  • the ionizing radiation conversion device 400 includes a third laminated body 30 in addition to the first laminated body 10 and the second laminated body 20.
  • the second laminated body 20 is arranged between the first laminated body 10 and the third laminated body 30.
  • the third laminated body 30 has a third substrate 31, a third ionizing radiation conversion layer 32, and a third electrode 33.
  • the third ionizing radiation conversion layer 32 is arranged between the third substrate 31 and the third electrode 33.
  • the ionizing radiation conversion device 400 has higher sensitivity to ionizing radiation. That is, the ionizing radiation conversion device 400 can more efficiently convert the ionizing radiation into electric charges.
  • the material constituting the third substrate 31 and the third electrode 33 may be the conductive material described in the first embodiment.
  • At least two laminates selected from the group consisting of the first laminate 10, the second laminate 20, and the third laminate 30 may be electrically connected in parallel with each other.
  • the parallel connection increases the current value taken out to the external circuit, so that the performance of the ionizing radiation conversion device 400 is improved.
  • the ionizing radiation conversion device of the present disclosure for example, four or more laminated bodies may be laminated in order to convert ionizing radiation more efficiently. That is, the ionizing radiation conversion device of the present disclosure may include four or more ionizing radiation conversion layers. In the ionizing radiation conversion device of the present disclosure, for example, 10 or more laminated bodies may be laminated. That is, the ionizing radiation conversion device of the present disclosure may include 10 or more ionizing radiation conversion layers.
  • the method for manufacturing an ionizing radiation conversion device includes a first step of preparing a first substrate 11 and a second step of forming a first ionizing radiation conversion layer 12 containing a perovskite compound on the first substrate 11.
  • the first substrate 11 is prepared.
  • the first substrate 11 may have a read-out circuit.
  • the pixel pitch is, for example, 125 micrometers.
  • the first ionizing radiation conversion layer 12 containing the first perovskite compound is formed on the first substrate 11.
  • a raw material is prepared so that the first perovskite compound has a desired composition.
  • the raw material of the first perovskite compound is dissolved in a solvent to obtain a precursor solution of the first ionizing radiation conversion layer 12.
  • the first ionizing radiation conversion layer 12 is formed.
  • the second step will be described.
  • raw materials for the first perovskite compound for example, 0.92 mol / L PbI 2 , 0.17 mol / L PbBr 2 , 0.83 mol / L formamidinium iodide, 0.17 mol / L methylammonium bromide. , And 0.05 mol / L CsI are prepared. These materials are dissolved in a mixed solvent of dimethyl sulfoxide and N, N-dimethylformamide. As a result, a precursor solution of the first ionizing radiation conversion layer 12 containing the perovskite compound is obtained.
  • the mixing ratio of dimethyl sulfoxide and N, N-dimethylformamide is, for example, 1: 4 (volume ratio).
  • the first ionizing radiation conversion layer 12 is formed by applying the precursor solution, for example, by an inkjet method.
  • the first electrode 13 is formed on the first ionizing radiation conversion layer 12.
  • a first electrode 13 made of gold is formed by a thin-film deposition method.
  • the first electrode 13 has a thickness of, for example, 100 nanometers. In this way, the first laminated body 10 is obtained.
  • the second laminated body 20 is obtained in the same manner as the first laminated body 10.
  • the second laminated body 20 By arranging the second laminated body 20 on the first laminated body 10, an ionizing radiation conversion device can be obtained. As described above, the second ionizing radiation conversion layer 22 having the second ionizing radiation conversion layer 22 arranged on the second substrate 21 is placed on the first laminated body 10 having the first ionizing radiation conversion layer 12 arranged on the first substrate 11. 2 The laminated body 20 may be formed.
  • 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 is, for example, the first laminated body 10 including the first ionizing radiation conversion layer 12 arranged on the first substrate 11 and the first substrate 11, and the second substrate 21 and the first.
  • An ionizing radiation conversion device containing 2 perovskite compounds and the second laminated body 20 being laminated on the first laminated body 10 is used.
  • the charge or light generated by irradiating the first perovskite compound and the second 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.

Abstract

This ionizing radiation conversion device comprises: a first layered body including a first substrate and a first ionizing radiation conversion layer arranged on the first substrate; and a second layered body including a second substrate and a second ionizing radiation conversion layer arranged on the second substrate. The first ionizing radiation conversion layer contains a first perovskite compound, the second ionizing radiation conversion layer contains a second perovskite compound, and the first ionizing radiation conversion layer is arranged between the first substrate and the second substrate.

Description

電離放射線変換デバイス、電離放射線の検出方法、及び電離放射線変換デバイスの製造方法Ionizing radiation conversion device, ionizing radiation detection method, and manufacturing method of ionizing radiation conversion device
　本開示は、電離放射線変換デバイス、電離放射線の検出方法、及び電離放射線変換デバイスの製造方法に関する。 The present disclosure relates to an ionizing radiation conversion device, a method for detecting ionizing radiation, and a method for manufacturing an ionizing radiation conversion device.
　Ｘ線のような電離放射線を電気信号に変えるデバイスは種々あり、物質から発せられる電離放射線の強度を測定すること、または電離放射線を物質に照射した結果、物質を透過する電離放射線を測定することで物質の内部情報を得ることができる。電離放射線を電気信号に変換する材料は種々考案され実用化されている。一般的にこの材料は原子番号が大きい原子を含むことが望ましい。現在、電離放射線を電気信号に変換する材料として使用されているのはアモルファスセレンまたはヨウ化セシウムである。近年、ヨウ化鉛メチルアンモニウムに代表されるペロブスカイト化合物がその材料として着目されている。 There are various devices that convert ionizing radiation such as X-rays into electrical signals, measuring the intensity of ionizing radiation emitted from a substance, or measuring the ionizing radiation that penetrates a substance as a result of irradiating the substance with ionizing radiation. You can get the inside information of the substance with. Various materials for converting ionizing radiation into electrical signals have been devised and put into practical use. Generally, it is desirable that this material contains an atom having a large atomic number. Amorphous selenium or cesium iodide is currently used as a material for converting ionizing radiation into electrical signals. In recent years, perovskite compounds typified by methylammonium lead iodide have been attracting attention as their materials.
　電離放射線を電気信号に変える場合、前述の材料を厚くすることで、その感度を上げることが可能である。 When converting ionizing radiation into an electrical signal, it is possible to increase its sensitivity by thickening the above-mentioned material.
　非特許文献１では、Ｘ線を電荷に変換するペロブスカイト化合物として、ヨウ化鉛メチルアンモニウムが使用されている。 In Non-Patent Document 1, methyl ammonium iodide is used as a perovskite compound that converts X-rays into electric charges.
　本開示の目的は、電離放射線に対して高い感度を有する電離放射線変換デバイスを提供することにある。 An object of the present disclosure is to provide an ionizing radiation conversion device having high sensitivity to ionizing radiation.
　本開示の一態様に係る電離放射線変換デバイスは、
　第１基板および前記第１基板上に配置された第１電離放射線変換層を含む第１積層体、並びに
　第２基板および前記第２基板上に配置された第２電離放射線変換層を含む第２積層体、を備え、
　前記第１電離放射線変換層は、第１ペロブスカイト化合物を含有し、
　前記第２電離放射線変換層は、第２ペロブスカイト化合物を含有し、
　前記第１電離放射線変換層は、前記第１基板および前記第２基板の間に配置されている。 The ionizing radiation conversion device according to one aspect of the present disclosure is
A first laminated body including a first substrate and a first ionizing radiation conversion layer arranged on the first substrate, and a second including a second substrate and a second ionizing radiation conversion layer arranged on the second substrate. With a laminate,
The first ionizing radiation conversion layer contains a first perovskite compound and contains.
The second ionizing radiation conversion layer contains a second perovskite compound and contains.
The first ionizing radiation conversion layer is arranged between the first substrate and the second substrate.
　本開示は、電離放射線に対して高い感度を有する電離放射線変換デバイスを提供する。 The present disclosure provides an ionizing radiation conversion device having high sensitivity to ionizing radiation.
図１は、第１実施形態による電離放射線変換デバイスの断面図を示す。FIG. 1 shows a cross-sectional view of the ionizing radiation conversion device according to the first embodiment. 図２は、第１実施形態による他の電離放射線変換デバイスの断面図を示す。FIG. 2 shows a cross-sectional view of another ionizing radiation conversion device according to the first embodiment. 図３は、第１積層体および第２積層体が互いに並列に接続された電離放射線変換デバイスの断面図を示す。FIG. 3 shows a cross-sectional view of an ionizing radiation conversion device in which the first laminated body and the second laminated body are connected in parallel with each other. 図４は、単一の積層体からなる電離放射線変換デバイスの断面図を示す。FIG. 4 shows a cross-sectional view of an ionizing radiation conversion device consisting of a single laminate. 図５は、第２実施形態による電離放射線変換デバイスの断面図を示す。FIG. 5 shows a cross-sectional view of the ionizing radiation conversion device according to the second embodiment.
　（本開示の基礎となった知見）
　吸収した電離放射線（例えば、Ｘ線）を電気信号に変換する場合、電離放射線は透過能が高いため、吸収能の観点では電離放射線変換層は厚い方が望ましい。一方で、電離放射線によって励起された電子と正孔を外部回路に取り出すためには、電離放射線変換層の膜厚をキャリア拡散長以下とすることが望ましい。電離放射線変換材料として、ペロブスカイト化合物を用いる場合、多結晶のペロブスカイト化合物のキャリア拡散長は、数百ｎｍから数μｍ、単結晶のペロブスカイト化合物のキャリア拡散長は、数μｍ程度である。これらのキャリア拡散長と同等以下の膜厚では、電離放射線変換層が電離放射線を十分に吸収しきれないという課題がある。また、電離放射線変換層をセンサとして利用する場合、外部電圧を印加してキャリアを取り出すことも可能であるが、電離放射線変換層の膜厚が大きいと、キャリア取り出しに必要な外部電圧は大きくなる。その結果、ダーク電流が大きくなることで、Ｓ／Ｎ比が低下するという問題が生じる。 (Findings underlying this disclosure)
When the absorbed ionizing radiation (for example, X-ray) is converted into an electric signal, 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. On the other hand, in order to extract electrons and holes excited by ionizing radiation to an external circuit, it is desirable that the film thickness of the ionizing radiation conversion layer be less than or equal to the carrier diffusion length. When a perovskite compound is used as the ionization radiation conversion material, the carrier diffusion length of the polycrystalline perovskite compound is several hundred nm to several μm, and the carrier diffusion length of the single crystal perobskite compound is about several μm. If the film thickness is equal to or less than the carrier diffusion length, there is a problem that the ionizing radiation conversion layer cannot sufficiently absorb the ionizing radiation. When the ionizing radiation conversion layer is used as a sensor, it is possible to apply an external voltage to take out the carrier, but if the film thickness of the ionizing radiation conversion layer is large, the external voltage required for taking out the carrier becomes large. .. As a result, there arises a problem that the S / N ratio decreases due to the increase in dark current.
　本開示の電離放射線変換デバイスでは、キャリア取り出しが容易な薄膜の電離放射線変換層を備えた積層体デバイスを複数積層させることで、十分に電離放射線を吸収するとともに、発生したキャリアを効率的に取り出すことが可能となる。 In the ionizing radiation conversion device of the present disclosure, by stacking a plurality of laminated devices having a thin film ionizing radiation conversion layer that facilitates carrier extraction, the ionizing radiation is sufficiently absorbed and the generated carriers are efficiently extracted. Is possible.
　本開示において、「電離放射線」とは、α線、β線、中性子線、陽子線、Ｘ線、またはγ線を意味する。 In the present disclosure, "ionizing radiation" means α ray, β ray, neutron beam, proton beam, X-ray, or γ ray.
　以下、本開示の実施形態が、図面を参照しながら説明される。 Hereinafter, embodiments of the present disclosure will be described with reference to the drawings.
　（第１実施形態）
　第１実施形態による電離放射線変換デバイス１００の構成について説明する。 (First Embodiment)
The configuration of the ionizing radiation conversion device 100 according to the first embodiment will be described.
　図１は、第１実施形態による電離放射線変換デバイス１００の断面図を示す。 FIG. 1 shows a cross-sectional view of the ionizing radiation conversion device 100 according to the first embodiment.
　電離放射線変換デバイス１００は、第１積層体１０および第２積層体２０を備える。ここで、第２積層体２０は、第１積層体１０上に配置されている。 The ionizing radiation conversion device 100 includes a first laminated body 10 and a second laminated body 20. Here, the second laminated body 20 is arranged on the first laminated body 10.
　第１積層体１０は、第１基板１１および第１基板１１上に配置されている第１電離放射線変換層１２を有する。 The first laminated body 10 has a first substrate 11 and a first ionizing radiation conversion layer 12 arranged on the first substrate 11.
　第２積層体２０は、第２基板２１および第２基板２１上に配置されている第２電離放射線変換層２２を有する。第１電離放射線変換層１２は、第１基板１１および第２基板２１の間に配置されている。 The second laminated body 20 has a second substrate 21 and a second ionizing radiation conversion layer 22 arranged on the second substrate 21. The first ionizing radiation conversion layer 12 is arranged between the first substrate 11 and the second substrate 21.
　以上の構成によれば、電離放射線変換デバイス１００は、電離放射線に対して高い感度を有する。すなわち、電離放射線変換デバイス１００は、電離放射線を効率よく電荷に変換することができる。 According to the above configuration, 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.
　電離放射線変換デバイス１００は、例えば、電離放射線検出器、撮像装置、線量計、またはベータボルタ電池として使用され得る。 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.
　電離放射線変換デバイス１００は、電荷を読み出す読み出し回路をさらに備えていてもよい。ここで、読み出し回路は、電離放射線変換デバイス１００に電気的に接続されている。 The ionizing radiation conversion device 100 may further include a read-out circuit that reads out the electric charge. Here, the readout circuit is electrically connected to the ionizing radiation conversion device 100.
　読み出し回路は、例えば、第１基板１１中に位置していてもよく、第１基板１１の外部に位置していてもよい。 The readout circuit may be located inside the first board 11 or may be located outside the first board 11, for example.
　図２は、第１実施形態による電離放射線変換デバイス２００の断面図を示す。 FIG. 2 shows a cross-sectional view of the ionizing radiation conversion device 200 according to the first embodiment.
　第１積層体１０は、第１電極１３をさらに備えていてもよい。ここで、第１電離放射線変換層１２は、第１基板１１および第１電極１３の間に配置されている。 The first laminated body 10 may further include a first electrode 13. Here, the first ionizing radiation conversion layer 12 is arranged between the first substrate 11 and the first electrode 13.
　第２積層体２０は、第２電極２３をさらに備えていてもよい。ここで、第２電離放射線変換層２２は、第２基板２１および第２電極２３の間に配置されている。 The second laminated body 20 may further include a second electrode 23. Here, the second ionizing radiation conversion layer 22 is arranged between the second substrate 21 and the second electrode 23.
　以下、図２を用いて直接変換方式の電離放射線変換デバイスの動作の概略を説明する。電離放射線変換デバイス２００に入射された電離放射線は、第１電離放射線変換層１２および第２電離放射線変換層２２でその一部のエネルギーを失い、電子正孔対を形成する。第１電離放射線変換層１２において生成された正孔および電子は、それぞれ第１基板１１および第１電極１３に到達し、外部回路に取り出される。第２電離放射線変換層２２において生成された正孔および電子は、それぞれ第２基板２１および第２電極２３に到達し、外部回路に取り出される。 Hereinafter, the outline of the operation of the direct conversion type ionizing radiation conversion device will be described with reference to FIG. The ionizing radiation incident on the ionizing radiation conversion device 200 loses a part of the energy in the first ionizing radiation conversion layer 12 and the second ionizing radiation conversion layer 22 to form electron hole pairs. The holes and electrons generated in the first ionizing radiation conversion layer 12 reach the first substrate 11 and the first electrode 13, respectively, and are taken out to an external circuit. The holes and electrons generated in the second ionizing radiation conversion layer 22 reach the second substrate 21 and the second electrode 23, respectively, and are taken out to an external circuit.
　第１基板１１および第２基板２１は、ガラスまたはプラスチックから構成されていてもよい。あるいは、第１基板１１および第２基板２１は、導電性材料から構成されていてもよい。 The first substrate 11 and the second substrate 21 may be made of glass or plastic. Alternatively, the first substrate 11 and the second substrate 21 may be made of a conductive material.
　導電性材料は、透光性を有していてもよく、透光性を有していなくてもよい。 The conductive material may or may not have translucency.
　透光性を有する導電性材料の例は、金属酸化物である。当該金属酸化物の例は、
（ｉ）インジウム－錫複合酸化物、
（ｉｉ）アンチモンがドープされた酸化錫、
（ｉｉｉ）フッ素がドープされた酸化錫、
（ｉｖ）ホウ素、アルミニウム、ガリウム、およびインジウムからなる群より選択される少なくとも１つの元素がドープされた酸化亜鉛、または
（ｖ）これらの複合物
である。 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.
　透光性を有しない導電性材料の例は、白金、金、銀、銅、アルミニウム、ロジウム、インジウム、チタン、鉄、ニッケル、スズ、亜鉛、あるいはこれらのいずれかを含む合金、または、導電性の炭素材料である。 Examples of 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.
　第１電極１３および第２電極２３は、いずれも導電性材料から構成される。導電性材料の例は、上述の通りである。 Both the first electrode 13 and the second electrode 23 are made of a conductive material. Examples of conductive materials are as described above.
　第１基板１１、第１電極１３、第２基板２１、および第２電極２３からなる群より選択される少なくとも１つは、透光性を有しない材料から構成されていてもよい。これにより、電極の抵抗値を低く抑えることができ、電離放射線変換デバイスの性能が向上する。 At least one selected from the group consisting of the first substrate 11, the first electrode 13, the second substrate 21, and the second electrode 23 may be made of a material having no translucency. As a result, the resistance value of the electrode can be suppressed to a low level, and the performance of the ionizing radiation conversion device is improved.
　第１基板１１がガラスまたはプラスチックから構成される場合、第１基板１１および第１電離放射線変換層１２の間にさらに電極を備えていてもよい。当該電極は、導電性材料から構成される。 When the first substrate 11 is made of glass or plastic, an electrode may be further provided between the first substrate 11 and the first ionizing radiation conversion layer 12. The electrode is made of a conductive material.
　第２基板２１がガラスまたはプラスチックから構成される場合、第２基板２１および第２電離放射線変換層２２の間にさらに電極を備えていてもよい。当該電極は、導電性材料から構成される。 When the second substrate 21 is made of glass or plastic, an electrode may be further provided between the second substrate 21 and the second ionizing radiation conversion layer 22. The electrode is made of a conductive material.
　電離放射線変換デバイス２００が外部回路に接続される場合、第１積層体１０は、第２積層体２０と直列に接続されていてもよく、あるいは、並列に接続されていてもよい。 When the ionizing radiation conversion device 200 is connected to an external circuit, the first laminated body 10 may be connected in series with the second laminated body 20 or may be connected in parallel.
　第１積層体１０は、第２積層体２０に接していなくてもよい。 The first laminated body 10 does not have to be in contact with the second laminated body 20.
　第１積層体１０と第２積層体２０との間に別の層が配置されていてもよい。別の層の例は、絶縁層であってもよい。当該絶縁層は、絶縁材料から構成される。絶縁材料は、有機絶縁材料であってもよく、無機絶縁材料であってもよい。有機絶縁材料の例は、エポキシ樹脂、シリコン樹脂、またはポリイミドである。無機絶縁材料の例は、酸化ケイ素、窒化ケイ素、酸窒化ケイ素、酸化ハフニウム、酸化アルミニウム、酸化タンタルである。 Another layer may be arranged between the first laminated body 10 and the second laminated body 20. An example of another layer may be an insulating layer. The insulating layer is composed of an insulating material. The insulating material may be an organic insulating material or an inorganic insulating material. Examples of organic insulating materials are epoxy resins, silicone resins, or polyimides. Examples of inorganic insulating materials are silicon oxide, silicon nitride, silicon nitride, hafnium oxide, aluminum oxide, and tantalum oxide.
　当該絶縁層は、ガラスまたはプラスチックから構成されていてもよい。 The insulating layer may be made of glass or plastic.
　図３は、第１積層体１０および第２積層体２０が互いに並列に電気的に接続された電離放射線変換デバイス２００の断面図を示す。 FIG. 3 shows a cross-sectional view of an ionizing radiation conversion device 200 in which the first laminated body 10 and the second laminated body 20 are electrically connected in parallel with each other.
　図３では、第１積層体１０は、リード線１４によって第２積層体２０と並列に電気的に接続されている。当該並列接続により、外部回路に取り出される電流値が増加するため、電離放射線変換デバイス２００の性能が向上する。 In FIG. 3, the first laminated body 10 is electrically connected in parallel with the second laminated body 20 by the lead wire 14. The parallel connection increases the current value taken out to the external circuit, so that the performance of the ionizing radiation conversion device 200 is improved.
　図４は、単一の積層体からなる電離放射線変換デバイス３００の断面図を示す。単一の積層体の一例として、第１積層体１０が示される。 FIG. 4 shows a cross-sectional view of an ionizing radiation conversion device 300 made of a single laminated body. As an example of a single laminated body, the first laminated body 10 is shown.
　電離放射線変換デバイス１００および２００は、複数の電離放射線変換層を有するため、電離放射線変換デバイス３００と比較して、電離放射線変換層を薄くできる。その結果、生成したキャリアが電極まで移動する距離が短くなるため、キャリアの損失が少なく、効率的にキャリアを外部回路に取り出すことができる。 Since the ionizing radiation conversion devices 100 and 200 have a plurality of ionizing radiation conversion layers, the ionizing radiation conversion layer can be made thinner as compared with the ionizing radiation conversion device 300. As a result, the distance that the generated carriers move to the electrodes is shortened, so that the carrier loss is small and the carriers can be efficiently taken out to the external circuit.
　第１ペロブスカイト化合物および第２ペロブスカイト化合物に電離放射線が照射されることにより発生した電荷を検出することで、電離放射線を検出してもよい。以上の検出方法によれば、感度よく電離放射線を検出できる。 Ionizing radiation may be detected by detecting the electric charge generated by irradiating the first perovskite compound and the second perovskite compound with ionizing radiation. According to the above detection method, ionizing radiation can be detected with high sensitivity.
　本開示において、「ペロブスカイト化合物」とは、ＡＢＸ3により表される化合物またはその類縁体である。 In the present disclosure, the "perovskite compound" is a compound represented by ABX 3 or an analog thereof.
　ＡＢＸ3により表される化合物は、例えば、ＢａＴｉＯ3、ＭｇＳｉＯ3、ＣｓＰｂＩ3、ＣｓＰｂＢｒ3または（ＣＨ3ＮＨ3）ＰｂＩ3である。以下、メチルアンモニウムカチオン（すなわち、ＣＨ3ＮＨ3 +）を「ＭＡ」という。 The compound represented by ABX 3 is, for example, BaTiO 3 , MgSiO 3 , CsPbI 3 , CsPbBr 3 or (CH 3 NH 3 ) PbI 3 . Hereinafter, the methylammonium cation (that is, CH 3 NH 3+ ) is referred to as “MA”.
　ＡＢＸ3により表される化合物の類縁体は、以下の（ｉ）または（ｉｉ）の構造を有する。
　（ｉ）ＡＢＸ3により表される化合物において、Ａサイト、Ｂサイト、またはＸサイトの一部が欠損した構造（例えば、ＭＡ3Ｂｉ2Ｉ9）
　（ｉｉ）ＡＢＸ3により表される化合物において、Ａサイト、Ｂサイト、またはＸサイトが異なる複数の価数の材料によって構成される構造（例えば、Ｃｓ（Ａｇ0.5Ｂｉ0.5）Ｉ3） The analog of the compound represented by ABX 3 has the following structure (i) or (ii).
(I) In the compound represented by ABX 3 , a structure in which A site, B site, or a part of X site is deleted (for example, MA 3 Bi 2 I 9 ).
(Ii) In the compound represented by ABX 3 , the structure in which the A site, the B site, or the X site is composed of a material having a plurality of different valences (for example, Cs (Ag 0.5 Bi 0.5 ) I 3 ).
　第１ペロブスカイト化合物および第２ペロブスカイト化合物は、それぞれ独立に、２種以上のカチオンおよび１種以上の１価のアニオンを含んでいてもよい。 The first perovskite compound and the second perovskite compound may independently contain two or more kinds of cations and one or more kinds of monovalent anions.
　ペロブスカイト化合物は、実質的に、２種以上のカチオンおよび１種以上の１価のアニオンからなっていてもよい。「ペロブスカイト化合物が、実質的に、２種以上のカチオンおよび１種以上の１価のアニオンからなる」とは、ペロブスカイト化合物を構成する全元素の合計の物質量に対して、２種以上のカチオンおよび１種以上の１価のアニオンの合計の物質量が９０モル％以上であることを意味する。ペロブスカイト化合物は、２種以上のカチオンおよび１種以上の１価のアニオンからなっていてもよい。 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.
　電離放射線に対する感度を高めるために、２種以上のカチオンは、Ｐｂ2+、Ｓｎ2+、Ｇｅ2+、およびＢｉ3+からなる群より選択される少なくとも１つを含んでいてもよい。 To increase the sensitivity to ionizing radiation, 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+ .
　１価のアニオンは、例えば、ハロゲンアニオンまたは複合アニオンである。ハロゲンアニオンの例は、フッ素アニオン、塩素アニオン、臭素アニオン、またはヨウ素アニオンである。複合アニオンの例は、ＳＣＮ-、ＮＯ3 -、またはＨＣＯＯ-である。 The monovalent anion is, for example, a halogen anion or a composite anion. Examples of halogen anions are fluorine anions, chlorine anions, bromine anions, or iodine anions. Examples of composite anions are SCN-, NO 3- , or HCOO- .
　ペロブスカイト化合物は、例えば、ＡＢＸ3（Ａは１価のカチオンであり、Ｂは２価のカチオンであり、かつ、Ｘはハロゲンアニオンである）により表される化合物であってもよい。このようなペロブスカイト化合物は、電離放射線の吸収能力が高く、かつキャリア拡散長が長くなるため、電離放射線を効率よく電気信号に変換できる。 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.
　１価のカチオンの例は、有機カチオンまたはアルカリ金属カチオンである。 Examples of monovalent cations are organic cations or alkali metal cations.
　有機カチオンの例は、ＭＡ、ホルムアミジニウムカチオン（すなわち、ＮＨ2ＣＨＮＨ2 +）、フェニルエチルアンモニウムカチオン（すなわち、Ｃ6Ｈ5Ｃ2Ｈ4ＮＨ3 +）、またはグアニジニウムカチオン（すなわち、ＣＨ6Ｎ3 +）である。 Examples of 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 + ).
　アルカリ金属カチオンの例は、セシウムカチオン（すなわち、Ｃｓ+）または、ルビジウムカチオン（すなわち、Ｒｂ+）である。 Examples of alkali metal cations are cesium cations (ie, Cs + ) or rubidium cations (ie, Rb + ).
　２価の金属カチオンの例は、鉛カチオン（すなわち、Ｐｂ2+）、錫カチオン（すなわち、Ｓｎ2+）、またはゲルマニウムカチオン（すなわち、Ｇｅ2+）である。電離放射線をより効率よく変換するために、２価の金属カチオンは、Ｐｂ2+であってもよい。 Examples of divalent metal cations are lead cations (ie, Pb 2+ ), tin cations (ie, Sn 2+ ), or germanium cations (ie, Ge 2+ ). For more efficient conversion of ionizing radiation, the divalent metal cation may be Pb 2+ .
　ペロブスカイト化合物は、例えば、ＣＨ3ＮＨ3ＰｂＩ3、ＣＨ3ＣＨ2ＮＨ3ＰｂＩ3、ＨＣ（ＮＨ2）2ＰｂＩ3、ＣＨ3ＮＨ3ＰｂＢｒ3、ＣＨ3ＮＨ3ＰｂＣｌ3、ＣｓＰｂＩ3、またはＣｓＰｂＢｒ3である。 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 .
　第１ペロブスカイト化合物のバンドギャップと第２ペロブスカイト化合物のバンドギャップとの差が、０．１ｅＶ以下であってもよい。これにより、並列接続時の各積層体にかかる電位が揃うために、効率よく電荷を取り出すことができる。 The difference between the band gap of the first perovskite compound and the band gap of the second perovskite compound may be 0.1 eV or less. As a result, the electric potentials applied to each of the laminated bodies at the time of parallel connection are aligned, so that the electric charge can be efficiently taken out.
　第１ペロブスカイト化合物は、第２ペロブスカイト化合物と同一であってもよい。これにより、並列接続時の各積層体にかかる電位が揃うために、より効率よく電荷を取り出すことができる。 The first perovskite compound may be the same as the second perovskite compound. As a result, since the potentials applied to the laminated bodies at the time of parallel connection are the same, the electric charge can be taken out more efficiently.
　第１電離放射線変換層１２および第２電離放射線変換層２２の各々は、０．１μｍ以上の厚みを有していてもよい。第１電離放射線変換層１２および第２電離放射線変換層２２の各々は、０．１μｍ以上かつ１ｃｍ以下の厚みを有していてもよい。第１電離放射線変換層１２および第２電離放射線変換層２２の各々は、１００μｍ以上かつ１ｍｍ以下の厚みを有していてもよい。 Each of the first ionizing radiation conversion layer 12 and the second ionizing radiation conversion layer 22 may have a thickness of 0.1 μm or more. Each of the first ionizing radiation conversion layer 12 and the second ionizing radiation conversion layer 22 may have a thickness of 0.1 μm or more and 1 cm or less. Each of the first ionizing radiation conversion layer 12 and the second ionizing radiation conversion layer 22 may have a thickness of 100 μm or more and 1 mm or less.
　第１電離放射線変換層１２は、第２電離放射線変換層２２とは異なる厚みを有していてもよい。 The first ionizing radiation conversion layer 12 may have a thickness different from that of the second ionizing radiation conversion layer 22.
　電離放射線に対する感度を高めるために、第１電離放射線変換層１２は、第１ペロブスカイト化合物を３０モル％以上含有していてもよい。第１電離放射線変換層１２は、第１ペロブスカイト化合物を８０モル％以上含有していてもよい。第１電離放射線変換層１２は、第１ペロブスカイト化合物のみからなっていてもよい。 In order to increase the sensitivity to ionizing radiation, the first ionizing radiation conversion layer 12 may contain 30 mol% or more of the first perovskite compound. The first ionizing radiation conversion layer 12 may contain 80 mol% or more of the first perovskite compound. The first ionizing radiation conversion layer 12 may be composed of only the first perovskite compound.
　電離放射線に対する感度を高めるために、第２電離放射線変換層２２は、第２ペロブスカイト化合物を３０モル％以上含有していてもよい。第２電離放射線変換層２２は、第２ペロブスカイト化合物を８０モル％以上含有していてもよい。第２電離放射線変換層２２は、第２ペロブスカイト化合物のみからなっていてもよい。 In order to increase the sensitivity to ionizing radiation, the second ionizing radiation conversion layer 22 may contain 30 mol% or more of the second perovskite compound. The second ionizing radiation conversion layer 22 may contain 80 mol% or more of the second perovskite compound. The second ionizing radiation conversion layer 22 may be composed of only the second perovskite compound.
　電離放射線変換デバイス１００または２００において、ペロブスカイト化合物はシンチレータとして使用されてもよい。例えば、第１積層体１０において、ペロブスカイト化合物を含む第１電離放射線変換層１２と第１基板１１との間に、フォトダイオードのような光を電気信号に変換する素子を配置することで、同様の効果が得られる。この場合、第１電極１１を備えず、かつ、第１基板１１は、ガラス基板またはプラスチック基板であってもよい。 In the ionizing radiation conversion device 100 or 200, the perovskite compound may be used as a scintillator. For example, in the first laminated body 10, the same can be achieved by arranging an element such as a photodiode that converts light into an electric signal between the first ionizing radiation conversion layer 12 containing the perovskite compound and the first substrate 11. The effect of is obtained. In this case, the first electrode 11 is not provided, and the first substrate 11 may be a glass substrate or a plastic substrate.
　（第２実施形態）
　第２実施形態による電離放射線変換デバイス４００の構成について説明する。第１実施形態において説明された事項は、適宜、省略され得る。 (Second Embodiment)
The configuration of the ionizing radiation conversion device 400 according to the second embodiment will be described. The matters described in the first embodiment may be omitted as appropriate.
　図５は、第２実施形態による電離放射線変換デバイス４００の断面図を示す。 FIG. 5 shows a cross-sectional view of the ionizing radiation conversion device 400 according to the second embodiment.
　電離放射線変換デバイス４００は、第１積層体１０および第２積層体２０に加えて、第３積層体３０を備える。第２積層体２０は、第１積層体１０および第３積層体３０の間に配置されている。 The ionizing radiation conversion device 400 includes a third laminated body 30 in addition to the first laminated body 10 and the second laminated body 20. The second laminated body 20 is arranged between the first laminated body 10 and the third laminated body 30.
　第３積層体３０は、第３基板３１、第３電離放射線変換層３２、および第３電極３３を有する。第３電離放射線変換層３２は、第３基板３１および第３電極３３の間に配置されている。 The third laminated body 30 has a third substrate 31, a third ionizing radiation conversion layer 32, and a third electrode 33. The third ionizing radiation conversion layer 32 is arranged between the third substrate 31 and the third electrode 33.
　以上の構成によれば、電離放射線変換デバイス４００は、電離放射線に対してより高い感度を有する。すなわち、電離放射線変換デバイス４００は、電離放射線をより効率よく電荷に変換することができる。 According to the above configuration, the ionizing radiation conversion device 400 has higher sensitivity to ionizing radiation. That is, the ionizing radiation conversion device 400 can more efficiently convert the ionizing radiation into electric charges.
　第３基板３１および第３電極３３を構成する材料は、第１実施形態において説明された導電性材料であってもよい。 The material constituting the third substrate 31 and the third electrode 33 may be the conductive material described in the first embodiment.
　第１積層体１０、第２積層体２０、および第３積層体３０からなる群より選択される少なくとも２つの積層体が、互いに並列に電気的に接続されていてもよい。当該並列接続により、外部回路に取り出される電流値が増加するため、電離放射線変換デバイス４００の性能が向上する。 At least two laminates selected from the group consisting of the first laminate 10, the second laminate 20, and the third laminate 30 may be electrically connected in parallel with each other. The parallel connection increases the current value taken out to the external circuit, so that the performance of the ionizing radiation conversion device 400 is improved.
　本開示の電離放射線変換デバイスにおいては、電離放射線をより効率よく変換するために、例えば、４つ以上の積層体が積層されていてもよい。すなわち、本開示の電離放射線変換デバイスは、４つ以上の電離放射線変換層を含んでいてもよい。本開示の電離放射線変換デバイスにおいては、例えば、１０個以上の積層体が積層されていてもよい。すなわち、本開示の電離放射線変換デバイスは、１０個以上の電離放射線変換層を含んでいてもよい。 In the ionizing radiation conversion device of the present disclosure, for example, four or more laminated bodies may be laminated in order to convert ionizing radiation more efficiently. That is, the ionizing radiation conversion device of the present disclosure may include four or more ionizing radiation conversion layers. In the ionizing radiation conversion device of the present disclosure, for example, 10 or more laminated bodies may be laminated. That is, the ionizing radiation conversion device of the present disclosure may include 10 or more ionizing radiation conversion layers.
　（電離放射線変換デバイスの製造方法）
　以下、電離放射線変換デバイスの製造方法が説明される。 (Manufacturing method of ionizing radiation conversion device)
Hereinafter, a method for manufacturing an ionizing radiation conversion device will be described.
　電離放射線変換デバイスの製造方法は、第１基板１１を用意する第１工程、および第１基板１１上にペロブスカイト化合物を含む第１電離放射線変換層１２を形成する第２工程を含む。 The method for manufacturing an ionizing radiation conversion device includes a first step of preparing a first substrate 11 and a second step of forming a first ionizing radiation conversion layer 12 containing a perovskite compound on the first substrate 11.
　第１工程では、第１基板１１を用意する。第１基板１１は、読み出し回路を有していてもよい。複数の画素を有する場合は、画素ピッチは、例えば、１２５マイクロメートルである。 In the first step, the first substrate 11 is prepared. The first substrate 11 may have a read-out circuit. When having a plurality of pixels, the pixel pitch is, for example, 125 micrometers.
　第２工程では、第１基板１１上に第１ペロブスカイト化合物を含む第１電離放射線変換層１２が形成される。 In the second step, the first ionizing radiation conversion layer 12 containing the first perovskite compound is formed on the first substrate 11.
　第２工程では、第１ペロブスカイト化合物が目的の組成を有するように、原料が用意される。第１ペロブスカイト化合物の原料を溶媒に溶解させ、第１電離放射線変換層１２の前駆体溶液が得られる。この前駆体溶液を第１基板１１上に塗布することで、第１電離放射線変換層１２が形成される。 In the second step, a raw material is prepared so that the first perovskite compound has a desired composition. The raw material of the first perovskite compound is dissolved in a solvent to obtain a precursor solution of the first ionizing radiation conversion layer 12. By applying this precursor solution on the first substrate 11, the first ionizing radiation conversion layer 12 is formed.
　第２工程の具体例が説明される。第１ペロブスカイト化合物の原料として、例えば、０．９２ｍｏｌ／ＬのＰｂＩ2、０．１７ｍｏｌ／ＬのＰｂＢｒ2、０．８３ｍｏｌ／Ｌのヨウ化ホルムアミジニウム、０．１７ｍｏｌ／Ｌの臭化メチルアンモニウム、および０．０５ｍｏｌ／ＬのＣｓＩが用意される。これらの材料を、ジメチルスルホキシドおよびＮ，Ｎ－ジメチルホルムアミドの混合溶媒に溶解する。これにより、ペロブスカイト化合物を含む第１電離放射線変換層１２の前駆体溶液が得られる。混合溶媒に関して、ジメチルスルホキシドおよびＮ，Ｎ－ジメチルホルムアミドの混合比は、例えば、１：４（体積比）である。前駆体溶液を、例えば、インクジェット法によりに塗布することで第１電離放射線変換層１２が形成される。 Specific examples of the second step will be described. As raw materials for the first perovskite compound, for example, 0.92 mol / L PbI 2 , 0.17 mol / L PbBr 2 , 0.83 mol / L formamidinium iodide, 0.17 mol / L methylammonium bromide. , And 0.05 mol / L CsI are prepared. These materials are dissolved in a mixed solvent of dimethyl sulfoxide and N, N-dimethylformamide. As a result, a precursor solution of the first ionizing radiation conversion layer 12 containing the perovskite compound is obtained. With respect to the mixed solvent, the mixing ratio of dimethyl sulfoxide and N, N-dimethylformamide is, for example, 1: 4 (volume ratio). The first ionizing radiation conversion layer 12 is formed by applying the precursor solution, for example, by an inkjet method.
　次いで、第１電離放射線変換層１２上に第１電極１３が形成される。例えば、蒸着法により、金からなる第１電極１３が形成される。第１電極１３は、例えば、１００ナノメートルの厚みを有する。このようにして、第１積層体１０が得られる。 Next, the first electrode 13 is formed on the first ionizing radiation conversion layer 12. For example, a first electrode 13 made of gold is formed by a thin-film deposition method. The first electrode 13 has a thickness of, for example, 100 nanometers. In this way, the first laminated body 10 is obtained.
　第１積層体１０と同様にして、第２積層体２０が得られる。 The second laminated body 20 is obtained in the same manner as the first laminated body 10.
　第２積層体２０を第１積層体１０上に配置することで、電離放射線変換デバイスが得られる。以上のように、第１基板上１１に配置された第１電離放射線変換層１２を有する第１積層体１０上に、第２基板２１上に配置された第２電離放射線変換層２２を有する第２積層体２０を形成してもよい。 By arranging the second laminated body 20 on the first laminated body 10, an ionizing radiation conversion device can be obtained. As described above, the second ionizing radiation conversion layer 22 having the second ionizing radiation conversion layer 22 arranged on the second substrate 21 is placed on the first laminated body 10 having the first ionizing radiation conversion layer 12 arranged on the first substrate 11. 2 The laminated body 20 may be formed.
　（電離放射線の検出方法）
　本開示の電離放射線の検出方法は、上述の本開示の電離放射線変換デバイスを用いて、電離放射線を検出する方法である。 (Detection method of ionizing radiation)
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.
　すなわち、本開示の電離放射線の検出方法は、例えば、第１基板１１および第１基板１１上に配置された第１電離放射線変換層１２を含む第１積層体１０、および第２基板２１および第２基板２１上に配置された第２電離放射線変換層２２を含む第２積層体２０を備え、第１電離放射線変換層１２は第１ペロブスカイト化合物を含有し、第２電離放射線変換層２２は第２ペロブスカイト化合物を含有し、第２積層体２０は第１積層体１０上に積層されている、電離放射線変換デバイスを用いる。本開示の電離放射線の検出方法では、当該電離放射線変換デバイスによって、第１ペロブスカイト化合物および第２ペロブスカイト化合物に電離放射線が照射されることにより発生した電荷または光を検出する。 That is, the method for detecting ionizing radiation of the present disclosure is, for example, the first laminated body 10 including the first ionizing radiation conversion layer 12 arranged on the first substrate 11 and the first substrate 11, and the second substrate 21 and the first. The second laminated body 20 including the second ionizing radiation conversion layer 22 arranged on the two substrates 21, the first ionizing radiation conversion layer 12 contains the first perovskite compound, and the second ionizing radiation conversion layer 22 is the second. An ionizing radiation conversion device containing 2 perovskite compounds and the second laminated body 20 being laminated on the first laminated body 10 is used. In the method for detecting ionizing radiation of the present disclosure, the charge or light generated by irradiating the first perovskite compound and the second perovskite compound with ionizing radiation by the ionizing radiation conversion device is detected.
　本開示の電離放射線変換デバイスは、例えば、電離放射線検出器において利用される。 The ionizing radiation conversion device of the present disclosure is used, for example, in an ionizing radiation detector.
１０　第１積層体
１１　第１基板
１２　第１電離放射線変換層
１３　第１電極
１４　リード線
２０　第２積層体
２１　第２基板
２２　第２電離放射線変換層
２３　第２電極
３０　第３積層体
３１　第３基板
３２　第３電離放射線変換層
３３　第３電極
１００、２００、３００、４００　電離放射線変換デバイス 10 1st laminated body 11 1st substrate 12 1st ionizing radiation conversion layer 13 1st electrode 14 lead wire 20 2nd laminated body 21 2nd substrate 22 2nd ionizing radiation conversion layer 23 2nd electrode 30 3rd laminated body 31 3 Substrate 32 3rd ionizing radiation conversion layer 33 3rd electrode 100, 200, 300, 400 Ionizing radiation conversion device

Claims (10)

  1. 　第１基板および前記第１基板上に配置された第１電離放射線変換層を含む第１積層体、並びに
    　第２基板および前記第２基板上に配置された第２電離放射線変換層を含む第２積層体、を備え、
    　前記第１電離放射線変換層は、第１ペロブスカイト化合物を含有し、
    　前記第２電離放射線変換層は、第２ペロブスカイト化合物を含有し、
    　前記第１電離放射線変換層は、前記第１基板および前記第２基板の間に配置されている、
    電離放射線変換デバイス。     A first laminated body including a first substrate and a first ionizing radiation conversion layer arranged on the first substrate, and a second including a second substrate and a second ionizing radiation conversion layer arranged on the second substrate. With a laminate,
    The first ionizing radiation conversion layer contains a first perovskite compound and contains.
    The second ionizing radiation conversion layer contains a second perovskite compound and contains.
    The first ionizing radiation conversion layer is arranged between the first substrate and the second substrate.
    Ionizing radiation conversion device.
  2. 　前記第１積層体は、第１電極をさらに含み、
    　前記第２積層体は、第２電極をさらに含み、
    　前記第１電離放射線変換層は、前記第１基板および前記第１電極の間に配置され、
    　前記第２電離放射線変換層は、前記第２基板および前記第２電極の間に配置されている、
    請求項１に記載の電離放射線変換デバイス。     The first laminated body further includes a first electrode, and the first laminated body further includes a first electrode.
    The second laminated body further includes a second electrode, and the second laminated body further includes a second electrode.
    The first ionizing radiation conversion layer is arranged between the first substrate and the first electrode.
    The second ionizing radiation conversion layer is arranged between the second substrate and the second electrode.
    The ionizing radiation conversion device according to claim 1.
  3. 　前記第１ペロブスカイト化合物および前記第２ペロブスカイト化合物は、それぞれ独立に、２種以上のカチオンおよび１種以上の１価のアニオンを含有する、
    請求項１または２に記載の電離放射線変換デバイス。     The first perovskite compound and the second perovskite compound each independently contain two or more cations and one or more monovalent anions.
    The ionizing radiation conversion device according to claim 1 or 2.
  4. 　前記２種以上のカチオンは、Ｐｂ2+、Ｓｎ2+、Ｇｅ2+、およびＢｉ3+からなる群より選択される少なくとも１つを含む、
    請求項３に記載の電離放射線変換デバイス。     The two or more cations include at least one selected from the group consisting of Pb 2+ , Sn 2+ , Ge 2+ , and Bi 3+ .
    The ionizing radiation conversion device according to claim 3.
  5. 　前記第１基板、前記第１電極、前記第２基板、および前記第２電極からなる群より選択される少なくとも１つは、透光性を有しない材料から構成される、
    請求項２に記載の電離放射線変換デバイス。     At least one selected from the group consisting of the first substrate, the first electrode, the second substrate, and the second electrode is composed of a material having no translucency.
    The ionizing radiation conversion device according to claim 2.
  6. 　前記第１積層体は、前記第２積層体と並列に接続されている、
    請求項１から５のいずれか一項に記載の電離放射線変換デバイス。     The first laminated body is connected in parallel with the second laminated body.
    The ionizing radiation conversion device according to any one of claims 1 to 5.
  7. 　前記第１ペロブスカイト化合物のバンドギャップと前記第２ペロブスカイト化合物のバンドギャップとの差が、０．１ｅＶ以下である、
    請求項１から６のいずれか一項に記載の電離放射線変換デバイス。     The difference between the band gap of the first perovskite compound and the band gap of the second perovskite compound is 0.1 eV or less.
    The ionizing radiation conversion device according to any one of claims 1 to 6.
  8. 　前記第１ペロブスカイト化合物は、前記第２ペロブスカイト化合物と同一である、
    請求項１から７のいずれか一項に記載の電離放射線変換デバイス。     The first perovskite compound is the same as the second perovskite compound.
    The ionizing radiation conversion device according to any one of claims 1 to 7.
  9. 　第１基板および前記第１基板上に配置された第１電離放射線変換層を含む第１積層体、並びに
    　第２基板および前記第２基板上に配置された第２電離放射線変換層を含む第２積層体、を備え、
    　前記第１電離放射線変換層は、第１ペロブスカイト化合物を含有し、
    　前記第２電離放射線変換層は、第２ペロブスカイト化合物を含有し、
    　前記第２積層体は、前記第１積層体上に積層されている、
    電離放射線変換デバイス、を用いて、前記第１ペロブスカイト化合物および前記第２ペロブスカイト化合物に電離放射線が照射されることにより発生した電荷または光を検出することを含む、
    電離放射線の検出方法。     A first laminated body including a first substrate and a first ionizing radiation conversion layer arranged on the first substrate, and a second including a second substrate and a second ionizing radiation conversion layer arranged on the second substrate. With a laminate,
    The first ionizing radiation conversion layer contains a first perovskite compound and contains.
    The second ionizing radiation conversion layer contains a second perovskite compound and contains.
    The second laminated body is laminated on the first laminated body.
    The ionizing radiation conversion device, comprising detecting the charge or light generated by the irradiation of the first perovskite compound and the second perovskite compound with ionizing radiation.
    How to detect ionizing radiation.
  10. 　第１基板上に配置された第１電離放射線変換層を含む第１積層体上に、第２基板上に配置された第２電離放射線変換層を含む第２積層体を形成すること、を含み、
    　前記第１電離放射線変換層は、第１ペロブスカイト化合物を含有し、
    　前記第２電離放射線変換層は、第２ペロブスカイト化合物を含有する、
    電離放射線変換デバイスの製造方法。     Including forming a second laminated body including a second ionizing radiation conversion layer arranged on a second substrate on a first laminated body including a first ionizing radiation conversion layer arranged on a first substrate. ,
    The first ionizing radiation conversion layer contains a first perovskite compound and contains.
    The second ionizing radiation conversion layer contains a second perovskite compound.
    How to manufacture an ionizing radiation conversion device.
PCT/JP2021/025295 2020-08-06 2021-07-05 Ionizing radiation conversion device, method for detecting ionizing radiation, and method for producing ionizing radiation conversion device WO2022030156A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2022541164A JPWO2022030156A1 (en) 2020-08-06 2021-07-05

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2020134153 2020-08-06
JP2020-134153 2020-08-06

Publications (1)

Publication Number Publication Date
WO2022030156A1 true WO2022030156A1 (en) 2022-02-10

Family

ID=80119739

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2021/025295 WO2022030156A1 (en) 2020-08-06 2021-07-05 Ionizing radiation conversion device, method for detecting ionizing radiation, and method for producing ionizing radiation conversion device

Country Status (2)

Country Link
JP (1) JPWO2022030156A1 (en)
WO (1) WO2022030156A1 (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019520565A (en) * 2016-06-08 2019-07-18 コーニンクレッカ フィリップス エヌ ヴェＫｏｎｉｎｋｌｉｊｋｅ Ｐｈｉｌｉｐｓ Ｎ．Ｖ． Analytical grating for phase contrast imaging and / or dark field imaging
JP2019526782A (en) * 2016-06-07 2019-09-19 コーニンクレッカ フィリップス エヌ ヴェＫｏｎｉｎｋｌｉｊｋｅ Ｐｈｉｌｉｐｓ Ｎ．Ｖ． Direct photon conversion detector
WO2020003603A1 (en) * 2018-06-26 2020-01-02 国立大学法人京都大学 Radiation detector and method for manufacturing radiation detector

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019526782A (en) * 2016-06-07 2019-09-19 コーニンクレッカ フィリップス エヌ ヴェＫｏｎｉｎｋｌｉｊｋｅ Ｐｈｉｌｉｐｓ Ｎ．Ｖ． Direct photon conversion detector
JP2019520565A (en) * 2016-06-08 2019-07-18 コーニンクレッカ フィリップス エヌ ヴェＫｏｎｉｎｋｌｉｊｋｅ Ｐｈｉｌｉｐｓ Ｎ．Ｖ． Analytical grating for phase contrast imaging and / or dark field imaging
WO2020003603A1 (en) * 2018-06-26 2020-01-02 国立大学法人京都大学 Radiation detector and method for manufacturing radiation detector

Also Published As

Publication number Publication date
JPWO2022030156A1 (en) 2022-02-10

Similar Documents

Publication Publication Date Title
He et al. Detecting ionizing radiation using halide perovskite semiconductors processed through solution and alternative methods
Wei et al. Halide lead perovskites for ionizing radiation detection
Wu et al. Metal halide perovskites for X-ray detection and imaging
JP6960907B2 (en) Radiation detector and manufacturing method of radiation detector
Kim et al. Printable organometallic perovskite enables large-area, low-dose X-ray imaging
Heiss et al. Perovskites target X-ray detection
US10656290B2 (en) Direct photon conversion detector
US10690786B2 (en) X-ray detector and manufacturing method thereof
TWI470262B (en) Radiographic detector formed on scintillator
JP6535271B2 (en) Radiation detector and method of manufacturing radiation detector
Wu et al. Halide Perovskite: A Promising Candidate for Next‐Generation X‐Ray Detectors
JPH01165984A (en) Apparatus for converting video to electric signal
CN112531116B (en) Perovskite ultra-fast X-ray detector and preparation method thereof
US20180246227A1 (en) Detection panel and detection apparatus
KR20170029371A (en) X-ray detector
KR101595429B1 (en) Optical semiconductor device having transition metal dechalcogenides
KR101653440B1 (en) Organic device for detecting x-ray image based on coplanar electrode structure and thereof manufacture method
WO2022030156A1 (en) Ionizing radiation conversion device, method for detecting ionizing radiation, and method for producing ionizing radiation conversion device
WO2022030157A1 (en) Ionizing radiation conversion device and ionizing radiation detection method
WO2022030158A1 (en) Ionizing radiation conversion device and ionizing radiation detection method
WO2022030141A1 (en) Ionizing radiation conversion device, method for manufacturing same, and ionizing radiation detection method
JP2022030278A (en) Ionizing radiation conversion device, manufacturing method thereof, and detection method for ionizing radiation
Tan et al. Self-powered X-ray detector based on lead halide perovskites under electric field poling effect
WO2022030154A1 (en) Ionizing radiation conversion device and method for detecting ionizing radiation
EP3730972A1 (en) Radiation detection device for detecting gamma or x-ray radiation quanta

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21852676

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2022541164

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21852676

Country of ref document: EP

Kind code of ref document: A1