WO1998036291A1 - Dispositif de detection de radiations et son procede de production - Google Patents
Dispositif de detection de radiations et son procede de production Download PDFInfo
- Publication number
- WO1998036291A1 WO1998036291A1 PCT/JP1998/000551 JP9800551W WO9836291A1 WO 1998036291 A1 WO1998036291 A1 WO 1998036291A1 JP 9800551 W JP9800551 W JP 9800551W WO 9836291 A1 WO9836291 A1 WO 9836291A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- light receiving
- resin
- protective film
- film
- radiation
- Prior art date
Links
- 230000005855 radiation Effects 0.000 title claims abstract description 45
- 238000001514 detection method Methods 0.000 title claims abstract description 11
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- 239000011347 resin Substances 0.000 claims abstract description 89
- 230000001681 protective effect Effects 0.000 claims abstract description 59
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- 238000000576 coating method Methods 0.000 claims description 29
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- 239000010408 film Substances 0.000 description 111
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
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- VRBFTYUMFJWSJY-UHFFFAOYSA-N 28804-46-8 Chemical compound ClC1CC(C=C2)=CC=C2C(Cl)CC2=CC=C1C=C2 VRBFTYUMFJWSJY-UHFFFAOYSA-N 0.000 description 1
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- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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- 229910052814 silicon oxide Inorganic materials 0.000 description 1
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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
- G01T1/20—Measuring radiation intensity with scintillation detectors
-
- 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
- G01T1/20—Measuring radiation intensity with scintillation detectors
- G01T1/2018—Scintillation-photodiode combinations
- G01T1/20188—Auxiliary details, e.g. casings or cooling
- G01T1/20189—Damping or insulation against damage, e.g. caused by heat or pressure
Definitions
- the present invention relates to a radiation detection element, and more particularly to a radiation detection element having a large-area light receiving unit used for medical X-ray photography and the like.
- a typical radiation detection element has a structure in which scintillation light is arranged on a one-dimensional or two-dimensionally arranged photodetector, and incident radiation is converted into light by scintillation and detected. ing.
- CsI a typical material of scintillator
- a hygroscopic material that absorbs and dissolves water vapor (moisture) in the air.
- the moisture sealing layer of the moisture-proof barrier is formed by coating a silicone coating material or the like in a liquid state on the scintillating layer, or inside the window material installed on the light receiving surface side of the radiation detecting element.
- a method of fixing the moisture sealing layer by disposing the window material on the scintillation layer after applying the silicone potting material or the like and before drying the moisture sealing layer is disclosed.
- an object of the present invention is to provide a radiation detecting element having a protective film that is uniform and easy to manufacture for moisture prevention in scintillation and a method of manufacturing the same.
- the radiation detection element of the present invention comprises: (1) a plurality of light-receiving elements arranged one-dimensionally or two-dimensionally on a substrate to form a light-receiving section, and each row or each row of the light-receiving section; A light-receiving element array in which a plurality of bonding pads electrically connected to the light-receiving elements in the row are arranged outside the light-receiving section; and (2) converting the radiation deposited on the light-receiving elements in the light-receiving section into visible light.
- the resin film covers at least the scintillation layer, and reaches at least the resin frame to at least the bonding pad portion.
- Exposing radiation Characterized in that it comprises a transparent moisture-resistant protective film.
- the incident radiation is converted to visible light in the scintillation layer.
- the scintillation layer has the property of deteriorating due to moisture absorption
- the scintillation layer is covered with a moisture-resistant protective film, and the moisture-resistant protective film is formed of a light receiving element array by a resin frame. Due to its close contact with the sea, the scintillation layer is completely sealed, isolated from the outside air, and protected from water vapor. Further, the bonding pad portion for connection to an external circuit is exposed.
- This resin frame is preferably formed in a rectangular shape surrounding the scintillation layer or a rectangular shape surrounding one or a plurality of bonding pad regions.
- a coating resin for covering the edge of the moisture-resistant protective film along the resin frame may be further provided.
- the edge of the moisture-resistant protective film is sandwiched from above and below by the resin frame and the covering resin, and is firmly bonded.
- the method for manufacturing a radiation detecting element includes: (1) forming a light receiving section by arranging a plurality of light receiving elements one-dimensionally or two-dimensionally on a substrate, and forming a light receiving section in each row or each column of the light receiving section; A first step of depositing a scintillator layer for converting radiation into visible light on a light receiving element of a light receiving section of a light receiving element array in which a plurality of bonding pads electrically connected to the light receiving section are arranged outside the light receiving section; (2) a second step of forming one or more closed frame-shaped resin frames for separating the scintillating layer and the bonding pad portion with resin on the light receiving element array; and (3) forming the entire light receiving element array.
- a fourth step of forming a radiation-permeable moisture-resistant protective film 5)
- the adhesion between the scintillation layer and the organic film is improved, and a uniform film is formed.
- Form a moisture-resistant protective film Then, by removing the protective film from the bonding pad portion, the bonding pad portion is reliably exposed.
- the resin frame formed under the protective film provides a margin for the cutting depth of the cutter when cutting the protective film. Further, the resin frame allows the edge of the protective film to be in close contact with the substrate, thereby ensuring sealing.
- a sixth step of covering and bonding the edge of the moisture-resistant protective film with the resin along the resin frame may be further provided.
- the edge of the moisture-resistant protective film is firmly bonded to the resin frame by being sandwiched between the resin and the resin frame.
- FIG. 1 is a top view of one embodiment of the present invention
- FIG. 2 is an enlarged cross-sectional view taken along line A-—.
- FIG. 3 to FIG. 11 are diagrams showing the manufacturing process of the embodiment according to FIG. 1 and FIG.
- FIG. 12 is a top view of another embodiment of the present invention
- FIG. 13 is an enlarged sectional view taken along line BB of FIG. BEST MODE FOR CARRYING OUT THE INVENTION
- FIG. 1 is a top view of an embodiment of the present invention
- FIG. 2 is an enlarged cross-sectional view taken along line AA of an outer peripheral portion thereof.
- Light receiving elements 2 that perform photoelectric conversion are two-dimensionally arranged on an insulating substrate, for example, a glass substrate 1 to form a light receiving section.
- the light receiving element 2 is composed of a photodiode (PD) and a thin film transistor (TFT) made of amorphous silicon.
- PD photodiode
- TFT thin film transistor
- Each of the light receiving elements 2 in each row or each column is electrically connected by a signal line 3 for signal reading.
- a plurality of bonding pads 4 for taking out a signal to an external circuit are arranged along the outer periphery of the substrate 1, for example, along two adjacent sides, and are connected via the signal line 3. Are electrically connected to the plurality of light receiving elements 2.
- an insulating passivation film 5 is formed on the light receiving element 2 and the signal line 3. It is preferable to use silicon nitride or silicon oxide for the nomination film 5. On the other hand, the bonding pad 4 is exposed for connection with an external circuit.
- this substrate and the circuit portion on the substrate are referred to as a light receiving element array 6.
- a scintillator 7 having a columnar structure for converting incident radiation into visible light is formed on the light receiving portion of the light receiving element array 6, a scintillator 7 having a columnar structure for converting incident radiation into visible light is formed.
- Various materials can be used for the scintillator 7, but a T 1 -doped C sI or the like having good luminous efficiency is preferable.
- a resin frame 8 made of a resin formed in a long and narrow frame shape is arranged at an inner position of the bonding pad so as to surround the light receiving portion of the light receiving element array 6.
- silicone resin such as KJR651 or KE4987 made by Shin-Etsu Chemical, TSE3997 made by Toshiba Silicon, DYMAX625T made by Sumitomo 3M, etc. can be used. preferable.
- the first organic film 9 and the second organic film 11 are made of polyparaxylylene resin (manufactured by ThreeBond, trade name Parylene), especially polyparachloroxylylene (manufactured by the company, trade name Parylene C). Is preferred.
- Norylene coating film has extremely low water vapor and gas permeability, high water repellency, high chemical resistance, excellent electrical insulation even in thin films, and is transparent to radiation and visible light. It has excellent features suitable for the organic films 9 and 11. Details of the coating by Parylene are described in ThreeBond's Technical News (issued on September 23, 1992), and its features are described here.
- Parylene can be coated by chemical vapor deposition (CVD), which is deposited on a support in a vacuum, similar to vacuum deposition of metals. This involves pyrolyzing the raw material P-xylene and quenching the product in an organic solvent such as toluene or benzene to obtain diparaxylylene called dimer. It consists of a process of generating xylylene gas and a process of adsorbing and polymerizing the generated gas on a material to polymerize and form a polyparaxylylene film having a molecular weight of about 500,000.
- CVD chemical vapor deposition
- the pressure at the time of parylene deposition is 0.1 to 0.2 Torr, which is higher than the pressure at the time of metal vacuum deposition of 0.01 Torr.
- a thin film with a thickness of 0.2 ⁇ m can be formed to a uniform thickness without pinholes, and it can be used for sharp corners, edges, and narrow gaps on the order of microns, which were impossible with liquids. Coating is also possible.
- heat treatment is not required during coating and coating can be performed at a temperature close to room temperature, no mechanical stress or thermal distortion due to curing occurs, and coating stability is excellent.
- coatings on most solid materials are possible.
- the inorganic film 10 is transparent to X-rays, various materials such as transparent, opaque, and reflective materials can be used for visible light, and an oxide film of Si, Ti, Cr, or gold can be used. Metal thin films of silver, aluminum, etc. can be used.
- a film that reflects visible light because it has an effect of preventing the fluorescence generated in the scintillator from leaking out and increasing the sensitivity.
- A1 which is easy to mold, will be described.
- a 1 itself is easily corroded in the air, but the inorganic film 10 is protected from corrosion because it is sandwiched between the first organic film 9 and the second organic film 11.
- the protective film 12 is formed by the above-described parylene coating. However, since the protective film 12 is formed by the CVD method, it is formed so as to cover the entire surface of the light receiving element array 6. Therefore, in order to expose the bonding pad 4, it is necessary to cut the protective film 12 formed by parylene coating inside the bonding pad 4 and remove the external protective film 12. As will be described later, by cutting the protective film 12 near the center of the frame portion of the resin frame 8, the outer peripheral portion of the protective film 12 is fixed by the resin frame 8, so that the protective film 12 peels off from the outer peripheral portion. Can be prevented. Further, the outer peripheral portion of the protective film 12 is coated with a coating resin 13 together with a resin frame 8 thereunder.
- the coating resin 13 is a resin having good adhesion to the protective film 12 and the resin frame 8, for example, WORLD ROCK No. 801 -SET 2 (70, OOO) manufactured by Kyoritsu Chemical Industry Co., Ltd., which is an acryl-based adhesive. cP) is preferred.
- the resin adhesive by ultraviolet irradiation of 10 OmW / cm 2 and cured at about 20 seconds, the cured film has flexibility and sufficient strength, moisture resistance, resistance to water, resistance to electric tactile properties, is excellent in migration resistance It has good adhesiveness to various materials, particularly to glass, plastics, and the like, and has preferable characteristics as the coating resin 13.
- the same silicone resin as the resin frame 8 may be used.
- the same acryl-based adhesive as that of the coating resin 13 may be used for the resin frame 8.
- a resin frame 8 is formed along the outer periphery of the light receiving unit. It is formed in an elongated frame shape with a height of 0.6 mm.
- an automatic XY coating device such as AutoShooter-3 manufactured by Iwashita Engineering may be used.
- Rough surface treatment includes scoring or forming many small depressions on the surface.
- the first organic film 9 is formed by wrapping the entire substrate with a 10 m-thick parylene by the CVD method. Although there is a gap in the columnar crystal of CsI, parylene penetrates into this narrow gap to some extent, so that the first organic film 9 is in close contact with the seven layers of scintillation. In addition, the parylene coating provides a precise thin film coating with a uniform thickness on the uneven surface of the scintillation layer. Further, as described above, parylene CVD formation can be performed at a lower vacuum than at the time of metal deposition and at room temperature, so that processing is easy.
- an Al film having a thickness of 0.2 ⁇ m is laminated on the surface of the first organic film 9 on the incident surface side by an evaporation method to form an inorganic film 10.
- the second organic film 11 is formed by covering the entire surface of the substrate with a thickness of 10 ⁇ m again by the CVD method (see FIG. 8). The second organic film 11 prevents the inorganic film 10 from deteriorating due to corrosion.
- the protective film 12 thus formed is cut along the longitudinal direction of the resin frame 8 with a cut 14 (see FIG. 9). Since the convex portion is formed in the resin frame 8, it is easy to confirm the cut position, and there is room for inserting the cut 14 by the thickness of the resin frame 8. Therefore, there is no danger of damaging the signal line 3 under the resin frame 8, processing is simplified, and the product yield is improved. Then, the protective film 12 on the outer side and the back side of the incident surface is removed from the cut portion to expose the bonding pad 4 for connection to an external circuit (see FIG. 10). Thereafter, a coating resin 13 made of an acrylic resin is coated so as to cover the outer peripheral portion of the protective film 12 and the exposed resin frame 8, and the coating resin 13 is cured by ultraviolet irradiation (see FIG. 11).
- the passivation film 5 and the first organic film 9 generally have poor adhesion.
- the first organic film 9 is formed of a resin frame 8 between the first organic film 9 and the passivation film 5 because the resin frame 8 is in close contact with both.
- the frame 8 makes close contact with the passive film 5.
- the protective film 12 is in close contact with the light receiving element array 12 via the resin frame 8.
- the protection film 12 includes the first organic film 9. Since the protective film 12 is sandwiched and fixed between the resin frame 8 and the coating resin 13, the adhesion of the protective film 12 on the light receiving element array 6 is further improved, which is preferable.
- the protective film 12 seals the scintillator 7, it is possible to reliably prevent moisture from entering the scintillator 7, and to prevent a reduction in the resolution of the element due to the moisture absorption deterioration of the scintillator 7. it can.
- X-rays (radiation) incident from the incident surface side pass through all of the first organic film 9, the inorganic film 10, and the second organic film 11, and reach the scintillator 7. These X-rays are absorbed by the scintillator and emit visible light proportional to the amount of X-rays. Of the emitted visible light, visible light that has traveled in the direction opposite to the X-ray incidence direction passes through the second organic film 11 and is reflected by the inorganic film 10. For this reason, almost all of the visible light generated in the scintillator 7 enters the light receiving element 2 via the passivation film 5. For this reason, efficient detection is possible.
- each light receiving element 2 an electric signal corresponding to the amount of this visible light is generated by photoelectric conversion and accumulated for a certain period of time.
- the amount of this visible light is In other words, the electrical signals accumulated in each light receiving element 2 correspond to the amount of incident X-rays, and an image signal corresponding to an X-ray image is obtained.
- This image signal stored in the light receiving element 2 is sequentially read out from the bonding pad 4 via the signal line 3, transferred to the outside, and processed by a predetermined processing circuit to display an X-ray image. be able to.
- the structure in which the inorganic film 10 is sandwiched between the first organic films 9 and 11 made of parylene as the protective film 12 has been described.
- the first organic film 9 and the second The material of the organic film 11 may be different.
- the second organic film 11 itself may not be provided.
- the resin frame 8 and the covering resin 13 are formed on the passivation film 5 outside the two light receiving elements of the light receiving element array 6, but the light receiving element 2 and the bonding pad 4 It is difficult to form the resin frame 8 at the boundary when the two are close to each other.
- the positions of the resin frame 8 and the coating resin 13 are shifted toward the light receiving element 2.
- the scintillator 7 is not formed on the entire surface of the light receiving element 2 but on the light receiving element 2 in an effective screen area excluding pixels near the bonding pad 4.
- the protection film 12 is formed so as to cover the entire layer of the formed scintillator 7 and reach the resin frame 8.
- the protective film 12 is cut along the longitudinal direction of the resin frame 8, the protective film 12 outside the effective screen area is removed, and the edge of the protective film 12 along the resin frame 8 is coated with the resin 13. Just coat it.
- the pixels in the vicinity of the bonding pad 4 are covered with the resin frame 8 and the covering resin 13 or have no scintillator 7 on the front surface, so that the sensitivity to the radiation is reduced.
- the number of effective pixels and the effective screen area of light receiving element 2 are reduced because they cannot be used.However, if light receiving element 2 has a large screen and a large number of pixels, the ratio of invalid pixels is small, and depending on the element configuration Is easy to manufacture There is a
- FIG. 12 is a top view of the radiation detecting element of this embodiment
- FIG. 13 is an enlarged cross-sectional view taken along the line BB.
- the basic configuration of this element is the same as the element of the embodiment shown in FIGS. 1 and 2, and only the differences will be described below.
- the protective film 12 is formed on the front surface on the light receiving surface side and the back surface side of the light receiving element array 6, and only the bonding array 4 is exposed.
- a resin frame 8 is formed so as to surround the exposed bonding array 4, and a coating resin 13 is coated on the resin frame 8 along the boundary (edge) of the protective film 12.
- the bonding pad 4 is reliably exposed, and the protective film 12 is securely adhered to the light receiving element array 6 by the resin frame 8 and the coating resin 13. Is sealed to prevent deterioration due to moisture absorption.
- a so-called front-incident type radiation detecting element in which radiation enters from the scintillating side on the light receiving element has been described.
- the present invention provides a so-called back-injecting type in which radiation enters from the substrate side. It is also possible to apply to the type radiation detecting element.
- Such a back-illuminated radiation detecting element can be used as a high-energy radiation detecting element.
- a protective film made of parylene or the like is formed over the scintillator to protect the scintillator having a high hygroscopic property. Since the resin layer is bonded to the light receiving element array, the scintillation layer is sealed. In particular, since peeling from the edge of the protective film is prevented, the moisture resistance is improved. Furthermore, if this edge is covered with a coating resin, the sealing performance is further improved and the moisture resistance is increased.
- the unnecessary portion is removed after the formation of the protective film, it is easier to form the protective film in a uniform state as compared with the case where the protective film is formed only on the necessary portion. Is surely exposed. Further, since the protective film penetrates into the gaps between the columnar crystals of the scintillating layer, the adhesion between the protective film and the scintillating layer increases. In addition, since there is enough cutting margin for the thickness of the resin layer at the time of cutting, the signal line for reading out the detection signal is not damaged without increasing the precision of the cutting tool, and the product yield is improved.
- the radiation detecting element of the present invention is applicable particularly to a large-area radiation imaging system used in medical and industrial X-ray photography. In particular, it can be used for chest X-ray photography, etc., instead of the widely used X-ray film at present.
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- Physics & Mathematics (AREA)
- 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)
Description
Claims
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU58788/98A AU5878898A (en) | 1997-02-14 | 1998-02-12 | Radiation detection device and method of producing the same |
EP98902186A EP0903590B1 (en) | 1997-02-14 | 1998-02-12 | Radiation detection device and method of producing the same |
CA002260041A CA2260041C (en) | 1997-02-14 | 1998-02-12 | Radiation detection device and method of producing the same |
JP10535567A JP3077941B2 (ja) | 1997-02-14 | 1998-02-12 | 放射線検出素子及びその製造方法 |
KR10-1998-0709606A KR100514547B1 (ko) | 1997-02-14 | 1998-02-12 | 방사선검출소자및그제조방법 |
DE69803344T DE69803344T2 (de) | 1997-02-14 | 1998-02-12 | Vorrichtung zum nachweis von strahlung und verfahren zu ihrer herstellung |
US09/247,299 US6262422B1 (en) | 1997-02-14 | 1999-02-10 | Radiation detection device and method of making the same |
US10/870,409 USRE40291E1 (en) | 1997-02-14 | 2004-06-17 | Radiation detection device and method of making the same |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3051097 | 1997-02-14 | ||
JP9/30510 | 1997-02-14 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/247,299 Continuation-In-Part US6262422B1 (en) | 1997-02-14 | 1999-02-10 | Radiation detection device and method of making the same |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1998036291A1 true WO1998036291A1 (fr) | 1998-08-20 |
Family
ID=12305818
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP1998/000551 WO1998036291A1 (fr) | 1997-02-14 | 1998-02-12 | Dispositif de detection de radiations et son procede de production |
Country Status (9)
Country | Link |
---|---|
US (2) | US6262422B1 (ja) |
EP (1) | EP0903590B1 (ja) |
JP (1) | JP3077941B2 (ja) |
KR (1) | KR100514547B1 (ja) |
CN (3) | CN1133881C (ja) |
AU (1) | AU5878898A (ja) |
CA (1) | CA2260041C (ja) |
DE (1) | DE69803344T2 (ja) |
WO (1) | WO1998036291A1 (ja) |
Cited By (27)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2000063722A1 (fr) * | 1999-04-16 | 2000-10-26 | Hamamatsu Photonics K.K. | Panneau scintillateur et capteur d'image radiologique |
JP2001053327A (ja) * | 1999-06-11 | 2001-02-23 | Koninkl Philips Electronics Nv | センサ |
WO2001075478A1 (en) * | 2000-03-30 | 2001-10-11 | Matsushita Electric Industrial Co., Ltd. | Radiation detector and method of manufacture thereof |
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TWI780129B (zh) * | 2017-03-22 | 2022-10-11 | 日商富士軟片股份有限公司 | 放射線檢測器及放射線圖像攝影裝置 |
WO2018173894A1 (ja) * | 2017-03-22 | 2018-09-27 | 富士フイルム株式会社 | 放射線検出器及び放射線画像撮影装置 |
US11644581B2 (en) | 2019-12-25 | 2023-05-09 | Hamamatsu Photonics K.K. | Radiation detector and method for manufacturing radiation detector |
US11762110B2 (en) | 2019-12-25 | 2023-09-19 | Hamamatsu Photonics K.K. | Radiation detector and method for manufacturing radiation detector |
JP2020177033A (ja) * | 2020-08-06 | 2020-10-29 | 浜松ホトニクス株式会社 | 放射線検出器 |
Also Published As
Publication number | Publication date |
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AU5878898A (en) | 1998-09-08 |
KR100514547B1 (ko) | 2005-12-14 |
DE69803344T2 (de) | 2002-08-14 |
EP0903590A1 (en) | 1999-03-24 |
CA2260041A1 (en) | 1998-08-20 |
KR20000065226A (ko) | 2000-11-06 |
USRE40291E1 (en) | 2008-05-06 |
DE69803344D1 (de) | 2002-02-28 |
EP0903590B1 (en) | 2002-01-02 |
JP3077941B2 (ja) | 2000-08-21 |
CN1220732A (zh) | 1999-06-23 |
CN1256596C (zh) | 2006-05-17 |
EP0903590A4 (en) | 1999-07-21 |
CN1844953B (zh) | 2012-06-27 |
CN1844953A (zh) | 2006-10-11 |
CN1133881C (zh) | 2004-01-07 |
CN1501095A (zh) | 2004-06-02 |
CA2260041C (en) | 2001-10-09 |
US6262422B1 (en) | 2001-07-17 |
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