CERAMIC SCINTILLATOR, PHOTON-COUNTING TYPE X-RAY DETECTOR, AND METHOD FOR MANUFACTURING CERAMIC SCINTILLATOR
20260050092 ยท 2026-02-19
Inventors
Cpc classification
H10F39/1898
ELECTRICITY
C09K11/00
CHEMISTRY; METALLURGY
International classification
Abstract
A ceramic scintillator according to an embodiment includes a garnet compound having a composition represented by (Lu.sub.1-xPr.sub.x).sub.a(Al.sub.1-y-zGa.sub.yM.sub.z).sub.bO.sub.1.5{a+b}, In the ceramic scintillator, M in the composition includes one kind or more of Si, Ge, and Sn, and x, y, and z respectively satisfy 0.002x0.500, 0.1y0.8, and 0.0010z0.1000.
Claims
1. A ceramic scintillator comprising: a garnet compound having a composition represented by (Lu.sub.1-xPr.sub.x).sub.a(Al.sub.1-y-zGa.sub.yM.sub.z).sub.bO.sub.1.5{a+b}, wherein M in the composition includes one kind or more of Si, Ge, and Sn, and x, y, and z respectively satisfy
2. The ceramic scintillator according to claim 1, wherein a and b in the composition satisfy
3. The ceramic scintillator according to claim 1, wherein a decay time constant of light emission is less than 10 [nsec], and a light yield is 2500 [ph/MeV] or more.
4. The ceramic scintillator according to claim 1, wherein a decay time constant of light emission is 17 [nsec] or less, and a light yield is 10000 [ph/MeV] or more.
5. A photon-counting type X-ray detector, comprising: the ceramic scintillator according to claim 1; and a silicon photomultiplier.
6. A photon-counting type X-ray detector, comprising: the ceramic scintillator according to claim 2; and a silicon photomultiplier.
7. A photon-counting type X-ray detector, comprising: the ceramic scintillator according to claim 3; and a silicon photomultiplier.
8. A photon-counting type X-ray detector, comprising: the ceramic scintillator according to claim 4; and a silicon photomultiplier.
9. A method for manufacturing the ceramic scintillator according to claim 1, comprising: a first step of filling an alumina container with a mixture of oxide powders of Lu, Pr, Al, Ga and M in the composition and mixing the mixture; a second step of firing the mixed mixture at a temperature of 1300 C. or higher; a third step of filling an alumina container with a product obtained by the second step, and firing the product at a temperature of 1200 C. or higher in a nitrogen/hydrogen mixed atmosphere; a fourth step of molding a product obtained by the third step; and a fifth step of sintering a product obtained by the fourth step to manufacture the ceramic scintillator.
10. A method for manufacturing the ceramic scintillator according to claim 2, comprising: a first step of filling an alumina container with a mixture of oxide powders of Lu, Pr, Al, Ga and M in the composition and mixing the mixture; a second step of firing the mixed mixture at a temperature of 1300 C. or higher; a third step of filling an alumina container with a product obtained by the second step, and firing the product at a temperature of 1200 C. or higher in a nitrogen/hydrogen mixed atmosphere; a fourth step of molding a product obtained by the third step; and a fifth step of sintering a product obtained by the fourth step to manufacture the ceramic scintillator.
11. A method for manufacturing the ceramic scintillator according to claim 3, comprising: a first step of filling an alumina container with a mixture of oxide powders of Lu, Pr, Al, Ga and M in the composition and mixing the mixture; a second step of firing the mixed mixture at a temperature of 1300 C. or higher; a third step of filling an alumina container with a product obtained by the second step, and firing the product at a temperature of 1200 C. or higher in a nitrogen/hydrogen mixed atmosphere; a fourth step of molding a product obtained by the third step; and a fifth step of sintering a product obtained by the fourth step to manufacture the ceramic scintillator.
12. A method for manufacturing the ceramic scintillator according to claim 4, comprising: a first step of filling an alumina container with a mixture of oxide powders of Lu, Pr, Al, Ga and M in the composition and mixing the mixture; a second step of firing the mixed mixture at a temperature of 1300 C. or higher; a third step of filling an alumina container with a product obtained by the second step, and firing the product at a temperature of 1200 C. or higher in a nitrogen/hydrogen mixed atmosphere; a fourth step of molding a product obtained by the third step; and a fifth step of sintering a product obtained by the fourth step to manufacture the ceramic scintillator.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] Each of
[0013]
[0014]
[0015]
[0016]
[0017]
[0018]
[0019]
[0020]
[0021]
[0022]
[0023]
[0024]
DETAILED DESCRIPTION
[0025] Hereinafter, embodiments of a ceramic scintillator, a photon-counting type X-ray detector, and a method for manufacturing the ceramic scintillator will be described in detail with reference to the drawings.
[0026] A ceramic scintillator according to an embodiment includes a garnet compound having a composition represented by (Lu.sub.1-xPr.sub.x).sub.a(Al.sub.1-y-zGa.sub.yM.sub.z).sub.bO.sub.1.5{a+b}, In the ceramic scintillator, M in the composition includes one kind or more of Si, Ge, and Sn, and x, y, and z respectively satisfy 0.002x0.500, 0.1y0.8, and 0.0010z0.1000.
(Photon-Counting Type X-Ray Detector)
[0027] Each of
[0028] Each of
[0029] The X-ray detector 1 is installed on a rotating frame of a holding device. The X-ray detector 1 is provided with n (n: a plurality) of X-ray detection elements 1n. The X-ray detection elements 1n are arranged two-dimensionally in a matrix form in the channel direction and the slice direction SL. The channel direction means a spread direction of fan beam X-rays emitted from the X-ray tube 2, and the slice direction means a thickness direction of the fan beam X-rays.
[0030] An X-ray incident surface of the X-ray detector 1 is formed by X-ray incident surfaces of the X-ray detection elements 1n. For example, about 1000 X-ray detection elements 1n are arranged in the channel direction CH, and 64 X-ray detection elements 1n are arranged in the slice direction SL.
[0031] The X-ray tube 2 is installed in a rotating frame of a holding device to face the X-ray detector 1. The X-ray tube 2 is a vacuum tube that generates X-rays by irradiating thermal electrons from a cathode (filament) to an anode (target) by applying a high voltage. For example, among X-ray tubes 2, there is a rotating anode type X-ray tube that generates X-rays by irradiating a rotating anode with thermal electrons.
[0032] A collimator device 3 has a plurality of collimator plates having a function of absorbing scattered X-rays. The plurality of collimator plates comprise plates that extend in the slice direction SL and are provided to be erected to divide the X-ray detection elements 1n in the channel direction CH (one-dimensional collimator). Alternatively, the plurality of collimator plates comprise plates that extend in the slice direction SL and are provided to be erected to divide the X-ray detection elements 1n in the channel direction CH, and plates that extend in the channel direction CH and are provided to be erected to divide the X-ray detection elements 1n in the slice direction SL (two-dimensional collimator). An inclination of the plate surface of the collimator plate is adjusted to be parallel to an X-ray irradiation direction E that is a direction in which X-rays from an X-ray focal point F of the X-ray tube 2 are irradiated.
[0033] The X-ray detector 1 may be configured by arrangement of a plurality of detector modules by modularizing a predetermined number of X-ray detection elements among the X-ray detection elements 1n. Likewise, the collimator device 3 may be configured by arrangement of a plurality of collimator modules by modularizing a predetermined number of collimator plates.
[0034]
[0035] The X-ray detection elements 1n are provided on a ceramic substrate 4. Each of the X-ray detection elements 1n includes a ceramic scintillator 11 and a photoelectric conversion element 12.
[0036] The ceramic scintillator 11 is an element that converts incident X-rays into photons and emits the photons. Here, X-rays usually have a predetermined X-ray energy distribution. An X-ray having a specific X-ray energy can be considered a mass of X-ray particles a number of which corresponds to a magnitude of the X-ray energy. The ceramic scintillator 11 converts the X-ray particles into photons with a predetermined probability while maintaining a mass of the X-ray particles. When X-rays are incident on the ceramic scintillator 11, the ceramic scintillator 11 emits substantially simultaneously photon groups in number corresponding to the X-ray energy according to X-ray energy.
[0037] The ceramic scintillator 11 is a light conversion element having a substantially rectangular parallelepiped or cubic shape. The ceramic scintillator 11 is disposed so that an X-ray incident surface thereof is substantially perpendicular to an X-ray irradiation direction, that is, the X-ray incident direction E, and a side surface parallel to the X-ray incident direction E is substantially parallel to the channel direction CH and the slice direction SL.
[0038] The photoelectric conversion element 12 has a substantially plate-shaped rectangular parallelepiped shape, converts incident photons into electrical signals, and outputs the electrical signals. The electrical signals are electrical pulse signals corresponding to the individual incident photons. When photon groups are simultaneously incident on the photoelectric conversion element 12, the photoelectric conversion element 12 outputs a pulse signal a wave height of which corresponds to a number of photons configuring the photon group. The photoelectric conversion element 12 is a semiconductor device suitable for so-called photon counting, and is, for example, a silicon photomultiplier (Si-PM). A silicon photomultiplier is a high-performance semiconductor photon detector that is capable of photon counting (photon counting) measurement, and is also applicable to analogue measurement such as scintillation detection. A silicon photomultiplier is an element in which a large number of pixels of avalanche photodiodes (APD) that operate in the Geiger mode are connected in parallel.
[0039] The photoelectric conversion element 12 receives photons emitted from the ceramic scintillator 11, and outputs electrical signals in a pulse form. When intensity of transmission X-rays of an object is sufficiently low, the photon groups according to X-ray energy are released in a scattered state in a time axis direction, in the ceramic scintillator 11. At this time, the photoelectric conversion element 12 outputs, for each X-ray energy, a pulse signal having a wave height corresponding to the magnitude of the X-ray energy in numbers corresponding to a dose of the X-rays having the X-ray energy, in a state dispersed in the time axis direction. Accordingly, if the pulse signals outputted in a fixed time are counted for each wave height, it is possible to know a dose of transmission X-rays of the object for each X-ray energy. If all the pulse signals outputted in a fixed time are counted regardless of wave heights, it is possible to know a dose of all transmission X-rays of the object.
[0040] To the photoelectric conversion element 12, conductor patterns (not illustrated) formed on the ceramic substrate 4 are respectively connected. The electrical signals from the photoelectric conversion element 12 are outputted to an external processing device (not illustrated) through these conductor patterns. The electrical signals outputted from the photoelectric conversion element 12 are used in collection of projection data by a photon-counting method.
[0041] Here, a detector used in the photon-counting method generally has a very high X-ray detection sensitivity. The detector has high sensitivity, that is, can obtain signals with sufficient S/N, even if the dose of X-rays is low, and a number of photons emitted from the scintillator is small. However, when the dose of X-rays is large, the pulse signals are superimposed, a phenomenon called pile-up (pile up) occurs, and it becomes impossible to resolve the signals in the time axis direction.
[0042] Among the photon counting methods, in the case of the indirect type, there is a problem of counting rate as in the case of the direct type. The counting rate indicates the number of incident X-ray photons per unit area per unit time. In order to realize imaging by a photon-counting type X-ray detector, a detector handling with a high counting rate is necessary. For example, a counting rate required in X-ray CT equipment is 10.sup.8 [cps/mm.sup.2] or more. This means that X-ray photons are incident on an area of 1 [mm.sup.2] at an average interval of 10 [nsec]. At present, a scintillator capable of handling with such a high counting rate has not been put into practical use. If the counting rate exceeds a capacity of the scintillator, pile-up occurs, and it becomes difficult to measure correct photon energy. On the other hand, suppressing the counting rate and performing measurement for a long time causes problems such as a decrease in throughput and a decrease in time resolution.
[0043] The counting rate of a scintillator is mainly determined by a response speed of the material. Therefore, there is an urgent need to develop materials for scintillators with improved response speeds so as not to cause pile-up while avoiding long-time measurements.
(Ceramic Scintillator and Manufacturing Method Thereof)
[0044] A main factor that determines the response speed of the indirect type is a decay time constant of light emission of a scintillator. In order to realize the aforementioned counting rate 10.sup.8 [cps/mm.sup.2], control of the decay time constant of light emission of the scintillator becomes particularly important, and it is preferable that the decay time constant of light emission is about 17 [nsec] or less. By making the decay time constant of light emission 17 [nsec] or less, it becomes possible to prevent pile-up and realize imaging at a practical level as described above. Thus, experiments were conducted with an aim of setting the decay time constant of light emission of the scintillator to about 17 [nsec] or less. As a result, it was found that a light yield of 10000 [ph/MeV] or more is good. This is because if the light yield is 10000 [ph/MeV] or more, there is no problem in both the S/N ratio and the energy resolution, and a detector with higher accuracy can be obtained.
[0045] In other words, it is desirable that the decay time constant is 17 [nsec] or less and the light yield is 10000 [ph/MeV] or more. For this purpose, a fluorescent material of the ceramic scintillator 11 that is applied as the light conversion element is a garnet compound having a composition represented by [0046] (Lu.sub.1-xPr.sub.x).sub.a(Al.sub.1-y-zGa.sub.yM.sub.z).sub.bO.sub.1.5{a+b}, wherein M in the composition includes one kind or more of Si, Ge, and Sn, and x, y, and z respectively satisfy all of
Here, the decay time constant is defined as a time it takes for the light emission intensity to decrease to 1/e (=0.3679) of a maximum light emission intensity when a time at which a light emission intensity generated by radiating radiation of a short-time pulse becomes maximum is zero. For example, a change with time of the light emission intensity is recorded by performing time-correlated signal photon counting method (Time-Correlated Single Photon Counting: TCSPC) using a pulsed X-ray tube, and the decay time constant can be calculated from a numeric value thereof.
[0047] Furthermore, in the garnet compound having the above-described composition, it is more desirable to include the following condition.
[0048] A coefficient of O in the composition is 1.5 times a sum of a and b, and therefore, if a=3, and b=5, the coefficient is 12.
[0049] As described above, in the aforementioned composition, M includes one kind or more of tetravalent elements Si, Ge, and Sn. Among light emission elements Pr, Pr.sup.3+ emits light, and Pr.sup.4+ does not emit light and absorbs visible light. Therefore, presence of Pr.sup.4+ is a factor of reducing the characteristics of the light yield and the decay time constant of the scintillator. Since Pr replaces Lu.sup.3+, most of it is Pr.sup.3+, but there is a problem that traces of Pr.sup.4+ remain. Here, if a divalent element is added, Pr tends to become tetravalent in order to maintain the charge balance, and therefore the characteristics of the light yield and the decay time constant of the scintillator are further reduced. On the other hand, if a tetravalent element is added, Pr tends to become trivalent in order to maintain the charge balance, and therefore, it is possible to stabilize Pr.sup.3+ by suppressing residual Pr.sup.4+ and improve the characteristics. A degree of addition of the tetravalent element is determined as the above-described conditions 1 to 4 based on the characteristics of the light yield and decay time constant which will be described later by using
[0050] Subsequently, results of producing fluorescent materials according to examples having the compositions that satisfy the above-described conditions 1 to 4, and fluorescent materials according to comparative examples that do not satisfy at least one of the above-described conditions 1 to 4, and investigating the characteristics of the light yield and the decay time constant of light emission will be described. The fluorescent materials according to the examples, and the fluorescent materials according to the comparative examples are produced through the following steps.
[0051] First, in a first step, a powder of a mixture (mixture of powders of oxides of Lu, Pr, Al, Ga, and M) of lutetium oxide, praseodymium oxide, alumina, gallium oxide, and an oxide of a tetravalent element M (for example, Si, Ge, Sn) is filled into an alumina container and mixed. In a second step, the mixed powder is fired at a temperature of 1300 [ C.] or higher. In a third step, the product obtained by the second step is filled into an alumina container and fired at a temperature of 1200 [ C.] or higher in a nitrogen/hydrogen mixed atmosphere. In a fourth step, the product obtained by the third step is molded. In a fifth step, a ceramic scintillator is manufactured by sintering the product obtained by the fourth step.
[0052] Sintering is done in one step. By performing sintering in one step, unlike the case of performing sintering in two steps or more, it is possible to obtain a ceramic scintillator that has little deviation in composition and good crystallinity, and has a small decay time constant because it can suppress volatilization of Ga.
[0053] The fluorescent materials comprise elements contained in the above-described composition, and do not contain any other elements except for unavoidable impurities. This is because the decay time constant of light emission changes depending on the contained elements, and therefore when a large amount of impurities is contained, the decay time constant of light emission may increase. Impurities of 100 ppm or more may be included as long as they comply with the required light yield and/or the required decay time constant of light emission. Here, when Si functions as a sintering aid, it remains as an impurity in grain boundaries of the ceramic scintillator as a finished product. Therefore, when Si remains in the grain boundaries, it can be determined that Si is added as a sintering aid, and when Si is present in a base material, it can be determined that it is added as a raw material. In the ceramic scintillator according to the embodiment, Si, Ge, and Sn compounds are not present in the grain boundaries except when several tens ppm of them are present as impurities, which means a garnet compound containing Si, Ge, or Sn in the base material.
(the Above-Described Conditions 1 to 3, that is, Variables x, y, z)
[0054] Changes in the light yield and decay time constant according to a type of a metal M and variables x, y, and z in the composition of (Lu.sub.1-xPr.sub.x).sub.a(Al.sub.1-y-zGa.sub.yM.sub.z).sub.bO.sub.1.5{a+b} will be described by using
[0055]
[0056] With x fixed to 0.001, and a/b to 0.60, y and z of the above-described conditions 2 and 3 are used as variables to find the light yields [ph/MeV] and the decay time constants [nsec]. Then, the ratios [%] of the light yields [ph/MeV] when z0.000 (for example, z=0.0005, 0.0010, 0.0500, 0.1000, and 0.1500), to the light yield [ph/MeV] when z=0.000 which is the standard, are obtained, and the ratios are classified into levels 0 to 3 in order from a lowest value to create the upper row in
TABLE-US-00001 TABLE 1 Ratio [%] of Light Yield to That of Standard Level Ratio of Light Yield < 95 0 95 Ratio of Light Yield < 105 1 105 Ratio of Light Yield < 125 2 125 Ratio of Light Yield 3
[0057] On the other hand, the ratios [%] of the decay time constants [nsec] when z0.000, to the decay time constant [nsec] when z=0.000 which is the standard, are obtained, and the ratios are classified into levels 0 to 3 in order from a highest value to create the lower row in
TABLE-US-00002 TABLE 2 Ratio [%] of Decay Time Constant to That of Standard Level 120 Ratio of Decay Time Constant 0 80 Ratio of Decay Time Constant < 120 1 60 Ratio of Decay Time Constant < 80 2 Ratio of Decay Time Constant < 60 3
[0058]
[0059] With x fixed to 0.002, and a/b to 0.60, y and z of the above-described conditions 2 and 3 are used as variables to find the light yields [ph/MeV] and the decay time constants [nsec]. The levels of the upper row and the lower row of
[0060]
[0061] With x fixed to 0.020, and a/b to 0.60, y and z of the above-described conditions 2 and 3 are used as variables to find the light yields [ph/MeV] and the decay time constants [nsec]. The levels of the upper row and the lower row of
[0062]
[0063] With x fixed to 0.250, and a/b to 0.60, y and z of the above-described conditions 2 and 3 are used as variables to find the light yields [ph/MeV] and the decay time constants [nsec]. The levels of the upper row and the lower row of
[0064]
[0065] With x fixed to 0.500, and a/b to 0.60, y and z of the above-described conditions 2 and 3 are used as variables to find the light yields [ph/MeV] and the decay time constants [nsec]. The levels of the upper row and the lower row of
[0066]
[0067] With x fixed to 0.550, and a/b to 0.60, y and z of the above-described conditions 2 and 3 are used as variables to find the light yields [ph/MeV] and the decay time constants [nsec]. The levels of the upper row and the lower row of
[0068] Referring to
[0069] Note that in
(Above-Described Condition 4, that is, Variable a/b)
[0070] The changes in the light yield and decay time constant according to the variable a/b in the composition of (Lu.sub.1-xPr.sub.x).sub.a(Al.sub.1-y-zGa.sub.yM.sub.z).sub.bO.sub.1.5{a+b} will be described by using
[0071]
[0072] With x fixed to 0.001 and z to 0.050, y and a/b in the above-described conditions 2 and 4 are used as variables to find the light yields [ph/MeV] and decay time constants [nsec]. Then, the ratios [%] of the light yields [ph/MeV] when a/b=0.60 (for example, a/b=0.45, 0.50, 0.70, and 0.75), to the light yield [ph/MeV] when a/b=0.60 are obtained, and the ratios are classified into levels 0 to 3 in order from a lowest value to create the upper row in
[0073] On the other hand, the ratios [%] of the decay time constants [nsec] when a/b0.60, to the decay time constant [nsec] when a/b=0.60 are obtained, and the ratios are classified into levels 0 to 3 in order from a highest value to create the lower row in
[0074]
[0075] With x fixed to 0.002, and z to 0.050, y and a/b of the above-described conditions 2 and 4 are used as variables to find the light yields [ph/MeV] and the decay time constants [nsec]. The levels in the upper row and the lower row in
[0076]
[0077] With x fixed to 0.020, and z to 0.050, y and a/b of the above-described conditions 2 and 4 are used as variables to find the light yields [ph/MeV] and the decay time constants [nsec]. The levels in the upper row and the lower row in
[0078]
[0079] With x fixed to 0.500, and z to 0.050, y and a/b of the above-described conditions 2 and 4 are used as variables to find the light yield [ph/MeV] and the decay time constant [nsec]. The levels in the upper row and the lower row in
[0080]
[0081] With x fixed to 0.550, and z to 0.050, y and a/b of the above-described conditions 2 and 4 are used as variables to find the light yields [ph/MeV] and the decay time constants [nsec]. The levels in the upper row and the lower row in
[0082] Referring to
[0083] If the variables x, y, z, a and b in the composition represented by (Lu.sub.1-xPr).sub.a(Al.sub.1-y-zGa.sub.yM.sub.z).sub.bO.sub.1.5{a+b} are in the above described ranges, it is possible to provide a fluorescent material with a small decay time constant of light emission. By applying the fluorescent material as a ceramic scintillator of an X-ray detector for a medical application, it is also possible to handle with required reactivity.
[0084] According to at least one embodiment described above, it is possible to provide a ceramic scintillator that can handle with a high counting rate, a photon-counting type X-ray detector equipped with it, and a method for manufacturing the ceramic scintillator.
[0085] The ceramic scintillator 11 is not limited to the case of being applied to a photon-counting type X-ray detector equipped with a silicon photomultiplier, in X-ray CT equipment. For example, the ceramic scintillator 11 may be applied to an X-ray detector equipped with photodiode, in X-ray CT equipment. The ceramic scintillator 11 may also be applied to a flat panel detector (FPD: Flat Panel Detector) equipped with CMOS (Complementary Metal Oxide Semiconductor). The ceramic scintillator 11 may be applied to a photon-counting type detector equipped with a silicon photomultiplier, in PET (Positron Emission Tomography) equipment. The ceramic scintillator 11 may be applied to imaging for industrial applications such as baggage inspection, and a nondestructive inspection.
[0086] While certain embodiments have been described, these embodiments have been presented by way of example only, and are not intended to limit the scope of the inventions. Indeed, the novel methods and systems described herein may be embodied in a variety of other forms; furthermore, various omissions, substitutions and changes in the form of the methods and systems described herein may be made without departing from the spirit of the inventions. The accompanying claims and their equivalents are intended to cover such forms or modifications as would fall within the scope and spirit of the inventions.