JPWO2015037726A1 - Scintillator crystal material, single crystal scintillator, radiation detector, imaging device and non-destructive inspection device - Google Patents

Abstract

A scintillator crystal material represented by (Gd1-x-yLaxCey) 2Si2O7, wherein x ranges from 0.2 ≦ x ≦ 0.45, and y ranges from 0.0001 ≦ y ≦ 0.05. [Selection] Figure 10

Description

  The present invention relates to a scintillator crystal material, a single crystal scintillator, a radiation detector, an imaging device, and a nondestructive inspection device.

  A scintillator is a substance that emits scintillation light by irradiating radiation with an energy that causes ionization, such as alpha rays, gamma rays, X-rays, or neutron rays, and these are combined with a photodetector as a radiation detector. Used. Examples of such a radiation detector include a positron emission tomography (PET) apparatus, a single photon emission tomography (SPECT), and various types of radiation in the field of high energy physics. Widely used in measuring devices and resource exploration devices.

  For example, in high energy physics and PET imaging systems, images are created based on the interaction between scintillators and radiation generated by radioactive decay. Here, in the PET imaging system, gamma rays resulting from the interaction of positrons in the subject and the corresponding electrons are incident on the scintillator and converted into photons that can be detected by the photodetector. The photons emitted from the scintillator are supplied by a photodiode (PD), a silicon photomultiplier (Si-Photomultiplier: Si-PM), a photomultiplier tube (Photomultiplier tube: PMT), or other photodetector. Can be detected using.

  PMT has high quantum efficiency (efficiency for converting photons into electrons (current signals)) in a wavelength region near 400 nm, and is mainly used in combination with a scintillator having an emission peak wavelength near 400 nm. For the scintillator array in which the scintillators are arranged in an array, a position sensitive PMT (PS-PMT) or the like is used in combination. Accordingly, it is possible to determine in which pixel of the scintillator array the photon is detected from the centroid calculation.

  On the other hand, semiconductor detectors such as photo diodes, avalanche photo diodes (APDs), and silicon photomultipliers have a wide range of applications, particularly in radiation detectors and imaging devices. Various semiconductor photodetectors are known.

  For example, some APDs composed of silicon semiconductors have quantum efficiencies exceeding 50% in the wavelength band from 350 nm to 900 nm, whereas the quantum efficiency of PMT is 45% at the maximum. Is expensive. Among the above wavelength bands, the wavelength band with high sensitivity is 500 nm to 700 nm, and the sensitivity is highest around 600 nm, and the quantum efficiency is about 80%.

  Therefore, these semiconductor photodetectors are used in combination with a scintillator having an emission peak wavelength between 350 nm and 900 nm centering around 600 nm. Similar to PMT, PD, APD, and Si-PM also have a PD array having position detection sensitivity, a position-sensitive avalanche photodiode (PSAPD), and an Si-PM array.

  These elements can also determine in which pixel of the scintillator array the photons were detected. Furthermore, for short-wavelength light emitting scintillators of 350 nm or less, there is a radiation detector that performs readout by a silicon semiconductor by converting the scintillator light into light in a wavelength region where the silicon semiconductor is sensitive, such as by using a wavelength conversion element. It is feasible.

  Scintillators suitable for these radiation detectors have high density from the point of detection efficiency, high atomic number (high photoelectric absorption ratio), high light emission from the point of high energy resolution, and the need for high-speed response Therefore, it is desired that the fluorescence lifetime (fluorescence decay time) is short.

  In addition, in recent systems, multiple scintillators need to be closely arranged in a long and narrow shape (for example, about 5 mm x 5 mm x 30 mm for PET) to increase the number of layers and increase the resolution. The price is also an important selection factor. It is also important that the emission wavelength of the scintillator matches the wavelength range where the detection sensitivity of the photodetector is high.

Currently, a preferred scintillator applied to various radiation detectors is a pyrosilicate scintillator Ce: Gd ₂ Si ₂ O ₇ . The scintillator has the advantages that it is chemically stable, has no cleavage or deliquescence, is excellent in workability, and has a high light emission amount. For example, a pyrosilicate scintillator described in Non-Patent Document 1 using light emission from the Ce ³⁺ 4f5d level has a short fluorescence lifetime of about 80 ns or less and a high light emission amount.

  However, on the other hand, as described in Non-Patent Document 1, because of the peritectic composition in the phase diagram, there is a problem that it is difficult to obtain a large transparent body because single crystal growth from the melt cannot be performed. Therefore, as described in Patent Document 1, it was previously assumed that a small amount of pyrosilicate scintillator was contained in a matrix such as glass.

  In the pyrosilicate scintillator described in Patent Document 2 and Non-Patent Document 2, attempts have been made to obtain a harmonic melt composition by replacing Ce with a site of a rare earth element. This makes it possible to produce a large single crystal by a melt growth method such as the floating zone method, the Czochralski method (pulling method), the micro pulling method, or the Bridgman method. However, when Ce is increased at the rare earth element site, there is a problem (concentration quenching) that the amount of light emission is drastically reduced.

In (Gd _1-x Ce _x ) ₂ Si ₂ O ₇ described in Patent Document 2, it is said that 0.1 <x <0.3 is desirable from the viewpoint of stable crystal growth, although the light emission amount is reduced. Still, an example is described in which a single crystal is taken out of the polycrystallized material.

  Non-Patent Document 3 describes an example of succeeding in taking out a single crystal by a floating zone method by substituting Ce for La to suppress a drastic decrease in light emission (concentration quenching) and by using a harmonic melting composition. Has been. However, although a single crystal can be obtained, its growth is still difficult, and it has been a challenge to grow a single crystal having a large size for application to a production method applied to crystal production in the industrial field.

Japanese Patent No. 3870418 JP 2009-074039 A

S. Kawamura, JHKaneko, M. Higuchi, T. Yamaguchi, J. Haruna, Y, Yagi, K. Susa, F. Fujita, A. Homma, S. Nishiyama, H. Ishibashi, K. Kurashige and M. Furusaka , IEEE Nuculear Science Symposium Conference Record, San Diego, USA, 29 October −5 November 2006, pp. 1160-1163. Sohan.Kawamura, Junichi H.Kaneko, Mikio Higuchi, Jun Haruna, Shohei Saeki, Fumiyuki Fujita, Akira Homma, Shusuke Nishiyama, Shunsuke Ueda, Kazuhisa Kurashige, Hiroyuki Ishibashi, and Michihiro Furusaka, IEEE TRANSACTIONS ON NUCLEAR SCIENCE, VOL. 56, NO. 1, FEBRUARY 2009. Akira Suzuki, Shunsuke Kurosawa, Toetsu Shishido, Jan Pejchal, Yuui Yokota, Yoshisuke Futami, and Akira Yoshikawa, Applied Physics Express 5 (2012) 102601-1 −102601-3.

  The crystal material used as a scintillator is required to have a high light emission amount and a short fluorescence lifetime, and from the viewpoint of cost to be widely applied to society, it has no cleaving property or deliquescence, that is, It is also required to have easy processability and mass productivity.

  The present invention has been made in view of the above, and is a scintillator crystal material having a high light emission amount and a short fluorescence lifetime, a single crystal scintillator having no cleavage and deliquescence using the scintillator crystal material, and It is an object of the present invention to provide a radiation detector, an imaging device, and a nondestructive inspection device that are used.

In order to solve the above-described problems and achieve the object, the inventors have made intensive efforts so far and have studied and led to the next invention. That is, the scintillation counter crystal material according to the present _invention are represented by _{(Gd 1-x-y La} x Ce y) 2 Si 2 O 7, the range of x is 0.2 ≦ x ≦ 0.45, the range of y It is a scintillator crystal material satisfying 0.0001 ≦ y ≦ 0.05.

  In the scintillator crystal material according to the present invention, it is further preferable that the range of x is 0.22 ≦ x ≦ 0.35 and the range of y is 0.0005 ≦ y ≦ 0.02.

  The scintillator crystal material according to the present invention, in the above invention, emits scintillation light by irradiation of radiation, and the predetermined fluorescent component contained in the scintillation light has a fluorescence wavelength of 200 nm to 900 nm and its fluorescence lifetime Is 1000 nanoseconds or less.

  In the scintillator crystal material according to the present invention, the scintillator crystal material emits scintillation light by irradiation of radiation in the above invention, and the predetermined fluorescent component contained in the scintillation light has a fluorescence wavelength of 300 nm to 700 nm and its fluorescence lifetime. Is 80 nanoseconds or less.

  The single crystal scintillator according to the present invention is characterized by comprising the scintillator crystal material according to the present invention.

  A radiation detector according to the present invention includes the scintillator made of the scintillator crystal material or the single crystal scintillator of the present invention, and a photodetector that receives the scintillation light from the scintillator.

  An imaging apparatus according to the present invention includes the radiation detector according to the above invention.

  In addition, a nondestructive inspection apparatus according to the present invention includes the radiation detector according to the above invention.

  According to the present invention, it is possible to provide a scintillator crystal material that has a high light emission amount and a fluorescence lifetime and is easy to grow a single crystal, and a radiation detector, an imaging device, and a nondestructive inspection device using the same.

FIG. 1 is a view showing a photograph of Example 1 after crystal growth. FIG. 2 is a view showing a photograph of Example 2 after crystal growth. FIG. 3 is a view showing a photograph of Example 3 after crystal growth. FIG. 4 is a view showing a photograph of Example 4 after crystal growth. FIG. 5 is a view showing a photograph of Example 5 after crystal growth. 6 is a view showing a photograph of Example 6 after crystal growth. FIG. 7 is a view showing a photograph of the first comparative example after crystal growth. FIG. 8 is a view showing a photograph of the comparative example 2 after crystal growth. FIG. 9 is a diagram showing a light emission characteristic profile of radioluminescence. FIG. 10 is a diagram showing a pulse height distribution spectrum obtained by irradiation with ¹³⁷ Cs gamma rays (662 keV). FIG. 11 is a diagram showing a fluorescence decay curve profile of Example 1. FIG.

  Hereinafter, embodiments of a scintillator crystal material, a single crystal scintillator, a radiation detector, an imaging device, and a nondestructive inspection device according to the present invention will be described in detail. Note that the present invention is not limited to the embodiments.

Scintillator crystal material according to the embodiment of the present _invention are represented by _{(Gd 1-x-y La} x Ce y) 2 Si 2 O 7, the range of x is 0.2 ≦ x ≦ 0.45, the y The range is 0.0001 ≦ y ≦ 0.05.

  The scintillator crystal material preferably further has an x range of 0.22 ≦ x ≦ 0.35 and a y range of 0.0005 ≦ y ≦ 0.02.

  As a result, the scintillator crystal material according to the present embodiment is a crystal material having a high emission amount of scintillation light generated by radiation irradiation and a short fluorescence lifetime.

In addition, although a known pyrosilicate scintillator is expected to have a high light emission amount, it does not become a harmonic melt composition unless Ce or La are replaced with sites of rare earth elements, so that it is very difficult to produce a transparent bulk body. There is a problem of becoming. However, on the other hand, there is a problem that the effective atomic number Z _eff is lowered by increasing La at the site of the rare earth element. On the other hand, the crystal material according to the present embodiment can solve these problems and can be applied to a production method applied to crystal production in an industrial field such as a micro-pulling-down method or a Czochralski method.

In addition, in response to the problem that the effective atomic number Z _eff is low, the pyrosilicate Si site is not limited to only Si, but may be replaced with another pyrochlore oxide substituted with Ge, Hf, or the like. In this case, the same effect as that according to the present invention is expected.

  Furthermore, the scintillator crystal material according to the present embodiment can easily grow a single crystal, and can be used as a radiation detector by combining a single crystal scintillator with a photodetector capable of receiving scintillation light. Become. Furthermore, it can be used as a radiation measuring apparatus or a resource exploration apparatus as a nondestructive inspection apparatus provided with these radiation detectors as radiation detectors.

  In addition, for the scintillator crystal material and the single crystal thereof according to the present embodiment, the predetermined fluorescent component contained in the scintillation light has a fluorescence wavelength of 200 nm to 900 nm and a fluorescence lifetime of 1000 nanoseconds or less. It can be. As described above, since the fluorescence lifetime is short, the sampling time for fluorescence measurement can be shortened, and the high time resolution, that is, the sampling interval can be reduced. In addition, by realizing high time resolution, the number of samplings per unit time can be increased. Such a crystal material having a short-lived emission can be suitably used as a scintillator for detecting radiation with a high-speed response for PET, SPECT and CT which are imaging devices.

  In addition, since the fluorescence peak wavelength of the fluorescence component is in the range of 250 nm to 900 nm, it can be detected in combination with a semiconductor photodetector such as PD, APD, or Si-PM composed of a silicon semiconductor. In particular, when the fluorescence peak wavelength of the fluorescent component is 400 nm or less, it is effective to use a wavelength conversion element to convert the wavelength to a wavelength of 300 nm to 900 nm, that is, a wavelength in a region where the wavelength sensitivity of the above-described photodetector is sufficient. .

  As the wavelength conversion element, for example, one using a plastic wavelength conversion optical fiber (for example, Y11 (200) MS manufactured by Kuraray Co., Ltd.) can be used. Further, the type of the photodetector to be combined can be appropriately used according to the fluorescence peak wavelength or the like. For example, PMT or PS-PMT may be used.

  Further, in the crystal material according to the present embodiment, if the fluorescence lifetime of the fluorescent component contained in the scintillation light is 80 nanoseconds or less and the fluorescence peak wavelength is in the range of 300 nm to 700 nm, further high resolution In addition, it is possible to detect scintillation light with high sensitivity. Adjustment of the fluorescence lifetime and the fluorescence peak wavelength can be realized by adjusting the composition of the crystal material. For example, the fluorescence lifetime can be shortened by increasing the Ce concentration.

  Further, in the scintillator crystal material according to the present embodiment, the light emission amount of the fluorescent component in the range of the ambient temperature from room temperature to 150 degrees Celsius when the light emission amount of the fluorescent component when the ambient temperature is 0 degrees Celsius is used as a reference. The attenuation ratio from the reference can be less than 20%. Therefore, the scintillator crystal material according to the present embodiment can be very useful as a scintillator crystal material used in a high-temperature environment because the attenuation of light emission can be reduced even in a high-temperature environment.

  A method for manufacturing a single crystal crystal material according to the present embodiment will be described below. In any method for producing a single crystal, a general oxide raw material can be used as a starting material, but when used as a single crystal for a scintillator, it has a high purity of 99.99% (4N) or more. It is particularly desirable to use raw materials. These starting materials are weighed and mixed so as to have a target composition at the time of melt formation, and used as a crystal growth material.

  Further, among these starting materials, those starting with as few impurities as possible other than the intended composition are particularly preferred. In particular, it is preferable to use a starting material that contains as little as possible an element that emits light in the vicinity of the scintillation light wavelength of the crystalline material or an element that easily changes its valence.

Crystal growth is preferably performed in an inert gas atmosphere such as Ar or N ₂ . Alternatively, a mixed gas of an inert gas and oxygen gas may be used. However, when the crystal is grown in the mixed gas atmosphere, the oxygen partial pressure is preferably 2% or less for the purpose of preventing the crucible from being oxidized.

  However, when a production method that does not use a crucible, such as the floating zone method, is used, the oxygen partial pressure can be set up to 100%. Note that oxygen gas, inert gas, and a mixed gas of oxygen gas and inert gas can be used in a subsequent process such as annealing after crystal growth. In the subsequent process, when a mixed gas is used, the oxygen partial pressure is not limited to 2% or less, and any mixture ratio from 0% to 100% oxygen partial pressure may be used.

  As a method for producing a single crystal of a crystal material according to the present embodiment, in addition to the micro pulling method, the Czochralski method (pulling method), the Bridgman method, the band melting method (zone melt method), and the edge limited thin film Examples thereof include a supply crystal growth (EFG) method and a floating zone method, but are not limited thereto, and various crystal growth methods can be used.

  In order to obtain a large single crystal, the Czochralski method or the Bridgman method is preferable. By using a large single crystal, it is possible to improve the yield of the single crystal and relatively reduce the processing loss. Therefore, compared with the method of taking out a single crystal from polycrystallized as described in Patent Document 2, a low-cost and high-quality crystal material can be obtained. However, the scintillator crystal material according to the present embodiment is not limited to a single crystal, and may be a polycrystalline sintered body such as ceramics.

  On the other hand, if only a small single crystal is used as the scintillator single crystal, there is no or little post-processing, so the floating zone method, the zone melt method, the EFG method, the micro pull-down method, or the Czochralski The method is preferred, and the micro-pulling method or the zone melt method is particularly preferred for reasons such as wettability with a crucible.

  Furthermore, from the viewpoint of industrial mass production of small single crystals as single crystals for scintillators, the micro pull-down method has the feature that it can grow single crystals at high speed and is easy to control the shape during growth. preferable.

  Examples of the crucible and afterheater material that can be used include platinum, iridium, rhodium, rhenium, and alloys thereof.

  In manufacturing a scintillator single crystal, a high-frequency oscillator, a condenser heater, and a resistance heater may be further used.

  Hereinafter, a single crystal manufacturing method using the Czochralski method and the micro-pulling-down method will be described as an example of a method for manufacturing a single crystal of the crystal material according to the present embodiment. The method for producing the crystal is not limited to this.

  The Czochralski method (pulling) method can be carried out using a known single crystal pulling apparatus of an atmosphere control type by high frequency induction heating. The single crystal pulling apparatus includes a crucible filled with a raw material melt, induction heating means for remotely heating the crucible (for example, a high frequency induction heating coil), a seed crystal holder provided on the crucible, and a seed crystal holder upward. It consists of a moving mechanism that pulls up and a rotating mechanism that rotates around the axis of the seed crystal holder.

  The crucible is filled with a crystal material, and the crucible is heated by a high-frequency heating method or a resistance heating method to melt the crystal material. When the raw material is melted to become a raw material melt, the seed crystal cut in a predetermined crystal orientation is brought into contact with the surface of the raw material melt, and the seed crystal is rotated at a predetermined rotational speed. A single crystal is grown by pulling up.

  The micro pull-down method can be performed using a known atmosphere control type micro pull-down apparatus using high-frequency induction heating. The micro-pulling device is, for example, a crucible for containing a raw material melt, a seed crystal holder for holding a seed crystal to be brought into contact with the raw material melt flowing out from a fine hole provided at the bottom of the crucible, and a seed crystal holder downward A single crystal manufacturing apparatus including a moving mechanism for moving, a moving speed control device for controlling the speed of the moving mechanism, and induction heating means (for example, a high frequency induction heating coil) for remotely heating the crucible. According to such a single crystal production apparatus, a single crystal can be produced by forming a solid-liquid interface immediately below the crucible and moving the seed crystal downward.

  In the single crystal pulling apparatus and the micro pulling method apparatus described above, the crucible is made of carbon, platinum, iridium, rhodium, rhenium, or an alloy thereof. In the micro pull-down method, an after heater, which is a heating element made of carbon, platinum, iridium, rhodium, rhenium, or an alloy thereof, is disposed on the outer periphery of the crucible bottom. Controlling the temperature and distribution of the solid-liquid boundary region of the raw material melt drawn from the fine holes provided at the bottom of the crucible by adjusting the heat output by adjusting the output of each induction heating means of the crucible and after-heater Can do.

The atmosphere control type single crystal pulling device and the atmosphere control type micro pulling device described above employ stainless steel (SUS) as the material of the chamber, quartz as the window material, and a rotary pump for enabling atmosphere control. And the internal vacuum degree can be reduced to 1 × 10 ⁻³ Torr or less before gas replacement. In addition, Ar, N ₂ , H ₂ , O ₂ gas, etc. can be introduced into the chamber at a flow rate precisely adjusted by an accompanying gas flow meter.

Using this apparatus, the crystal growth raw material prepared by the above method is put into a crucible, the inside of the furnace is evacuated to a high vacuum, and then N ₂ gas, Ar gas, or a mixed gas of Ar gas and O ₂ gas is used. Is introduced into the furnace to make the inside of the furnace an inert gas atmosphere or a low oxygen partial pressure atmosphere. Next, the crucible is slowly heated by gradually applying high-frequency power to the high-frequency induction heating coil to completely melt the raw material in the crucible.

  In the micro pull-down method, the seed crystal held by the seed crystal holder is gradually raised at a predetermined speed by a moving mechanism. Then, when the tip of the seed crystal is brought into contact with the fine hole at the lower end of the crucible and sufficiently blended, the crystal is grown by lowering the seed crystal while adjusting the melt temperature.

  As the seed crystal, it is preferable to use a seed crystal that is equivalent to or similar in structure and composition to the crystal growth object, but is not limited thereto. Moreover, it is preferable to use a crystal with a clear crystal orientation as a seed crystal.

  Crystal growth is completed when all of the prepared crystal growth raw materials are crystallized and the melt is exhausted. On the other hand, for the purpose of keeping the composition of the crystal to be grown uniform and for the purpose of lengthening it, a device for continuously charging the crystal growth raw material may be incorporated. Thereby, the crystal can be grown while charging the crystal growth raw material.

  Hereinafter, examples and comparative examples of the present invention will be described in detail with reference to the drawings, but the present invention is not limited thereto. In the following examples, the Ce concentration is either a concentration in a specific crystal or a concentration in a melt or (preparation). In each example, the concentration in the crystal is 1 In contrast, there was a relationship such that the concentration at the time of charging was about 1 to 10.

Example 1
A crystal represented by a composition of (Ce _0.01 La _0.44 Gd _0.55 ) ₂ Si ₂ O ₇ (x = 0.44, y = 0.01) was grown by the micro-pulling down method. This crystal is a pyrosilicate crystal which is a kind of pyrochlore type oxide represented by A ₂ B ₂ O ₇ . FIG. 1 is a view showing a photograph of a grown (Ce _0.01 La _0.44 Gd _0.55 ) ₂ Si ₂ O ₇ crystal. As shown in FIG. 1, the grown crystal was partially transparent. The transparent crystal had a transparent bulk body, and the pattern under it was seen through. Moreover, it was confirmed that this crystal is a single crystal without cleaving or deliquescence.

(Example 2)
A crystal represented by a composition of (Ce _0.01 La _0.34 Gd _0.65 ) ₂ Si ₂ O ₇ (x = 0.34, y = 0.01) was grown by a micro-pulling down method. This crystal is a pyrosilicate crystal which is a kind of pyrochlore type oxide represented by A ₂ B ₂ O ₇ . FIG. 2 is a view showing a photograph of the grown (Ce _0.01 La _0.34 Gd _0.65 ) ₂ Si ₂ O ₇ crystal. As shown in FIG. 2, the grown crystal was partially transparent. The transparent crystal had a transparent bulk body, and the pattern under it was seen through. Moreover, it was confirmed that this crystal is a single crystal without cleaving or deliquescence.

(Example 3)
A crystal represented by a composition of (Ce _0.01 La _0.29 Gd _0.7 ) ₂ Si ₂ O ₇ (x = 0.29, y = 0.01) was grown by the micro-pulling down method. This crystal is a pyrosilicate crystal which is a kind of pyrochlore type oxide represented by A ₂ B ₂ O ₇ . FIG. 3 is a view showing a photograph of the grown (Ce _0.01 La _0.29 Gd _0.7 ) ₂ Si ₂ O ₇ crystal. As shown in FIG. 3, a partially transparent crystal was obtained from the grown crystal. The transparent crystal had a transparent bulk body, and the pattern under it was seen through. Moreover, it was confirmed that this crystal is a single crystal without cleaving or deliquescence.

Example 4
A crystal represented by a composition of (Ce _0.01 La _0.22 Gd _0.77 ) ₂ Si ₂ O ₇ (x = 0.22, y = 0.01) was grown by a micro-pulling down method. This crystal is a pyrosilicate crystal which is a kind of pyrochlore type oxide represented by A ₂ B ₂ O ₇ . FIG. 4 is a photograph showing a grown (Ce _0.01 La _0.22 Gd _0.77 ) ₂ Si ₂ O ₇ crystal. As shown in FIG. 4, the grown crystal was partially transparent. The transparent crystal had a transparent bulk body, and the pattern under it was seen through. Moreover, it was confirmed that this crystal is a single crystal without cleaving or deliquescence.

(Example 5)
A crystal represented by a composition of (Ce _0.005 La _0.30 Gd _0.695 ) ₂ Si ₂ O ₇ (x = 0.30, y = 0.005) was grown by the micro-pulling down method. This crystal is a pyrosilicate crystal which is a kind of pyrochlore type oxide represented by A ₂ B ₂ O ₇ . FIG. 5 is a view showing a photograph of the grown (Ce _0.005 La _0.30 Gd _0.695 ) ₂ Si ₂ O ₇ crystal. As shown in FIG. 5, the grown crystal was partially transparent. The transparent crystal had a transparent bulk body, and the pattern under it was seen through. Moreover, it was confirmed that this crystal is a single crystal without cleaving or deliquescence.

(Example 6)
A crystal represented by a composition of (Ce _0.03 La _0.30 Gd _0.67 ) ₂ Si ₂ O ₇ (x = 0.30, y = 0.03) was grown by the micro-pulling down method. This crystal is a pyrosilicate crystal which is a kind of pyrochlore type oxide represented by A ₂ B ₂ O ₇ . FIG. 6 is a photograph showing a grown (Ce _0.03 La _0.30 Gd _0.67 ) ₂ Si ₂ O ₇ crystal. As shown in FIG. 6, the grown crystal was partially transparent. The transparent crystal had a transparent bulk body, and the pattern under it was seen through. Moreover, it was confirmed that this crystal is a single crystal without cleaving or deliquescence.

(Comparative Example 1)
A crystal represented by a composition of (Ce _0.01 La _0.49 Gd _0.50 ) ₂ Si ₂ O ₇ was grown by a micro-pulling down method. This crystal is a pyrosilicate crystal which is a kind of pyrochlore type oxide represented by A ₂ B ₂ O ₇ . FIG. 7 is a view showing a photograph of the grown (Ce _0.01 La _0.49 Gd _0.50 ) ₂ Si ₂ O ₇ crystal. As shown in FIG. 7, the grown crystal was cracked as a whole and was a brittle crystal.

(Comparative Example 2)
A crystal represented by a composition of (Ce _0.01 La _0.19 Gd _0.80 ) ₂ Si ₂ O ₇ was grown by a micro-pulling down method. This crystal is a pyrosilicate crystal which is a kind of pyrochlore type oxide represented by A ₂ B ₂ O ₇ . FIG. 8 is a photograph showing a grown (Ce _0.01 La _0.19 Gd _0.80 ) ₂ Si ₂ O ₇ crystal. As shown in FIG. 8, the grown crystal was cracked in a certain direction with respect to the growing direction, and cleavage occurred.

(Comparative Example 3)
As a comparative example of a known single crystal scintillator, a commercially available (Ce _0.01 Gd _0.99 ) ₂ SiO ₅ (Ce 1%: GSO) crystal having a size of 5 mm × 5 mm × 5 mm was used.

When Example 1 to Example 6 were carried out, a transparent bulk body could be stably grown, whereas Comparative Example 1 and Comparative Example 2 could not be stably grown. . Comparative Example 1 is a case where La is large, but the ionic radii of Gd and La (Shannon's ionic radius) are different from 0.94 angstrom and 1.03 angstrom, respectively. Becomes larger and more easily broken. Although Comparative Example 2 is a case where La is small, although it is close to the harmonic melt composition, this composition approaches the unstable peritectic composition of Gd ₂ Si ₂ O ₇ , so that crystal growth becomes unstable.

For the grown crystals of Examples 1 to 6 and Comparative Example 3, the light emission characteristics of each scintillation light were measured by light emission (radioluminescence) by radiation excitation. A spectroscope (type: Instrument FSL920) manufactured by Edingur was used for the luminescence measurement. As a radiation source used for excitation, ²⁴¹ Am (radioactivity: 1 MBq) which is an alpha ray source of 5.5 MeV was used.

  FIG. 9 is a diagram showing the obtained profiles of Example 1, Example 2, and Example 3. In FIG. 9, the horizontal axis represents the emission wavelength, and the vertical axis represents the count number (normalized) in which the maximum value of each peak is normalized by 1, which represents the emission intensity. As shown in FIG. 9, all of the crystals of the examples had emission peak wavelengths in the range of 300 nm to 400 nm.

Furthermore, the light emission amount of the crystals obtained in Examples 1 to 6 was estimated. Here, each crystal is optically mounted on a photomultiplier tube (R7600-200 manufactured by Hamamatsu Photonics), which is a photodetector, with optical grease (Applied Koken 6262A) and ¹³⁷ Cs having a radioactivity of 1 MBq. A sealed ray source (gamma ray source) or ²⁴¹ Am was used to excite and emit light by irradiating gamma rays.

  Note that 650 V to 700 V was applied to the photomultiplier tube to convert the scintillation light into an electrical signal. Here, the electric signal output from the photomultiplier tube is a pulse-like signal reflecting the received scintillation light, and the pulse height represents the emission intensity of the scintillation light. The electric signal output from the photomultiplier tube was shaped and amplified by a shaping amplifier in this way, and then input to a multi-wave height analyzer (multi-channel analyzer: MCA) for analysis to create a wave height distribution spectrum. A wave height distribution spectrum was similarly created for the crystal of Comparative Example 3.

FIG. 10 is a diagram showing wave height distribution spectra (Example 1, Example 3, Example 5, Example 6, and Comparative Example 3) obtained by irradiating the above-mentioned ¹³⁷ Cs with gamma rays (662 keV). In FIG. 10, the horizontal axis represents the channel number of the MCA and represents the signal magnitude. Regarding the horizontal axis, the photoelectric absorption peak derived from the 662 keV gamma ray is higher on the right side in the figure, indicating that the light emission amount is higher.

  As can be seen from FIG. 10, the crystal of the example had higher light emission than the crystal of the comparative example. In FIG. 10, the light emission amount of Example 1 was 39,000 photon / MeV. A light emission amount of 30,000 photon / MeV or more is regarded as a good characteristic. From Example 1 to Example 6 were all good.

Next, the decay time of scintillation light of the crystals of Examples 1 to 6 was determined. Here, the crystal was optically bonded to the photomultiplier tube with the optical grease, and was excited and emitted by irradiating the gamma ray with the ¹³⁷ Cs gamma ray. Then, the time distribution of the signal from the photomultiplier tube was measured with an oscilloscope (Tektronix TDS 3034B) to determine the decay time. Here, 1000 nanoseconds or less is good, and 80 nanoseconds or less is particularly good.

  FIG. 11 is a graph showing a fluorescence decay curve profile of the crystal of Example 1. FIG. In FIG. 11, the horizontal axis represents time, and the vertical axis represents the voltage corresponding to the emission intensity. The gray line is the actual measurement, and the black line is the result of fitting with the following function I (t) with the time t as a variable in order to obtain the attenuation constant (fluorescence lifetime).

I (t) = A ₁ × exp (−t / τ ₁ (ns)) + A ₂ × exp (−t / τ ₂ (ns)) + c

Here, when the measurement result of Example 1 was fitted, the high-speed component fluorescence lifetime τ ₁ of the crystal was 75 nanoseconds, and a high-speed scintillator could be constructed. Moreover, it was 80 nanoseconds or less in all Examples from Example 2 to Example 6, and was especially favorable.

From the results of Examples 1 to 6, in the scintillator crystal material represented by (Gd _1-xy La _x Ce _y ) ₂ Si ₂ O ₇ , x = 0.2 to 0.45, preferably 0.22 By setting to ˜0.35, more preferably 0.22 to 0.34, a crystalline material having an emission peak wavelength in the range of 300 to 400 nm and a preferable characteristic of a fluorescence lifetime of 80 nanoseconds or less can be obtained. I was able to confirm.

(Example 7)
In the scintillator crystal material represented by (Gd _1-xy La _x Ce _y ) ₂ Si ₂ O ₇ , the same as in Examples 1 to 6 except that y was changed to 0.0001 to 0.05. A scintillator crystal material was prepared and subjected to the same test. In Example 7, as in Examples 1 to 6, a partially transparent crystal was obtained, and it was confirmed that the crystal was a single crystal having no cleavage or deliquescence.

  In Example 7, by setting y within the range of 0.0001 to 0.05, a scintillator crystal material having a fluorescence wavelength of 200 nm to 900 nm and a fluorescence lifetime of 1000 nanoseconds or less can be obtained. I was able to confirm. Furthermore, it was confirmed that by setting y in the range of 0.0005 to 0.02, a scintillator crystal material having a fluorescence wavelength of 300 nm to 700 nm and a fluorescence lifetime of 80 nanoseconds or less can be obtained.

  As described above, the scintillator crystal material and the single crystal scintillator according to the present invention are particularly useful for industrial production methods such as the Czochralski method and the micro pull-down method.

Claims (8)

Is represented by _{(Gd 1-x-y La} x Ce y) 2 Si 2 O 7, the range of x is 0.2 ≦ x ≦ 0.45, the range of y is at 0.0001 ≦ y ≦ 0.05 Scintillator crystal material.   2. The scintillator crystal material according to claim 1, wherein the range of x is 0.22 ≦ x ≦ 0.35 and the range of y is 0.0005 ≦ y ≦ 0.02.   The scintillator crystal material emits scintillation light when irradiated with radiation, and the predetermined fluorescent component contained in the scintillation light has a fluorescence wavelength of 200 nm to 900 nm and a fluorescence lifetime of 1000 nanoseconds or less. Or the scintillator crystal material of Claim 2.   The scintillator crystal material emits scintillation light when irradiated with radiation, and the predetermined fluorescent component contained in the scintillation light has a fluorescence wavelength of 300 nm to 700 nm and a fluorescence lifetime of 80 nanoseconds or less. The scintillator crystal material according to claim 3.   A single crystal scintillator made of the scintillator crystal material according to any one of claims 1 to 4.   A scintillator composed of the scintillator crystal material according to any one of claims 1 to 4 or the single crystal scintillator according to claim 5, and a photodetector that receives scintillation light from the scintillator. A radiation detector characterized by.   An imaging apparatus comprising the radiation detector according to claim 6.   A nondestructive inspection apparatus comprising the radiation detector according to claim 6.