SCINTILLATOR AND METHOD FOR MANUFACTURING THE SAME
20220363988 · 2022-11-17
Inventors
Cpc classification
C30B11/002
CHEMISTRY; METALLURGY
C30B11/003
CHEMISTRY; METALLURGY
International classification
C30B11/00
CHEMISTRY; METALLURGY
Abstract
A scintillator, a preparation method therefor, and an application thereof are disclosed wherein the scintillator has a chemical formula of Tl.sub.aA.sub.bB.sub.c:yCe, wherein: A is at least one rare earth element selected from trivalent rare earth elements; B is at least one halogen element selected from halogen elements; a=1, b=2 and c=7, a=2, b=1 and c=5, or a=3, b=1 and c=6; and y is greater than or equal to 0 and less than or equal to 0.5. According to another embodiment, the scintillator has a chemical formula of Tl.sub.aA.sub.bB.sub.c:yEu, wherein: A is an alkaline earth metal element; B is a halogen element; a=1, b=2 and c=5, or a=1, b=1 and c=3; and y is greater than or equal to 0 mol % and less than or equal to 50 mol %.
Claims
1. A scintillator comprising: a matrix material including thallium, at least one alkaline earth metal element, and at least one halogen element.
2. The scintillator of claim 1, further comprising: an activator, with which the matrix material is doped, wherein the activator includes europium.
3. The scintillator of claim 1, wherein a chemical formula of the scintillator is Tl.sub.aA.sub.bB.sub.c:yEu, and wherein A is at least one alkaline earth metal element selected from divalent alkaline earth metal elements, B is at least one halogen element selected from halogen elements, a is 1, b is 2, and c is 5 or a is 1, b is 1, and c is 3, and y is equal to or more than 0 mol % and equal to or less than 50 mol %.
4. The scintillator of claim 1, wherein the alkaline earth metal element includes at least one of Ca, Ba, and Sr.
5. The scintillator of claim 1, wherein the halogen element includes at least one of Cl, Br, and I.
6. The scintillator of claim 1, wherein the matrix material includes thallium halide and alkaline earth halide.
7. A method of manufacturing a scintillator, the method comprising: manufacturing a matrix material including thallium, at least one alkaline earth metal element, and at least one halogen element.
8. The method of claim 7, wherein the manufacturing of the matrix material includes: mixing thallium halide and alkaline earth halide at a mole fraction of 1:2 or 1:1.
9. The method of claim 7, further comprising: doping the matrix material with an activator, wherein the doping the matrix material with the activator includes: doping the matrix material with europium halide.
10. The method of claim 7, further comprising: growing the matrix material into a single crystal, wherein the growing the matrix material into the single crystal includes: descending an ampoule, in which the matrix material is sealed, while heating the ampoule in a Bridgman electric furnace, and wherein the crystal is grown as the ampoule descends a crystal growth part in the Bridgman electric furnace, a product of a descent speed of the ampoule in the Bridgman electric furnace and a temperature gradient of the crystal growth part in the Bridgman electric furnace is in a range of 0.05 to 2.0° C./hr, and the temperature gradient of the crystal growth part is a a ratio of a change rate of a temperature with respect to a locational change at a crystal growth location in the Bridgman electric furnace.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DETAILED DESCRIPTION
[0053] The above and other aspects, features and advantages of the invention will become apparent from the following description of the following embodiments given in conjunction with the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below, and the present invention is defined by the scope of the claims. Although not defined, all the terms (including technical or scientific terms) used herein may have the same meanings that are generally accepted by the common technologies in the field to which the present invention pertains. A general description of the known configurations may be omitted not to make the essence of the present invention obscure. In the drawings of the present invention, the same reference numerals are used to denote the same or similar configurations if possible. For easy understanding of the present invention, some configurations may be rather exaggerated or downscaled in the drawings.
[0054] The terminologies used herein are provided only to describe specific embodiments and are not intended to limit the present invention. The terms of a singular form may include plural forms unless otherwise specified. The terms “including” and “having” are used to designate that the features, the numbers, the steps, the operations, the elements, the parts, or combination thereof described in the specification are present, and may be understood that one or more other features, numbers, step, operations, elements, parts, or combinations thereof may be added.
[0055] The present invention relates to a thallium rare earth halide scintillation crystal doped with an activator (for example, cerium) based on a matrix material (parent body material) including thallium (Tl), rare earth elements (Gd, Lu, Y, Sc, and Ce), halogen elements and in which an alkaline element is not contained as a main substance. A process of making a single crystal of a scintillator based on thallium is a process that requires a very difficult and high-level technology. The inventor(s) succeeded in developing an advanced material scintillator having excellent characteristics based on thallium and obtaining a single crystal through long-term studies and experiments. The inventor(s) could manufacture an advanced scintillator material that has never been present until now, through a growth temperature (melt temperature) condition and a crystal growth condition (a correlation between a descent speed of an ampoule and a temperature gradient of a crystal growth part) of the scintillator.
[0056] The scintillator according to an embodiment of the present invention is a scintillating material, the chemical formula is Tl.sub.aA.sub.bB.sub.c:yCe. A is at least one rare earth element selected from the group including Gd, Lu, Y, Sc, and Ce, B is at least one halogen element selected from the group including Cl, Br, and I. The mole fraction a:b:c of thallium, a rare earth element, and a halogen element may be 1:2:7, 2:1:5 or 3:1:6. y is a mole fraction (concentration) of ions of an activator (Ce) that is doped with impurities to generate a scintillation phenomenon, and may have a value of more than 0 and not more than 50 mol % for a proper amount of scintillation.
[0057] The scintillator according to an embodiment of the present invention may be manufactured through a process of manufacturing a matrix material by mixing thallium halide and rare earth halide at a mole fraction of 1:2, 2:1, or 3:1, and doping the matrix material with an activator including cerium halide and growing the matrix material into a single crystal. As a result of many experiments and trials and errors, the inventor(s) could come to know that a descent speed of an ampoule and a temperature gradient of a crystal growth part complexly influence the growth of crystals significantly when the mixture of the matrix material and the activator are grown into a single crystal, and a growth condition of the crystal growth part, that is, a melt temperature and a product of a descent speed of an ampoule and a temperature gradient of the crystal growth part has to be set to a specific range to grow the mixture of a thallium-based matrix material and an activator into a single crystal.
[0058] In an embodiment of the present invention, it is preferable that the product of the descent speed of the ampoule and the temperature gradient of the crystal growth part is set to a range of 0.05˜2.0° C./hr, and this is because productivity is bad when the product of the descent speed of the ampoule and the temperature gradient of the crystal growth part is less than 0.05° C./hr, and crystals are broken or crystal characteristics deteriorate when the product of the descent speed of the ampoule and the temperature gradient of the crystal growth part is more than 2.0° C./hr so that an amount of scintillation and fluorescent damping time characteristics deteriorate. Further, it is preferable that the melt temperature of the mixture of the matrix material and the activator is set to a range of 550 to 750° C. Then, the melt temperature may be properly adjusted according to a rare earth element or a halide element. When the melt temperature of an oxide scintillator according to the related art is generally 1,000 to 2,000° C. or higher, the scintillator according to the embodiment has an advantage of reducing process costs because a scintillator may be grown in a low melt temperature condition of 650° C. or less.
[0059] The scintillator according to the embodiment may be utilized in various application fields for detecting radioactive rays. The radioactive ray detection efficiency is determined according to an interaction between the input radioactive ray and the scintillator detector. It is a photoelectric effect that is most important in detection efficiency when an X-ray is detected, and because the photoelectric effect is proportional to the third to fifth power of the atomic number of the scintillator material, a detection efficiency for an X-ray or a gamma ray rapidly increases as the atomic number of the material becomes higher. Accordingly, the present invention developed an advanced scintillator having a high detection efficiency for a radioactive ray, in particular, an X-ray or a gamma ray based on thallium having an atomic number of 81.
[0060] The optical yield is a value related to the strength of a detection signal generated when the scintillator detects a radioactive ray, and because a signal to noise ratio (SNR) increases as the optical yield becomes higher, an excellent measurement result may be obtained with a small amount of rays. In particular, an exposure dose of a human body may be reduced when the scintillator is used as an image sensor for medical radioactive rays. The elements that determine an optical yield of the scintillator include the kind and the concentration of doped impurities, and crystal characteristics and transparency of the single crystal. In the scintillator, particularly, the crystal characteristics and transparency of the scintillator is a very important element. Generally, a material of a high atomic number has a low transparency, but according to the present invention, a scintillator having a transparency that shows an excellent optical yield may be developed by optimizing the kinds, the mole fractions, the crystal growth conditions, and the atmospheres of a main substance that forms the matrix material of the scintillator and the activator doped as impurities.
[0061] When the crystal structure of the scintillation crystal is a monoclinic system or a hexagonal system or a growth temperature of the crystal structure is high, it is difficult to grow a single crystal of a high quality, the price of the scintillation crystal is high, and a single crystal is broken easily to a specific crystal surface even though the single crystal is grown. Further, damping time characteristics may be longer because of emission of light due to self-trap excitation if the crystal characteristics and transparency deteriorate, and an output signal decreases because the emitted light generated by radioactive rays is absorbed in the scintillator. Accordingly, it is preferable that a crystal structure, such as a tetragonal system or a hexagonal system, which is advantageous for growth of crystals is selected when a single crystal is grown. Further, it is very important to optimize a crystal growth condition. All combinations of elements are not grown to a single crystal, and a process of making a single crystal having excellent scintillation characteristics is a process that is very difficult and requires a high-level technology even though they are materials that are grown to a single crystal.
[0062] Further, in the case of scintillators, the characteristics of a scintillator, such as light emission wavelength or light emission time, appears very differently according to the kinds of other components constituting the matrix material or a fine difference of the matrix material or the doping materials. The matrix material of the scintillator according to the embodiment does not include an alkaline element as a main element, and the process condition of the scintillator, in which a scintillation crystal of a sufficient size may be grown, is different from that of an existing scintillator including an alkaline element and the characteristics of the scintillators are totally different. The main substance in the specification refers to a substance that is intentionally added to grow a single crystal of a scintillator, except for impurities that are inevitably mixed in a scintillator single crystal growing process.
[0063] Based on many trials and errors, experiences, and theories, after selecting candidate elements through the radius of ions, the atomic numbers, and the melting points of the atoms, and the phase diagram, the X-ray diffraction (XRD), and the differential thermal analysis (DSC) of the crystal, the inventor(s) succeeded in developing a halide scintillation crystal based on thallium rare earth having excellent scintillation characteristics through experiments using various combinations of elements and established crystal growth conditions, such as a temperature condition, an atmosphere, and a crystal growth speed when the scintillation crystal is grown. In the X-ray diffraction analysis result, it was identified that the developed crystal of the scintillator is an advanced material that is not present in an XRD database.
[0064] The fluorescent damping time characteristics of the scintillator are determined according to energy transition characteristics of an energy band level of a matrix material and an energy level of doping impurities functioning as the center of emitted light. Many rare earth elements are used as doping impurities functioning as the center of emitting light, and a material in which the energy level of doping impurities and the energy level of a matrix material of a scintillator are well matched and energy may be well transited between the two energy levels has to be selected. In particular, fluorescent damping time characteristics are very important elements in application fields, such PET, which requires quick time characteristics. Further, because the wavelength of the emitted light is related to an energy level of doped impurities, it is required to select a material that is well suitable for photon efficiency characteristics of a photoelectron multiplier or a photodiode that is a passive element. Accordingly, thallium, a rare earth element, or a halogen element was selected as a main substance of the base, and cerium ions were selected as doping impurities. Cerium ions have a relatively high optical yield and quick time characteristics through a transition of 4f->5d, and the energy level of the cerium ions is well matched with the energy level of Tl.sub.aA.sub.bB.sub.c that is used as the matrix.
[0065] The thallium rare earth-based halide scintillator according to the present invention has a high atomic number and a high optical yield, and in particular, the scintillator has a high detection efficiency for X-rays or gamma rays, has excellent fluorescent damping time characteristics, easily grows a single crystal, and reduces an exposure dose for a human body when being utilized in a medical image field. Accordingly, the scintillator according to the embodiment may be utilized as an advance material scintillator for various medical radioactive ray images, such as CT, PET, SPECT, and a gamma camera, and may be utilized as a radioactive ray sensor for various industrial fields. In particular, the scintillator according to the embodiment of the present invention may be applied to a field, such as a positron emitting tomography device, which requires quick damping time characteristics because it has a short fluorescent damping time.
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[0068] The heating temperatures of the upper heater and the lower heater may be set such that the temperature of the crystal growth location becomes the melting temperature of the material of the scintillator and the product of the descent speed of the ampoule and the temperature gradient of the crystal growth part becomes 0.05 to 2.0° C./hr. Then, the crystal growth location of the scintillator may be formed at a location between the upper heater and the lower heater. In the embodiment of the present invention, the temperature gradient of the crystal growth part may mean a value obtained by measuring a ratio (rate) of a change of the temperature with respect to a change of the location of the crystal growth location.
[0069] In an aspect of productivity, it is preferable that the descent speed of the ampoule is set to 0.1 mm/hr or higher. Then, although being different according to the descent speed of the ampoule, the product of the descent speed of the ampoule and the temperature gradient of the crystal growth part may be set to 0.05˜2.0° C./hr and the temperature gradient of the crystal growth part may be set to a range of 30° C./cm or lower. In the embodiment of the present invention, the melt temperature may be 550 to 750° C. The melt temperature is a temperature that is much lower than a melt temperature for growing scintillators used in the related art, and according to the present invention, the costs may be remarkably lowered when a scintillator is manufactured because a single crystal may be grown at a low temperature of 550 to 750° C.
Embodiment 1
[0070] A thallium rare earth halide (Tl.sub.aGd.sub.bCl.sub.c:yCe) scintillation crystal was manufactured by doping a matrix material of thallium halide (TlCl) and 3 trivalent rare earth halide (GdCl.sub.3) with cerium. In order to manufacture a thallium rare earth halide scintillator, after thallium halide and rare earth halide are mixed at a mole fraction of 1:2 and a specific amount of cerium chloride is mixed, it was sealed in a quartz ampoule into a vacuum state of about 10.sup.−5 torr. The scintillator was manufactured by making the mole fraction of cerium chloride (CeCl.sub.3) 0, 1 mol % with respect to the mole fraction of thallium. The sealed quartz ampoule was grown to a thallium rare earth halide (TlGd.sub.2Cl.sub.7:yCe) scintillator in a Bridgman electric furnace. Then, a crystal growth condition of a product of the descent speed of the ampoule and the temperature gradient of the crystal growth part was 0.05˜2.0° C./hr.
[0071] When a single crystal is grown through a Bridgman method, the temperature and the temperature gradient of a single crystal growth point, and the descent speed of the sample are very important. The temperature of the single crystal growth point has a close relationship with the melt temperature of the sample. Because a single crystal of a TlGd.sub.2Cl.sub.7:yCe scintillator is grown at a low temperature as compared with generally used scintillators, costs may be remarkably reduced when the scintillator is manufactured. The quartz ampoule containing a sample was machined such that a seed crystal of a single crystal that will be grown may be easily generated by making one end of the quartz ampoule sharp. The grown single crystal was cut into a specific size and all the sections thereof were polished on polishing cloth by using aluminum oxide (Al.sub.2O.sub.3) to investigate scintillation characteristics.
[0072] A relative optical yield and a fluorescent damping time at a room temperature were measured by a pulse height analysis system using RBCs photoelectron multiplier (Electron tube Ltd. D726Uk). A signal exiting from the photoelectron multiplier was analyzed by using a ROOT program after being amplified by using an amplifier (×10, ×100) manufactured directly by the inventor(s) and passing through a 400 MHz flash analog to digital converter (FADC) and a field programmable gate array (FPGA) was used as a trigger.
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Embodiment 2
[0076] A thallium rare earth halide (Tl.sub.aCe.sub.bBr.sub.c) scintillation crystal was manufactured while taking thallium halide (TlBr) and trivalent rare earth halide (CeBr.sub.3) as a matrix. In order to manufacture a thallium rare earth halide scintillator, after thallium halide (TlBr) and rare earth halide (CeBr.sub.3) are mixed at a mole fraction of 1:2, it was sealed in a quartz ampoule into a vacuum state of about 10.sup.−5 torr. The sealed quartz ampoule was grown to a thallium rare earth halide (TlCe.sub.2Br.sub.7) scintillator in a Bridgman electric furnace. Then, a crystal growth condition of a product of the descent speed of the ampoule and the temperature gradient of the crystal growth part was 0.05˜2.0° C./hr.
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Embodiment 3
[0078] A thallium rare earth halide (Tl.sub.aY.sub.bCl.sub.c:yCe) scintillation crystal was manufactured by doping a matrix material of thallium halide (TlCl) and trivalent rare earth halide (YCl.sub.3) with cerium. In order to manufacture a thallium rare earth halide scintillator, after thallium halide and rare earth halide are mixed at a mole fraction of 1:2 and a specific amount of cerium chloride is mixed, it was sealed in a quartz ampoule into a vacuum state of about 10.sup.−5 torr. The scintillator was manufactured by making the mole fraction of cerium chloride (CeCl.sub.3) 0, 1 mol % with respect to the mole fraction of thallium. The sealed quartz ampoule was grown to a thallium rare earth halide (TlY.sub.2Cl.sub.7:yCe) scintillator in a Bridgman electric furnace. Then, a crystal growth condition of a product of the descent speed of the ampoule and the temperature gradient of the crystal growth part was 0.05˜2.0° C./hr, and the melt temperature was 550° C.
[0079] When a single crystal is grown through a Bridgman method, the temperature and the temperature gradient of a single crystal growth point, and the descent speed of the sample are very important. The temperature of the single crystal growth point has a close relationship with the melt temperature of the sample. Because a single crystal of a Tl.sub.aA.sub.bB.sub.c:yCe scintillator is grown at a low temperature as compared with generally used scintillators, costs may be remarkably reduced when the scintillator is manufactured. The quartz ampoule containing an example are machined such that a seed crystal of a single crystal that will be grown may be easily generated by making one end of the quartz ampoule sharp. The grown single crystal was cut into a specific size and all the sections thereof were polished on polishing cloth by using aluminum oxide (Al.sub.2O.sub.3) to investigate scintillation characteristics.
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[0081] As an application example of a scintillator, a positron emission tomography (PET) device has to have a high gamma detection efficiency and high scintillation output characteristics of a scintillator radioactive ray sensor to reduce an exposure dose of the patient and obtain a meaningful radioactive image and has to have quick fluorescent damping time characteristics because two gamma rays generated by a pair annihilation of a positron have to be measured at the same time. The optical yield of the scintillator according to the embodiment was two times as high as that of a common LYSO (Lu.sub.2(1-x)Y.sub.2xSiO.sub.5:Ce) scintillator, and the scintillator showed relatively quick characteristics of a fluorescent damping time of 97 ns when the concentration of Ce ions is 1 mol %. From the above-mentioned characteristics, it can be seen that the scintillator according to the embodiment of the present invention is useful in a single photon emission tomography device and a positron emission tomography device. Because the light emission wavelength area well coincides with the photon efficiency characteristics of a photodiode, a photodiode instead of a photoelectron multiplier may be utilized as a light receiving element. Because a PET sensor may be miniaturized by using a photodiode, a location resolution may be improved when the PET sensor is used as a radioactive image sensor.
[0082] Lu-based scintillators (LSO, Lu.sub.2SiO.sub.5:Ce) (LYSO, Lu.sub.2(1-x)Y.sub.2xSiO.sub.5:Ce) used as PET scintillators have high densities and effective atomic numbers and short fluorescent damping times, but it is difficult to grow a single crystal because a crystal growth temperature is very high, energy resolution characteristics are bad, and there exists a background radioactive ray by natural radioisotopes. GSO (Gd.sub.2SiO.sub.5:Ce) has a low optical yield, bad energy resolution characteristics, and a high crystal growth temperature.
[0083] The scintillator according to an embodiment of the present invention takes thallium as a matrix, and because the atomic number of thallium is a very high number of 81, the detection efficiency of thallium for an radioactive ray, such as an X-ray, a gamma ray, an ultraviolet ray, an alpha ray, or a beta ray is high so that an exposure dose for a human body may be reduced when the scintillator is used in a medical field. Further, manufacturing costs of the scintillator may be reduced because a scintillation crystal growth temperature is low and the number of elements is small so that a single crystal may be easily grown, and the scintillator may be applicable in a field, such as a positron emission tomography device, which requires quick time characteristics because fluorescent damping time is short.
[0084] Further, the scintillator according to the embodiment may be used in computed tomography (CT), positron emission tomography (PET), single photon emission computed tomography (SPECT), or an anger camera because the light emission wavelength range thereof is well matched with photon efficiency characteristics of a photodiode and the scintillator has a quick fluorescent damping time and a high optical yield. In particular, the embodiment of the present invention is suitable for positron emission tomography (PET) because the scintillator has a short fluorescent damping time and a high optical yield. Further, the scintillator material may be used for a radioactive ray senor for measuring radioactive rays of various kinds, such as an ultraviolet ray, an electron ray, alpha particles, and beta particles.
[0085] On the other hand, the present invention discloses a thallium alkaline earth halide (Tl.sub.aA.sub.bB.sub.c:yEu) scintillation crystal doped with an activator (for example, europium) based on thallium (Tl), an alkaline earth metal element (Ca, Ba, or Sr), or a halogen element (Cl, Br, or I). A process of making a single crystal of a scintillator based on thallium is a process that is very difficult to perform and requires a high-level technology, and the inventor(s) succeeded in developing an advance material scintillator having excellent characteristics based on thallium and alkaline earth metal elements and growing the scintillator into a single crystal through long-term studies and experiments.
[0086] The inventor(s) could manufacture an advanced scintillator material that has never been present until now, through a growing temperature (melt temperature) condition and a crystal growth condition (a correlation between an ampoule descent speed and a temperature gradient of a crystal growth part) of the scintillator. The scintillator according to the embodiment of the present invention is a scintillation material, of which the chemical formula is Tl.sub.aA.sub.bB.sub.c:yEu, and here, A is at least one alkaline earth metal element selected from the group including Ca, Ba, and Sr and B is at least one halogen element selected from the group including Cl, Gr, and I. The mole fraction a:b:c of thallium, an alkaline earth metal element, and a halogen element may be 1:2:5 or 1:1:3. y is a mole fraction (concentration) of ions of an activator (Eu) that is doped with impurities to generate a scintillation phenomenon, and may have a value of more than 0 and not more than 50 mol % for a proper amount of scintillation.
[0087] The scintillator according to an embodiment of the present invention may be manufactured through a process of manufacturing a matrixmatrix material by mixing thallium halide and alkaline earth halide at a mole fraction of 1:2 or 1:1 and doping the matrix material with an activator including europium halide and growing the matrix material into a single crystal. As a result of many experiments and trials and errors, the inventor(s) could come to know that an ampoule descent speed and a temperature gradient of a crystal growth part complexly influence the growth of crystals significantly when the mixture of the matrix material and the activator are grown into a single crystal, and a growth condition of the crystal growth part, that is, a melt temperature and a product of an ampoule descent speed and a temperature gradient of the crystal growth part has to be set to a specific range to grow the mixture of a thallium-based matrix material and an activator into a single crystal.
[0088] In an embodiment of the present invention, it is preferable that the product of the ampoule descent speed and the temperature gradient of the crystal growth part is set to a range of 0.05˜2.0° C./hr, and this is because productivity is bad when the product of the ampoule descent speed and the temperature gradient of the crystal growth part is less than 0.05° C./hr, and crystals are broken or crystal characteristics deteriorate when the product of the ampoule descent speed and the temperature gradient of the crystal growth part is more than 2.0° C./hr so that an amount of scintillation and fluorescent damping time characteristics deteriorate. Further, it is preferable that the melt temperature of the mixture of the matrix material and the activator is set to a range of 510 to 840° C. Then, the melt temperature may be properly adjusted according to an alkaline earth metal element or a halide element. When the melt temperature of an oxide scintillator according to the related art is generally 1,000 to 2,000° C. or higher, the scintillator according to the embodiment has an advantage of reducing process costs because a scintillator may be grown in a relatively low melt temperature condition.
[0089] The scintillator according to the embodiment may be utilized in various application fields for detecting radioactive rays. The radioactive ray detection efficiency is determined according to an interaction between the input radioactive ray and the scintillator detector. It is a photoelectric effect that is most important in detection efficiency when an X-ray is detected, and because the photoelectric effect is proportional to the fourth to fifth power of the atomic number of the scintillator material, a detection efficiency for an X-ray or a gamma ray rapidly increases as the atomic number of the material becomes higher. Accordingly, the present invention developed an advanced scintillator having a high detection efficiency for a radioactive ray, in particular, an X-ray or a gamma ray based on thallium having an atomic number of 81.
[0090] The optical yield is a value related to the strength of a detection signal generated when the scintillator detects a radioactive ray, and because a signal to noise ratio (SNR) increases as the optical yield becomes higher, an excellent measurement result may be obtained with a small amount of rays. In particular, an exposure dose of a human body may be reduced when the scintillator is used as an image sensor for medical radioactive rays. The elements that determine an optical yield of the scintillator include the kind and the concentration of doped impurities, and crystal characteristics and transparency of the single crystal. In the scintillator, particularly, the crystal characteristics and transparency of the scintillator are a very important element. Generally, a material of a high atomic number has a low transparency, but according to the present invention, a scintillator having a transparency that shows an excellent optical yield may be developed by optimizing the kinds, the mole fractions, the crystal growth conditions, and the atmospheres of a main substance that forms the matrix material of the scintillator and the activator doped as impurities.
[0091] When the crystal structure of the scintillation crystal is a monoclinic system or a hexagonal system or a growth temperature of the crystal structure is high, it is difficult to grow a single crystal of a high quality, the price of the scintillation crystal is high, and a single crystal is broken easily to a specific crystal surface even though the single crystal is grown. Further, damping time characteristics may be longer because of emission of light due to self-trap excitation if the crystal characteristics and transparency deteriorate, and an output signal decreases because the emitted light generated by radioactive rays is absorbed in the scintillator. Accordingly, it is preferable that a crystal structure, such as a tetragonal system or a hexagonal system, which is advantageous for growth of crystals is selected when a single crystal is grown. Further, it is very important to optimize a crystal growth condition. All combinations of elements are not grown to a single crystal, and a process of making a single crystal having excellent scintillation characteristics is a process that is very difficult and requires a high technology even though they are materials that are grown to a single crystal.
[0092] Based on many trials and errors, experiences, and theories, after selecting candidate elements through the radius of ions, the atom numbers, and the melting points of the atoms, and the phase diagram, the X-ray diffraction (XRD), and the differential thermal analysis (DSC) of the crystal, the inventor(s) succeeded in developing a halide scintillation crystal based on a thallium alkaline earth metal element having excellent scintillation characteristics through experiments using various combinations of elements and established crystal growth conditions, such as a temperature condition, an atmosphere, and a crystal growth speed when the scintillation crystal is grown. Because the wavelength of the emitted light is related to an energy level of doped impurities, it is required to select a material that is well suitable for photon efficiency characteristics of a photoelectron multiplier or a photodiode. Accordingly, thallium, an alkaline earth metal element, or a halogen element was selected as a main substance of the matrix, and europium ions were selected as doping impurities. The europium ions have a high optical yield through 4f5d transition, and the energy level was well matched with the material used as a matrix.
[0093] Because the thallium alkaline earth metal element based halide scintillator according to the present invention easily grows a single crystal, has a high optical yield, and has a main substance of Tl, the atomic number of which is a very high number of 81, it has a high detection efficiency for an X-ray or a gamma ray so that an exposure dose for a human body may be reduced when it is utilized in a medical image field. Accordingly, the scintillator according to the embodiment may be utilized as an advance material scintillator for various medical radioactive ray images, such as CT, PET, SPECT, and a gamma camera, and may be utilized as a radioactive ray sensor for various industrial fields.
[0094]
[0095] Then, an end of the quartz ampoule, in which a sample is contained, may be machined to be sharp in advance such that a seed crystal of the single crystal, which will be grown in the Bridgman electric furnace is easily generated. When a single crystal is grown through a Bridgman method, a temperature of a single crystal growth point, a temperature gradient, and a descent speed of the sample is very important, and the temperature of the single crystal growth point is closely related to a melt temperature of the sample. The inventor(s) identified through experiments that it is effective in growing a single crystal of a scintillator based on thallium having excellent characteristics to make a product of the descent speed of the ampoule and the temperature gradient of the crystal growth part.
[0096] Referring to
[0097] In an aspect of productivity, it is preferable that the descent speed of the ampoule is set to 0.1 mm/hr or higher. Then, although being different according to the descent speed of the ampoule, the product of the descent speed of the ampoule and the temperature gradient of the crystal growth part may be set to 0.05˜2.0° C./hr and the temperature gradient of the crystal growth part may be set to a range of 30° C./cm or lower. In the embodiment of the present invention, the melt temperature may be 510 to 840° C. The melt temperature is a temperature that is much lower than a melt temperature for growing scintillators used in the related art, and according to the present invention, the costs may be remarkably lowered when a scintillator is manufactured because a single crystal may be grown at a low temperature of 510 to 840° C.
Embodiment 4
[0098] A thallium alkaline earth halide (Tl.sub.aCa.sub.bCl.sub.c:yEu) scintillation crystal was manufactured by doping a matrix material of thallium halide (TlCl) and 2 divalent alkaline earth halide (CaCl.sub.2) with europium (EuCl.sub.3). In order to manufacture a thallium alkaline earth halide scintillator, after thallium halide (TlCl) and alkaline earth halide (CaCl.sub.2) are mixed at a mole fraction of 1:2 and a specific amount of europium chloride (EuCl.sub.3) is mixed, it was sealed in a quartz ampoule into a vacuum state of about 10.sup.−5 torr. The mole fraction of europium chloride (EuCl.sub.3) was 0.5 m %. The sealed quartz ampoule was grown to a thallium alkaline earth halide (TlCa.sub.2Cl.sub.5:yEu) scintillator in a Bridgman electric furnace. Then, a crystal growth condition of a product of the descent speed of the ampoule and the temperature gradient of the crystal growth part was 0.05˜2.0° C./hr.
[0099] When a single crystal is grown through a Bridgman method, the temperature and the temperature gradient of a single crystal growth point, and the descent speed of the sample are very important. The temperature of the single crystal growth point has a close relationship with the melt temperature of the sample. Because a single crystal of a TlCa.sub.2Cl.sub.5:yEu scintillator is grown at a low temperature as compared with generally used scintillators, costs may be remarkably reduced when the scintillator is manufactured. The quartz ampoule containing an example are machined such that a seed crystal of a single crystal that will be grown may be easily generated by making one end of the quartz ampoule sharp. The grown single crystal was cut into a specific size and all the sections thereof were polished on polishing cloth by using aluminum oxide (Al.sub.2O.sub.3).
[0100]
Embodiment 5
[0101] A thallium alkaline earth halide (Tl.sub.aCa.sub.bCl.sub.c:yEu) scintillation crystal was manufactured by doping a matrix material of thallium halide (TlCl) and 2 divalent alkaline earth halide (CaCl.sub.2) with europium (EuCl.sub.3). After thallium halide (TlCl) and alkaline earth halide (CaCl.sub.2) are mixed at a mole fraction of 1:1 and a specific amount of europium chloride (EuCl.sub.3) is mixed, it is sealed in a quartz ampoule into a vacuum state of about 10.sup.−5 torr. The mole fraction of europium chloride (EuCl.sub.3) was 0.5 m %. The sealed quartz ampoule was grown to a thallium alkaline earth halide (TlCaCl.sub.3:Eu.sub.0.005) scintillator in a Bridgman electric furnace. Then, a crystal growth condition of a product of the descent speed of the ampoule and the temperature gradient of the crystal growth part was 0.05˜2.0° C./hr.
[0102]
Embodiment 6
[0103] A thallium alkaline earth halide (Tl.sub.aSr.sub.bBr.sub.c) scintillation crystal was manufactured while taking thallium halide (TlBr) and divalent alkaline earth halide (SrBr.sub.2). After thallium halide (TlBr) and alkaline halide (SrBr.sub.2) are mixed at a mole fraction of 1:2, they are sealed in a quartz ampoule at a vacuum state of about 10.sup.−5 torr. The sealed quartz ampoule was grown to a thallium alkaline earth halide (TlSr.sub.2Br.sub.5) scintillator in a Bridgman electric furnace. Then, a crystal growth condition of a product of the descent speed of the ampoule and the temperature gradient of the crystal growth part was 0.05˜2.0° C./hr.
[0104]
[0105]
Embodiment 7
[0106] A thallium alkaline earth halide (Tl.sub.aSr.sub.bI.sub.c:yEu) scintillation crystal was manufactured by doping a matrix material of thallium halide (TlCl) and 2 divalent alkaline earth halide (SrI.sub.2) with europium (EuI.sub.3). After thallium halide (TlCl) and alkaline earth halide (SrI.sub.2) are mixed at a mole fraction of 1:2 and a specific amount of europium chloride (EuI.sub.3) is mixed, it is sealed in a quartz ampoule into a vacuum state of about 10.sup.−5 torr. The mole fraction of europium chloride (EuI.sub.3) was 0.5 m %. The sealed quartz ampoule was grown to a thallium alkaline earth halide (TlSr.sub.2I.sub.5:yEu) scintillator in a Bridgman electric furnace. Then, a crystal growth condition of a product of the descent speed of the ampoule and the temperature gradient of the crystal growth part was 0.05˜2.0° C./hr.
[0107]
Embodiment 8
[0108] A thallium alkaline earth halide (Tl.sub.aSr.sub.bI.sub.c) scintillation crystal was manufactured while taking thallium halide (TlI) and divalent alkaline earth halide (SrI.sub.2). After thallium halide (TlI) and alkaline halide (SrI.sub.2) are mixed at a mole fraction of 1:2, they are sealed in a quartz ampoule at a vacuum state of about 10.sup.−5 torr. The sealed quartz ampoule was grown to a thallium alkaline earth halide (TlSr.sub.2I.sub.5) scintillator in a Bridgman electric furnace. Then, a crystal growth condition of a product of the descent speed of the ampoule and the temperature gradient of the crystal growth part was 0.05˜2.0° C./hr.
Embodiment 9
[0109] A thallium alkaline earth halide (Tl.sub.aBa.sub.bI.sub.c:yEu) scintillation crystal was manufactured by doping a matrix material of thallium halide (TlCl) and 2 divalent alkaline earth halide (TlI) with europium (BaI.sub.2). After thallium halide (TlCl) and alkaline earth halide (BaI.sub.2) are mixed at a mole fraction of 1:2 and a specific amount of europium chloride (EuI.sub.3) is mixed, it is sealed in a quartz ampoule into a vacuum state of about 10.sup.−5 torr. The mole fraction of europium chloride (EuI.sub.3) was 0.5 m %. The sealed quartz ampoule was grown to a thallium alkaline earth halide (TlBa.sub.2I.sub.5:yEu) scintillator in a Bridgman electric furnace. Then, a crystal growth condition of a product of the descent speed of the ampoule and the temperature gradient of the crystal growth part was 0.05˜2.0° C./hr.
Embodiment 10
[0110] A thallium alkaline earth halide (Tl.sub.aBa.sub.bBr.sub.c) scintillation crystal was manufactured while taking thallium halide (TlBr) and divalent alkaline earth halide (BaBr.sub.2). After thallium halide (TlBr) and alkaline halide (BaBr.sub.2) are mixed at a mole fraction of 1:2, they are sealed in a quartz ampoule at a vacuum state of about 10.sup.−5 torr. The sealed quartz ampoule was grown to a thallium alkaline earth halide (TlBa.sub.2Br.sub.5) scintillator in a Bridgman electric furnace. Then, a crystal growth condition of a product of the descent speed of the ampoule and the temperature gradient of the crystal growth part was 0.05˜2.0° C./hr.
Embodiment 11
[0111] A thallium alkaline earth halide (Tl.sub.aBa.sub.bCl.sub.c:yEu) scintillation crystal was manufactured by doping a matrix material of thallium halide (TlCl) and 2 divalent alkaline earth halide (CaCl.sub.2) with europium (BaCl.sub.2). After thallium halide (TlCl) and alkaline earth halide (BaCl.sub.2) are mixed at a mole fraction of 1:2 and a specific amount of europium chloride (EuCl.sub.3) is mixed, it is sealed in a quartz ampoule into a vacuum state of about 10.sup.−5 torr. The mole fraction of europium chloride (EuCl.sub.3) was 0.5 m %. The sealed quartz ampoule was grown to a thallium alkaline earth halide (TlBa.sub.2Cl.sub.5:yEu) scintillator in a Bridgman electric furnace. Then, a crystal growth condition of a product of the descent speed of the ampoule and the temperature gradient of the crystal growth part was 0.05˜2.0° C./hr.
[0112]
[0113] The scintillator according to an embodiment of the present invention takes thallium as a matrix, and because the atomic number of thallium is a very high number of 81, the detection efficiency of thallium for an radioactive ray, such as an X-ray, a gamma ray, an ultraviolet ray, an alpha ray, or a beta ray is high so that an exposure dose for a human body may be reduced when the scintillator is used in a medical field. Further, the present invention may reduce manufacturing costs by easily growing a scintillation crystal and may be applied to fields that require quick time characteristics, such as a positron emission tomography device. Further, because the range of the wavelength of the emitted light of the scintillator according to the embodiment is well matched with the positron efficiency characteristics, the material of the scintillator may be used as a radioactive sensor for measuring radioactive rays of various kinds, such as an ultraviolet ray, an electron ray, alpha particles, and beta particles. The radioactive image equipment may be used for computed tomography (CT), positron emission tomography (PET), single photon emission tomography, or an anger camera.
[0114] It is noted that the above embodiments are suggested for understanding of the present invention and do not limit the scope of the present invention, and various modifiable embodiments also fall within the scope of the present invention. It should be understood that the technical protection range of the present invention has to be determined by the technical spirit of the claims, and the technical protection range of the present invention is not limited to the lexical meaning of the claims but reaches even to the equivalent inventions.