WO2002050211A1 - Oxide phosphor and radiation detector using it, and x-ray ct device - Google Patents
Oxide phosphor and radiation detector using it, and x-ray ct device Download PDFInfo
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- WO2002050211A1 WO2002050211A1 PCT/JP2001/011176 JP0111176W WO0250211A1 WO 2002050211 A1 WO2002050211 A1 WO 2002050211A1 JP 0111176 W JP0111176 W JP 0111176W WO 0250211 A1 WO0250211 A1 WO 0250211A1
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Definitions
- the present invention relates to a radiation detector for detecting X-rays, ⁇ -rays and the like, particularly an oxide phosphor suitable for a radiation detector such as an X-ray CT device and a positive-port camera, and a radiation detector using the same. And X-ray CT equipment. Background technology '' '
- xenon Gasuchi Enba, bismuth germanate (BG0 single crystal) and a combination of the optoelectronic ⁇ tube, Csl: T1 monocrystalline or CdW0 4 single crystal and photo Diode combinations have been used.
- rare-earth phosphors with high radiation-to-light conversion efficiency have been developed, and radiation detectors combining such phosphors with photodiodes have been put into practical use.
- the rare-earth phosphor is a rare-earth oxide or rare-earth oxysulfide as a base material to which an activator, which is a luminescent component, is added, and is described as a rare-earth oxide phosphor in JP-A-3-50991 or the like.
- the characteristics required for scintillator materials used in radiation detectors include high luminous efficiency, short afterglow, and high X-ray stopping power. Some of the above phosphors have high luminous efficiency, but the afterglow time is relatively long. In applications of X-ray CT equipment, if the afterglow of the scintillator used in the X-ray detector is large, the obtained information becomes unclear in the time axis direction. Of the many characteristics of a conventional scintillator materials, but a problem that afterglow is large has been made, the phosphor described in WO W099Z33934 (GdhCe ⁇ sAls- y Ga y 0 12 (0.
- An object of the present invention is to solve the problem of the instability of the scintillator characteristics, which is a drawback of the phosphor having the composition of Gd Cex Al ⁇ GayC ⁇ , and to eliminate the problem of X-rays even in the case of a thick plate or a block shape suitable for mass production.
- Another object of the present invention is to provide a phosphor having high luminous efficiency, extremely low afterglow, and excellent reproducibility of characteristics, and using the phosphor as a scintillator of a radiation detector provided with a photodetector. Accordingly, an object is to obtain a low afterglow radiation detector having a large optical output.
- a further object of the present invention is to provide a high-resolution, high-quality tomographic image by applying this radiation detector to an X-ray CT apparatus. Disclosure of the invention
- An oxide comprising at least Gd, Ce, Al, Ga, and 0, wherein the crystal structure of the oxide is a garnet structure, and (Gd + Ce) I (Al + Ga + Gd +
- the atomic ratio of Ce) is greater than 0.375 and 0.44 or less, and the atomic ratio of Ce / (Ce + Gd) is 0.0005 or more and 0.02 or less.
- the oxide phosphor of (1) and the sintered body thereof are larger than 0 and smaller than 1.0.
- the oxide phosphor of (1) or (2) and the sintered body thereof have a perovskite structure as an impurity phase.
- the intensity of the main diffraction line of the perovskite structure measured by X-ray diffraction measurement is 50% of the intensity of the main diffraction line of the garnet structure. % Or less.
- the present invention provides a radiation detector comprising a ceramic scintillator and a photodetector for detecting light emission of the scintillator, wherein the ceramic scintillator has the oxide fluorescence described in any one of (1) to (4) above.
- a body-based radiation detector comprising a ceramic scintillator and a photodetector for detecting light emission of the scintillator, wherein the ceramic scintillator has the oxide fluorescence described in any one of (1) to (4) above.
- the present invention provides an X-ray source, an X-ray detector placed opposite to the X-ray source, holding the X-ray source and the X-ray detector, and driven to rotate around the subject.
- An X-ray CT apparatus comprising: a rotating disk; and image reconstruction means for reconstructing a tomographic image of the subject based on the intensity of the X-rays detected by the X-ray detector.
- An X-ray CT apparatus using the radiation detector described above as an output device is provided.
- Phosphor of the present invention previously phosphor 1 ⁇ 2 described in WO W099Z33934 of the international application by the present applicant - x Ce x) 3 Al 5 - y Ga y 0 12 (0.0005 ⁇ x ⁇ 0.02, 0 ⁇ y ⁇ 5) is an oxide phosphor containing Gd, Al, and Ga as basic elements and Ce as a light-emitting component. It is characterized by having a non-stoichiometric composition, while the one described is a stoichiometric phosphor.
- Figure 3 shows the composition of the (Gd, Ce) -A1-Ga ternary system.
- the phosphor of the present invention has a non-stoichiometric composition region K indicated by hatching in FIG.
- the atomic ratio of (Gd + Ce) / (A1 + Ga + Gd + Ce) is greater than 0.375 and 0.44 or less
- the atomic ratio of Ce / (Ce + Gd) is not less than 0.0005 and not more than 0.02.
- the afterglow in the scintillator characteristics increases to about 100 times, and the luminous output decreases by 30% or more. I do.
- the atomic ratio of (Gd + Ce) / (A1 + Ga + Gd + Ce) exceeds 0.44, 300 ms after shutting down the excitation source.
- the decay rate of afterglow is 4 X is a 10 5 degree and stability to low values, the perovskite structure Gd (Ga, Al) 0 3 phase as a secondary phase in the host crystal of garnet structure produces more than 50%, light output of about 40% Deterioration results.
- the atomic ratio of Ga / (Al + Ga) is preferably greater than 0 and less than 1.0. If the atomic ratio is outside the above range, sufficient light emission intensity cannot be obtained even if Ce is doped. .
- Figure 4 shows the garnet structure of the theoretical stoichiometry represented by (Gd ⁇ Ce ⁇ Als-yGayOu.
- the ionic radii of Gd and Ce are 0.97A and 1.07A, respectively.
- Al and Ga are 0.5 lA and 0.62 A, respectively.
- Stoichiometric composition (Gd, Ce): (Al, Ga) 3: A case of non-stoichiometric composition shifted in composition from 5 .
- GdA10 perovskite structure 3 Is formed as a heterophase in the garnet structure, which is the mother crystal.
- the Gd component is less than the stoichiometric composition, that is, when the (Al, Ga) component is in excess of the stoichiometric composition, the A1 or Ga ion having a small ionic radius becomes a Gd site. To form a garnet structure.
- the change in the characteristics of the light emission output and the afterglow can be explained as follows. If the Gd component is excessive, a non-luminescent non-emission phase (absorber) is generated in the mother crystal with an increase in the Gd component, so that the luminescence output gradually decreases. And to force, since the secondary phase GdA10 3 not involved in light emission, have little effect on the decay characteristic.
- the Gd component is less than the theoretical composition, the crystal structure remains the garnet structure, but the A1 or Ga ion substituted for the Gd site is an impurity ion in the garnet crystal and therefore has a lower energy band in the crystal. The structure is deformed, Create an energy level that allows child transitions. Therefore, it is considered that afterglow increases, the energy transfer efficiency from the host crystal to Ce 3+ , which is the emission center, decreases, and the emission output also decreases.
- the effect of the composition shift that occurs during sintering is preliminarily made by excessively adding the (Gd + Ce) component of the phosphor powder composition within a range where good scintillator characteristics can be obtained. This makes it possible to manufacture phosphor elements with low afterglow, even in thick sintered bodies.
- the phosphor of the present invention is not particularly limited to a crystal form, and may be a single crystal or a polycrystal. However, a polycrystal is desirable in view of easiness of production and small variation in characteristics. .
- the polycrystalline body can be obtained a phosphor material through 1) a process of synthesizing a powder as a raw material of a scintillator, and 2) a sintering process using the powder.
- the crystal grain size of the synthetic powder is preferably as small as possible, and is preferably 1.0 / xm or less.
- Powders were synthesized by 1) a method mainly based on the ordinary oxide mixing method, 2) a method via a liquid phase such as the coprecipitation method and the Sorge / Le method, and 3) a method based on the oxide mixing method. There is a method of mechanically refining the powder again.
- the usual oxide mixing method for example, it can be manufactured as follows. Gd 2 0 3 as raw material powder, Ce 2 0 3, A1 2 0 3, and Ga 2 0 3, etc., after the powder containing metal ingredients were weighed in predetermined amounts, wet-mixed by for example, a ball mill or an automatic mortar. This mixed powder is fired for several hours in air at 1000 ° C to 1700 ° C or in an oxygen atmosphere. To produce a scintillator synthetic powder. If necessary, the formation of a Gd—Ce—Al—Ga—0-based garnet structure can be promoted by using a flux such as K 2 SO 4 or a fluoride such as BaF 2 as a flux.
- a flux such as K 2 SO 4 or a fluoride such as BaF 2 as a flux.
- the following can be synthesized as an example.
- Predetermined amounts of gadolinium nitrate, alumina nitrate, gallium nitrate, and cerium nitrate are weighed to make a composite nitrate aqueous solution, and urea equivalent to 15 times the total amount of metal ion concentration coexists with sulfate ion.
- the aqueous solution is heated to 70 to 100 ° C. to hydrolyze urea and precipitate a Gd_Ce-Al-Ga-0 precursor.
- the drying temperature may be at least 90 ° C at which moisture evaporates, and the calcining temperature may be at least 900 ° C at which a garnet structure is formed. Heat treatment at high temperatures that causes the resulting garnet structure grains to grow must be avoided.
- the raw materials for the coprecipitation method are not limited to nitrates, and nitrates, sulfates, oxalates and the like of various metals can be used. In some cases, these metal salts can be used as a mixture of several kinds. In addition, ammonium bicarbonate can be used instead of urea.
- 1) urea and ammonium lactate, 2) ammonium bicarbonate and aqueous ammonia, or 3) ammonium sulfate and aqueous ammonia, 4) hydrogen peroxide as a masking agent Gd-Ce-Al-Ga-0 precursor can also be precipitated by adding ammonia water and ammonium sulfate.
- mechanical refinement of the raw material powder is a suitable method for obtaining a garnet structure by sintering. That is, as in the case of the above-described oxide mixing method, a predetermined amount of the oxide of the constituent metal component is weighed, and then mixed in an automatic mortar for about 30 minutes. After calcining the mixed powder at a temperature of about 1500 ° C, mechanical pulverization is performed.
- the sintering of the powder synthesized in this manner can be performed by a hot press method, a HIP method, a normal pressure sintering method, or a combination method of the normal pressure sintering method and the HIP method.
- the relative density of the sintered body is preferably at least 99.0%, more preferably at least 99.5%.
- Relative density is the actual density expressed as a percentage when the theoretical density of the material is 100. 'When the relative density is low, light scattering is large and light transmittance is extremely small, so that sufficient light output cannot be obtained. Therefore, it is desirable to keep the above range.
- the above-mentioned synthetic powder is molded into a compact by molding at a pressure of about 500 kgf m 2 , and then set in a hot press mold, and is subjected to 1000 ° C in a vacuum, air, or oxygen atmosphere. Sinter at a sintering temperature of C to 1700 ° C for several hours with a pressure of about 500 kgf / cm 2 . As a result, a phosphor having a relative density of 99.5% or more can be easily obtained.
- synthetic powder is placed in a capsule made of iron or metal such as W or Mo, sealed in a vacuum, and sintered at a temperature of about 1400 ° C and a pressure of about 2000 atm.
- the pressureless sintering method the synthetic powder was die-molded at 500 kgf / cm 2 pressure of about, after the isostatic pressing (CIP) at 3000 kgf / cm 2 pressure of about, 1,400-1,800 ° C before and after Sintering is performed for several to several tens of hours at a temperature. When the temperature exceeds 1800 ° C, the sample dissolves.
- CIP isostatic pressing
- the sintering density becomes about 90%, and a sufficient sintering density cannot be obtained.
- the relative density is about 93.0% or more due to normal pressure sintering, the pores become closed pores. If necessary, the capsule-free HIP method that does not require metal capsules can be used to increase the relative density. 99.5% or more of the phosphor can be easily obtained.
- the phosphor of the present invention obtained by the method as described above is a material in which the mother crystal has a garnet structure and the main peak of the emission spectrum is at about 535 nm, and is 300 ms after the excitation source is cut off. attenuation rate of the afterglow becomes 1 X 10- 4 or less.
- This oxide phosphor has a high emission output and an extremely low afterglow, and thus is suitable for a radiation detector that detects X-rays and the like, particularly a radiation detector such as an X-ray CT apparatus and a positive-open camera.
- a PIN type diode is used as a light detector. Since the photodiode has a high sensitivity, a fast response time, and a wavelength sensitivity in a range from the visible light to the near infrared region, the phosphor of the present invention has good matching with the emission wavelength.
- the above-mentioned radiation detector is used as the X-ray detector.
- the X-ray detector since the X-ray Dekiru detect with high detection efficiency can be greatly improved sensitivity Te ratio base on X-ray CT apparatus using a conventional scintillator (e.g. CdW0 4), also Since the afterglow is extremely small, it is possible to obtain high quality and high resolution images.
- FIG. 1 is a diagram showing a configuration of an embodiment of a radiation detector (X-ray detector) using the scintillator of the present invention
- FIG. 2 is a diagram showing a configuration of an embodiment of an X-ray CT apparatus of the present invention.
- FIG. 3 is a diagram showing a ternary composition of (Gd + Ce) —Al_Ga in the oxide phosphor of the present invention.
- FIG. 4 is a crystal structure of a garnet structure of the oxide phosphor of the present invention.
- FIG. 5 is a diagram showing the composition dependence of the emission characteristics of the oxide phosphor of the present invention.
- FIG. 1 shows an example of an X-ray detector 10 using the scintillator of the present invention.
- the scintillator 11 is adhered to the photodiode 13 and further covered with a shielding member 12 for preventing the light emitted from the scintillator from escaping to the outside.
- the shielding member 12 is made of aluminum or the like, which is a material that transmits X-rays and reflects light.
- the scintillator 11 is made of the phosphor of the present invention, has extremely low afterglow, has a high luminous output as compared with a conventional scintillator, and has a high sensitivity compared to the sensitivity wavelength of a Si photodiode. Close to the target wavelength of 535nm Since the scintillator 11 has an emission peak, when the scintillator 11 absorbs X-rays, it is photoelectrically converted by the photodiode with high efficiency. For this reason, the X-ray detector of the present invention has high sensitivity and excellent performance with very little afterglow.
- FIG. 2 shows an outline of the X-ray CT apparatus of the present invention.
- This apparatus includes a gantry section 18, an image reconstruction section 22, and a monitor 23.
- the gantry section 18 has a rotating disk 19 provided with an opening 20 into which a subject is loaded, and a rotating disk 19
- An X-ray tube 16 mounted, a collimator 17 attached to the X-ray tube and controlling the direction of emission of X-rays, an X-ray detector 15 mounted on a rotating disk facing the X-ray tube, and
- the system includes a detector circuit 21 for converting the X-ray dose detected by the X-ray detector 15 into a specific electric signal, and a scan control circuit 24 for controlling the rotation of the rotating disk and the width of the X-ray flux.
- the X-ray detector 15 has a structure in which a plurality of detecting elements, each of which is a combination of the scintillator 11 of the present invention and a photodiode 13 as shown in FIG. 1, are arranged in the circumferential direction of the rotating disk 19. Detects the X-ray dose that has been transmitted through the subject.
- the image reconstruction unit 22 is an input device 25 for inputting the subject's name, examination 0, examination conditions, etc., and an image for performing CT processing on the measurement data sent from the detector circuit 21 to perform CT image reconstruction.
- Arithmetic circuit (not shown), image information adding unit (not shown) for adding information such as the subject's name, examination date and time, and examination conditions input from input device 25 to the CT image created by this image arithmetic circuit ), And a display circuit (not shown) for adjusting the display gain of the CT image signal to which the image information has been added and outputting the adjusted gain to the moter 23.
- X-rays are emitted from the X-ray tube 16 with the subject lying on a bed (not shown) provided in the opening 20.
- This X-ray obtains directivity by the collimator 17 and is detected by the X-ray detector 15.
- X-rays are detected while changing the irradiation direction of the X-rays, and a tomographic image is created by the image reconstruction unit 22 and displayed on the monitor 23.
- the X-ray detector 15 is a detector using the phosphor of the present invention and having a low afterglow and a high emission intensity, the image is not deteriorated due to the afterglow, and high image quality and high resolution are obtained. Image can be obtained.
- the weighed raw material powder, alumina balls, and ion-exchanged water were put into a polyethylene container, and the raw material powder was mixed by a ball mill for about 12 hours.
- This mixed powder was transferred to an evaporating dish and dried, and the dried powder was sized through a nylon sieve.
- the sized powder was filled in an alumina crucible fc and calcined in oxygen at 1500 ° C. for 4 hours.
- the synthetic powder was irradiated with X-rays from an X-ray source (120, 0.5 mA), and afterglow and emission intensity were measured.
- X-rays from an X-ray source (120, 0.5 mA)
- afterglow and emission intensity were measured.
- a detector using a photodiode was placed 15 cm away from the X-ray source, and the light amount was measured.
- the afterglow is the decay rate 300 ms after X-ray cutoff, and the emission intensity is shown as a relative value.
- the amount of the generated heterophase was determined from a powder X-ray diffraction experiment.
- the amount of heterophase was defined as the ratio of the intensity of the main diffraction line of the garnet crystal structure, which is a matrix, to the intensity of the main diffraction line of the perovskite crystal structure, which is a heterophase.
- Figure 5 shows these results.
- the atomic ratio (Gd + Ce) / (Al + Ga + Gd + Ce) is larger than the stoichiometric composition of 0.375, the deviation from the stoichiometric composition with the amount of heterophasic GdA10 3 was produced.
- the atomic ratio (Gd + Ce) I (Al + Ga + Gd + Ce) stably had an extremely good value hardly changes about 4 X 10- 5 be changed to 0.44 a Was.
- the emission characteristics gradually deteriorated as the (Gd + Ce) component increased.
- the emission output will be about 60% or less compared to the stoichiometric composition, which is a different phase in the phosphor.
- the perovskite phase ratio also exceeded 50%, indicating that it was not suitable as a phosphor material.
- the (Gd + Ce) component was smaller than the stoichiometric composition, the afterglow characteristics and the luminescence characteristics were greatly deteriorated even with a slight change in the composition.
- This mixed powder was transferred to an evaporating dish and dried, and the dried powder was sized through a nylon sieve.
- the sized powder was filled in an alumina crucible and fired in oxygen at 1500 ° C for 4 hours.
- This synthetic powder was molded at a pressure of 500 kgf m 2 using a mold having an inner diameter of 160 mra to obtain a molded body.
- Set in a hot press die perform hot press sintering in vacuum at 1475 ° C for 4 hours at a pressure of 500 kgf / cm 2 , thickness 4.7 mm (Example 2) and thickness 15
- the sintered body of Example 3) was obtained.
- the relative density of each of these sintered bodies was 99.9% or more.
- the obtained sintered body is sliced in the thickness direction, and one and five pieces each having a diameter of 160 mm are cut out, cut into a predetermined size, and machined to a thickness of 108 to obtain a scintillator plate.
- the afterglow and emission intensity were measured by combining the scintillator plate produced above with a photodiode to produce a detector, and placing the detector 110 cm away from an X-ray source (120 kV, 150 mA). evaluated. Afterglow attenuation rate after 300ms and then cut the X-ray and the emission intensity is shown by relative values when the 1 value of CdW0 4.
- Sintered bodies were manufactured in the same manner as in Examples 2 and 3 except that the atomic ratios of Gd, Ce, Al, and Ga were as shown in Table 2.
- the atomic ratio Ga / (A1 + Ga) was 0.44, but in Comparative Examples 4 to 7 and Examples 4 to 8, 0.70, In Comparative Examples 8 to 11 and Examples 9 to 13, the value was 0.30.
- the Ce concentration was constant with the atomic ratio Ce / (Ce + Gd) being 0.004, and the (Gd + Ce) / (Al + Ga + Gd + Ce) ratio was changed.
- the thickness of all sintered bodies was 15 nim.
- the obtained sintered body was sliced in the thickness direction, cut, and then machined to a thickness of 1.8 mm to form a scintillator plate, which was annealed at 1300 ° C.
- the amount of the different phase of the ⁇ -plate was evaluated using the intensity ratio between the main peak of the diffraction line from the garnet structure obtained by the X-ray diffractometer and the main peak of the diffraction line of the different phase.
- a detector was fabricated by combining the obtained scintillator plate and the photodiode, and the detector was placed 110 cm away from the X-ray source (120 kV s 150raA) as in Example 23, and the emission intensity was set.
- Afterglow were evaluated.
- Luminous intensity is a relative value when the one value of CdW0 4, afterglow indicated by attenuation rate after 300ms and then cut the X-ray. The results are shown in Tables 2 and 3.
- the scintillators of Examples 4 to 13 of the present invention have extremely short afterglow at 300 ms and high emission intensity, which means that they have excellent scintillator characteristics.
- a detector was fabricated by combining the obtained scintillator plate and photodiode, and the detector was placed 110 cm away from the X-ray source (120 kV, 150 mA) to evaluate the afterglow and emission intensity.
- the afterglow is the decay rate 300 ms after blocking the X-rays, and the emission intensity is shown as a relative value when the value of CdTO 4 is set to 1. Table 4 shows the results.
- the scintillators of Examples 14 to 17 are excellent in both afterglow and emission intensity, but the scintillators having the atomic ratio Ga / (Al + Ga) of 0 or 1.0 (Comparative Examples 12 and 13) The luminous intensity was remarkably reduced, indicating that it was not suitable as a scintillator.
- the scintillators of Examples 18 to 21 and Comparative Examples 14 and 15 were produced in the same manner as in Examples 2 and 3, except that the atomic ratio Ce / (Ce + Gd) was changed from 0.002 to 0.04.
- the atomic ratio (Gd + Ce) I (Al + Ga + Gd + Ce) is fixed at 0.38, and the atomic ratio Ga (Al + Ga) is also 0.44. It was fixed.
- the thickness of the sintered body was 15 mm. Table 5 shows the results.
- the scintillators of Examples 18 to 21 are excellent in both afterglow and emission intensity, but Comparative Examples 14 and in which the atomic ratio Ce / (Ce + Gd) was set to a value less than 0.0005 or greater than 0.02.
- the scintillator of No. 15 has a remarkably reduced luminous intensity, indicating that it is not suitable as a scintillator.
- (Gd ⁇ CeJ 3 Al 5 _ y Ga y 0 12 reduces the influence of the set formed deviation at the time of sintering, which is a phosphor of the disadvantages of the composition, afterglow is extremely small, and the emission efficiency of
- this phosphor as a scintillator for a radiation detector equipped with a photodetector, a high-power radiation detector with low afterglow can be obtained.
- High resolution and high quality tomographic images can be obtained by applying to X-ray CT.
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Description
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Priority Applications (2)
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US10/451,247 US7076020B2 (en) | 2000-12-21 | 2001-12-20 | Oxide phosphor and radiation detector using it, and X-ray CT device |
EP01271422.6A EP1347032B1 (en) | 2000-12-21 | 2001-12-20 | Oxide phosphor and radiation detector using it, and x-ray ct device |
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JP2000-389343 | 2000-12-21 | ||
JP2000389343A JP4683719B2 (ja) | 2000-12-21 | 2000-12-21 | 酸化物蛍光体及びそれを用いた放射線検出器、並びにx線ct装置 |
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US (1) | US7076020B2 (ja) |
EP (1) | EP1347032B1 (ja) |
JP (1) | JP4683719B2 (ja) |
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WO2004077098A1 (ja) * | 2003-02-27 | 2004-09-10 | Kabushiki Kaisha Toshiba | X線検出器とそれを用いたx線検査装置 |
US8025960B2 (en) * | 2004-02-02 | 2011-09-27 | Nanosys, Inc. | Porous substrates, articles, systems and compositions comprising nanofibers and methods of their use and production |
CN102127440A (zh) | 2004-12-21 | 2011-07-20 | 日立金属株式会社 | 荧光材料及其制造方法,使用荧光材料的放射线检测器,与x射线ct装置 |
CN101128563B (zh) * | 2005-02-28 | 2012-05-23 | 三菱化学株式会社 | 荧光体、其制造方法及其应用 |
JP4692890B2 (ja) * | 2006-02-14 | 2011-06-01 | 日立金属株式会社 | 蛍光材料およびそれを用いた放射線検出器 |
US7442938B2 (en) * | 2007-01-16 | 2008-10-28 | General Electric Company | X-ray detector fabrication methods and apparatus therefrom |
JP5212115B2 (ja) | 2007-02-02 | 2013-06-19 | 日立金属株式会社 | 蛍光材料およびそれを用いたシンチレータ並びに放射線検出器 |
US8153025B2 (en) * | 2007-02-06 | 2012-04-10 | Koninklijke Philips Electronics N.V. | Red emitting luminescent materials |
JP5521412B2 (ja) | 2008-07-31 | 2014-06-11 | 日立金属株式会社 | 蛍光材料およびそれを用いたシンチレータ並びに放射線検出器 |
US8377335B2 (en) | 2009-02-23 | 2013-02-19 | Kabushiki Kaisha Toshiba | Solid scintillator, radiation detector, and tomograph |
KR101423249B1 (ko) * | 2009-07-28 | 2014-07-24 | 드미트리 유리예비치 소코로프 | 고체 백색 광원들을 위한 무기 발광물질 |
JP5712768B2 (ja) * | 2010-05-10 | 2015-05-07 | 信越化学工業株式会社 | 波長変換部材、発光装置、及び波長変換部材の製造方法 |
CN102869748B (zh) | 2010-10-29 | 2015-01-07 | 日立金属株式会社 | 软x射线检测用多晶闪烁器及其制造方法 |
US8969812B2 (en) | 2011-01-31 | 2015-03-03 | Furukawa Co., Ltd. | Garnet-type crystal for scintillator and radiation detector using the same |
US9145517B2 (en) | 2012-04-17 | 2015-09-29 | General Electric Company | Rare earth garnet scintillator and method of making same |
EP3489328A1 (en) * | 2012-11-14 | 2019-05-29 | Koninklijke Philips N.V. | Scintillator material |
EP2898043B1 (en) * | 2013-03-26 | 2016-06-01 | Koninklijke Philips N.V. | Mixed oxide materials |
US10961452B2 (en) * | 2015-12-01 | 2021-03-30 | Siemens Medical Solutions Usa, Inc. | Method for controlling gallium content in gadolinium-gallium garnet scintillators |
WO2018009712A2 (en) * | 2016-07-06 | 2018-01-11 | Nutech Ventures | Monolithic integration of hybrid perovskite single crystals with silicon for highly sensitive x-ray detectors |
KR101960227B1 (ko) | 2018-10-16 | 2019-03-19 | 경희대학교 산학협력단 | 밴드 옵셋 구조를 포함하는 엑스선 검출기 |
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WO1999033934A1 (fr) * | 1997-12-24 | 1999-07-08 | Hitachi Medical Corporation | Luminophores et detecteurs de rayonnement et unites de tomodensitometrie formes a partir de ces luminophores |
JP2001004753A (ja) * | 1999-06-23 | 2001-01-12 | Hitachi Medical Corp | 酸化物蛍光体及びそれを用いた放射線検出器、並びにx線ct装置 |
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US3699478A (en) * | 1969-05-26 | 1972-10-17 | Bell Telephone Labor Inc | Display system |
DE3704813A1 (de) * | 1987-02-16 | 1988-08-25 | Philips Patentverwaltung | Einkristall auf basis von seltenerdmetall-aluminium-granat |
CA2042263A1 (en) * | 1990-06-29 | 1991-12-30 | Charles D. Greskovich | Transparent polycrystalline garnets |
TW383508B (en) * | 1996-07-29 | 2000-03-01 | Nichia Kagaku Kogyo Kk | Light emitting device and display |
US6246744B1 (en) * | 1999-05-06 | 2001-06-12 | General Electric Company | Cubic garnet host with PR activator as a scintillator material |
US6538371B1 (en) * | 2000-03-27 | 2003-03-25 | The General Electric Company | White light illumination system with improved color output |
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2000
- 2000-12-21 JP JP2000389343A patent/JP4683719B2/ja not_active Expired - Lifetime
-
2001
- 2001-12-20 US US10/451,247 patent/US7076020B2/en not_active Expired - Lifetime
- 2001-12-20 EP EP01271422.6A patent/EP1347032B1/en not_active Expired - Lifetime
- 2001-12-20 WO PCT/JP2001/011176 patent/WO2002050211A1/ja active Application Filing
Patent Citations (2)
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WO1999033934A1 (fr) * | 1997-12-24 | 1999-07-08 | Hitachi Medical Corporation | Luminophores et detecteurs de rayonnement et unites de tomodensitometrie formes a partir de ces luminophores |
JP2001004753A (ja) * | 1999-06-23 | 2001-01-12 | Hitachi Medical Corp | 酸化物蛍光体及びそれを用いた放射線検出器、並びにx線ct装置 |
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JP2002189080A (ja) | 2002-07-05 |
EP1347032B1 (en) | 2017-08-16 |
US20040066883A1 (en) | 2004-04-08 |
EP1347032A1 (en) | 2003-09-24 |
EP1347032A4 (en) | 2008-04-02 |
US7076020B2 (en) | 2006-07-11 |
JP4683719B2 (ja) | 2011-05-18 |
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