• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    A scintillator material (10) comprises a matrix phase (12, 18, 22) and scintillator portions (14) dispersed in the matrix phase (12, 18, 22). The scintillator parts contain fine particles of monocrystal. In the above aspect, since the scintillator portions containing the single crystal fine particles are dispersed in the matrix phase, it is possible to reduce an influence from an environment.
    公开号:FR3072389A1
    申请号:FR1859429
    申请日:2018-10-11
    公开日:2019-04-19
    发明作者:Hisayoshi Daicho
    申请人:Koito Manufacturing Co Ltd；
    IPC主号:
    专利说明:

    CROSS REFERENCE TO A RELATED REQUEST
    This application claims priority from Japanese patent application No. 2017-199343 filed on October 13, 2017.
    FIELD This disclosure relates to a scintillator material.
    In the related art, a scintillator is known as a material which is excited by radiation and emits fluorescence or phosphorescence. For example, as a highly sensitive and high resolution material of the scintillator, we know the single crystal of Srl 2 doped with Eu (see patent document 1).
    Patent document 1: JP-A-2016-56030 [0004] However, as the scintillator material including Srl 2 , there is a material with high deliquescence, so it is necessary to design a manufacturing process for this and that there is still a need for improvement in terms of moisture resistance over long term use.
    The present disclosure has been made in view of the above situations, and an object thereof is to provide a new scintillator material having excellent resistance to humidity.
    SUMMARY In order to achieve the above object, a scintillator material according to one aspect of the present disclosure comprises a matrix phase, and scintillator portions dispersed in the matrix phase. The scintillator parts contain fine particles of single crystal.
    According to the above aspect, as the scintillator parts containing the fine single crystal particles are dispersed in the matrix phase, it is possible to reduce an influence of an environment.
    The scintillator parts can be distributed eccentrically in a crystal region in which part of the matrix phase is crystallized. It is therefore possible to form the scintillator parts in the matrix phase relatively conveniently.
    The matrix phase can be silica, and the crystal region can have a cristobalite structure in which part of the silica is crystallized. It is therefore possible to use silica, which is relatively stable, as a raw material.
    The fine single crystal particles may be in a deliquescent compound. In the related art, the fine single crystal particle formed from a deliquescent compound has a lifetime during which it functions like the scintillator which is extremely short. However, according to the above aspect, it is possible to use different compounds having low moisture resistance, which cannot be used in the related art, as long as it is possible to satisfy the performance initial for the scintillator.
    The compound can be a luminescent material expressed by SrI 2 : Eu.
    The compound can be a luminescent material expressed by CsI: TI.
    Another aspect of the present disclosure is a radiation detector. The radiation detector includes a substrate, the scintillator material which is provided on one side of the substrate and a photoelectric conversion element which is provided on the other side of the substrate. In the substrate, a transmissivity of light having a peak wavelength of the light emitted from the scintillator material is 50% or higher. It is therefore possible to use a radiation detector having excellent resistance to humidity.
    Meanwhile, any combination of the constitutional elements described above and a method, device, system and the like to be expressed by the present disclosure are also effective as aspects of the present disclosure.
    It is possible according to the present disclosure to provide a radiation detector having excellent resistance to humidity.
    BRIEF DESCRIPTION OF THE DRAWINGS [0016] FIG. IA is a schematic view of a plate-shaped scintillator, FIG. IB is a schematic view of a fiber-shaped scintillator, and FIG. IC is a schematic view of a particle-shaped scintillator.
    FIGS. 2A to 2D are schematic views of a mechanism by which a nano-composite type scintillator material is formed.
    FIG. 3 represents an X-ray diffraction pattern of a nano-composite according to Example 1.
    FIG. 4 represents a luminescence spectrum of the nanocomposite according to Example 1.
    FIG. 5 represents an SEM image of the nano-composite according to Example 1.
    FIG. 6 shows a result of a lifetime test of the nano-composite type scintillator material.
    FIG. 7 shows a schematic configuration of a radiation detector according to the embodiment.
    DETAILED DESCRIPTION A description will be given below in detail with reference to the drawings, of an embodiment for implementing the present disclosure. In the description of the drawings, the same elements are indicated by the same reference signs, and their duplicated descriptions are appropriately omitted.
    (Scintillator)
    We first describe a schematic configuration of a luminescent material of nano-composite type according to one embodiment. FIG. IA is a schematic view of a plate-shaped scintillator, FIG. IB is a schematic view of a fiber-shaped scintillator, and FIG. IC is a schematic view of a particle-shaped scintillator.
    The scintillator is a luminescent material which absorbs radiation (X-rays, γ rays, neutron rays) to emit ultraviolet light or visible light. A material having high resistivity and resolution is preferred as a scintillator. That is, the scintillator must efficiently convert the radiation into light and have a short lifetime of light emission. There is SrI 2 : Eu 2+ as one of the materials actually achieving the characteristics. However, as SrI 2 : Eu 2+ has a severe deliquescence, it is very difficult to manufacture and handle it. The inventors have therefore devised a configuration for reducing or eliminating deliquescence by dispersing scintillator parts in a matrix phase.
    A scintillator material 10 shown in FIG. IA comprises a plate-shaped matrix phase 12, and scintillator parts 14 dispersed in the matrix phase 12. The scintillator part 14 comprises a luminescent material formed from fine single crystal particles. A scintillator material 16 shown in FIG. IB includes a fiber-shaped matrix phase 18, and the scintillator portions 14 dispersed in the matrix phase 18. A scintillator material 20 shown in FIG. IC comprises a particle-shaped matrix phase 22, and the scintillator parts 14 dispersed in the matrix phase 22.
    In each scintillator material, the scintillator parts 14 containing the fine single crystal particles are dispersed in the matrix phase. For this reason, compared to a configuration where the scintillator portion 14 is exposed alone, an influence from an environment is reduced, so that the moisture resistance is improved.
    A method of forming the scintillator material of the nano-composite type containing the fine single crystal particles is then described in detail. A configuration in which the matrix phase is silica is described in the following. FIGS. 2A to 2D are schematic views of a mechanism by which a nano-composite type scintillator material is formed.
    The silica has an amorphous structure having a basic skeleton in which a SiO 4 tetrahedron is coupled by Si-O-Si bonds. A Si-O-Si bonding angle is 145 ° ± 10 ° (FIG. 2A). When the silica is heated, the rate of thermal expansion is low up to a temperature of approximately 1000 ° C., but increases moderately from a temperature exceeding 1000 ° C. The reason for this is that active hydrogen atoms are produced from groups
    OH on a silica surface and that a rupture and a rearrangement of the Si-O-Si bonds appear. At this time, the Si-O-Si bonding angle becomes 180 ° and large voids are formed in the SiO 4 interconnection network (FIG. 2B). The vacuum becomes a pocket for a metal cation 24, such as Sr 2+ , Cs + , Ca 2+ , Eu 2+ , Tl + and the like, and an anion 26, such as a halogen, so that the ions correspondents are introduced into the SiO 4 interconnection network (FIG. 2C).
    The cation 24 and the anion 26 introduced are linked by thermal diffusion so that an ion crystal nucleus 28 is produced (FIG. 2D). As the nuclei of ionic crystals 28 are produced, the silica of the matrix phase is also crystallized, so that cristobalite is produced. It is assumed that the nano-composite type scintillator material is produced in this way. Meanwhile, the matrix phase may be formed of tridymite, quartz or the like, in place of cristobalite, and the scintillator portions may be provided therein.
    Similarly, part of the silica, which is the matrix phase, is crystallized at least at an interface between the scintillator part of the embodiment and the matrix phase, so that a cristobalite structure is formed. Since it is possible to distribute the scintillator parts eccentrically in the matrix phase in a relatively practical manner, it is therefore possible to further stabilize the scintillator parts contained in the scintillator material. It is also possible to use silica, which is relatively stabilized, as the raw material for the matrix phase.
    The present disclosure is then described in more detail with reference to each example.
    (Example 1)
    A nano-composite of Example 1 contains SrI 2 : Eu 2+ , as a luminescent component, in the crystalline silica matrix. In a manufacturing process thereof, amorphous silica (average particle size: 10 µm) having a crystallization temperature of 1350 ° C, Srl 2 (melting point: 402 ° C) and EuU have been precisely weighed so that a molar ratio was 6 / 0.75 / 0.05, were deposited in a quartz mortar under an atmosphere of Ar gas and were sprayed and mixed. The mixed powders were then placed in an alumina crucible and baked at 1000 ° C for 10 hours in a nitrogen atmosphere containing hydrogen (a volume ratio N 2 / H 2 = 95/5). After cooking, the powders were washed with lukewarm pure water to remove excess iodide, so that a sample of the nano-composite of Example 1 was obtained.
    The sample obtained was then subjected to an X-ray powder diffraction measurement. FIG. 3 shows an X-ray diffraction pattern of the nano-composite according to Example 1. By analyzing the peaks shown in FIG. 3, the nano-composite of Example 1 consisted of powders in which Γα-cristobalite, which is a layer of silica crystal at high temperature, is a main phase. By irradiation with an ArF excimer laser having a peak wavelength of 193 nm from the nano-composite, it was possible to observe a blue luminescence having a peak wavelength of 432 nm originating from Eu 2+ doped in Srl 2 . FIG. 4 represents a luminescence spectrum of the nano-composite according to Example 1.
    The nano-composite of Example 1 was then cut using a focused ion beam device (“focused ion beam” or FIB in English) and a section of it was observed with a microscope SEM scanning electronics (“scanning electron microscope” or SEM). FIG. 5 represents an SEM image of the nano-composite according to [Example 1.
    The nano-composite shown in FIG. 5 shows two phases of a gray matrix part and white point parts dispersed in a center of the matrix part. The respective parts were subjected to a composition analysis using an energy dispersive X-ray spectroscopic device (EDX) annexed to the SEM. It follows that the matrix part was SiO 2 , and that the white point parts had contents expressed as percentages of Sr, I and Eu increased, in comparison with the environment. That is, the sample of [Example 1 was a nano-composite material in which the nano-order SrI 2 : Eu 2+ was distributed eccentrically.
    On the other hand, the scintillator parts are distributed eccentrically in a crystal region in which part of the matrix phase is crystallized. For this reason, SrI 2 : Eu 2+ , which is a luminescent part (the scintillator part), is protected by the crystalline SiO 2 cristobalite and thus has sufficient resistance to humidity. FIG. 6 shows a result of a lifetime test of the nano-composite scintillator material. The lifetime test was performed in environments of 85 ° C and 85% humidity, and the luminescence intensity was measured at all times when luminescence was continuously produced up to 2 000 h. As a result, the nano-composite scintillator material of Example 1 retains an intensity of 98% of the initial intensity after 2000 h, and exhibits remarkably improved moisture resistance.
    In this way, the fine single crystal particle of SrI 2 : Eu 2+ was a deliquescent compound and had a lifetime for which it functions as a scintillator which is extremely short. The scintillator material of Example 1 may, however, use different compounds with low moisture resistance, which cannot be used in the related art, as long as the initial performance for the scintillator can be satisfied .
    FIG. 7 shows a schematic configuration of a radiation detector according to the embodiment. A radiation detector 100 shown in FIG. 7 comprises a transparent substrate 102 having a high light transmissivity around a wavelength of 430 nm, the scintillator material 10 which is supplied on one side of the transparent substrate 102, and a photoelectric conversion element 104 which is supplied on the other side of the transparent substrate 102. The transparent substrate 102 can be any substrate whose transmissivity of light which has a peak wavelength (for example, 430 nm) of the light emitted from the material of scintillator 10, is 50% or more. The transparent substrate 102 preferably has a light transmissivity of 70% or more, and more preferably still 85% or more. It is therefore possible to implement a radiation detector having excellent resistance to humidity and high sensitivity.
    (Example 2)
    A nano-composite of Example 2 contains CsI: TI + , as a luminescent constituent, in the crystalline silica matrix. In a manufacturing process thereof, amorphous silica (average particle size: 10 µm) having a crystallization temperature of 1350 ° C, Csl (melting point: 621 ° C) and TU were precisely weighed so that a molar ratio was 6 / 0.45 / 0.05, were deposited in the quartz mortar under an atmosphere of Ar gas and were sprayed and mixed. The mixed powders were then placed in the alumina crucible and baked at 1000 ° C for 10 hours in a nitrogen atmosphere containing hydrogen (a volume ratio N 2 / H 2 = 95/5). After cooking, the powders were cleaned with lukewarm pure water to remove excess iodide, so that a sample of the nano-composite of Example 2 was obtained.
    The sample obtained was then subjected to an X-ray powder diffraction measurement. The nano-composite of [Example 2] consisted of powders in which Γα-cristobalite, which is a layer of silica crystal at high temperature, is a main phase. By irradiation with an ArF excimer laser having a peak wavelength of 193 nm from the nano-composite, it was possible to observe a green luminescence having a peak wavelength of 550 nm originating from doped Tl + in Csl.
    The nano-composite of Example 2 was then cut using the focused ion beam device (FIB) and a section of it was observed with the scanning electron microscope (SEM).
    The nano-composite of [Example 2 has two phases of a gray matrix part and of white point parts dispersed in a center of the matrix part, as in Example 1. The respective parts were subjected to a composition analysis using the energy dispersive X-ray spectroscopic device (EDX) annexed to the SEM. It follows that the matrix part was SiO 2 , and that the white point parts had contents expressed as a percentage of Cs, I and Tl increased, in comparison with [surrounding. That is, the sample of Example 2 was a nanocomposite material in which the nano-order CsI: TI + was distributed eccentrically.
    On the other hand, the radiation detector of Example 2 comprises a transparent substrate 102 having a high transmissivity of light around a wavelength of 550 nm, the scintillator material 10 which is supplied on one side of the transparent substrate 102, and a photoelectric conversion element 104 which is provided on the other side of the transparent substrate 102, like the radiation detector 5 100 described in example 1. The transparent substrate 102 can be any substrate whose transmissivity of light which has a peak wavelength (for example, 550 nm) of the light emitted from the scintillator material 10, is 50% or more. The transparent substrate 102 preferably has a light transmissivity of 70% or more, and more preferably still 85% or more. It is therefore possible to use a radiation detector having excellent resistance to humidity and high sensitivity.
    (Example 3)
    A nano-composite of Example 3 contains SrI 2 : Eu 2+ as a luminescent component in the crystalline silica matrix. A manufacturing process thereof is different from Example 1.
    In the process for manufacturing the nano-composite of Example 3, a quartz glass having a dimension of 30 mm x 30 mm and a thickness of 3 mm is prepared like the matrix phase and a surface of that -this is made rough (arithmetic mean roughness Ra = 10 pm) by sandblasting. In the meantime, the roughness can be appropriately selected in the range of 5 to 20 µm. On the other hand, the glass surface is preferably cleaned with pure water. 1 g of mixed raw material is then placed in a uniform thickness on the glass.
    The glass was then moved to a baking oven and was baked at 1000 ° C for 10 hours in a nitrogen atmosphere containing hydrogen (volume ratio N 2 / H 2 = 95/5 ). After cooking, the glass was cleaned with lukewarm pure water to remove excess iodide. As a result, about 1.5 mm of the quartz glass from the roughened surface was transformed into cristobalite and became cloudy in appearance. By irradiation with an ArF excimer laser having a peak wavelength of 193 nm from the nano-composite, it was possible to observe a blue luminescence having a peak wavelength of 432 nm originating from Eu 2 + doped in Srl 2 .
    Meanwhile, a compound capable of presenting its function can be dispersed as nano-polycrystals in the matrix phase, in place of nano-single crystals.
    The present disclosure has been described with reference to the embodiment and the respective examples. The embodiment and the respective examples are only examples, and those skilled in the art can understand that combinations of the respective constitutional elements and respective processing steps can be varied in various ways and that these modifications are also included in the scope of this disclosure.
    权利要求:
    Claims (7)
    [1" id="c-fr-0001]
    1. Scintillator material (10) comprising:
    a matrix phase (12, 18, 22); and scintillator parts (14) dispersed in the matrix phase (12, 18, 22), wherein the scintillator parts (14) contain fine particles of single crystal.
    [2" id="c-fr-0002]
    2. The scintillator material (10) according to claim 1, wherein the scintillator parts (14) are distributed eccentrically in a crystal region in which part of the matrix phase (12,18, 22) is crystallized .
    [3" id="c-fr-0003]
    The scintillator material (10) according to claim 2, wherein the matrix phase (12, 18, 22) is silica, and wherein the crystal region comprises a cristobalite structure in which a portion of the silica is crystallized.
    [4" id="c-fr-0004]
    4. A scintillator material (10) according to any one of claims 1 to 3, in which the fine single crystal particles are made of a deliquescent compound.
    [5" id="c-fr-0005]
    5. A scintillator material (10) according to claim 4, wherein the compound is a luminescent material expressed by SrI 2 : Eu.
    [6" id="c-fr-0006]
    6. A scintillator material (10) according to claim 4, wherein the compound is a luminescent material expressed by CsI: TI.
    [7" id="c-fr-0007]
    7. Radiation detector comprising:
    a substrate (102);
    the scintillator material (10) according to any of claims 1 to 6, which is provided on one side of the substrate (102); and a photoelectric conversion element (104), which is provided on the other side of the substrate, wherein the substrate (102) is configured so that transmissivity of light having a peak wavelength of the light emitted from the scintillator material (10) is 50% or more.
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    法律状态:
    2019-08-28| PLFP| Fee payment|Year of fee payment: 2 |
    2020-08-26| PLFP| Fee payment|Year of fee payment: 3 |
    2020-12-25| PLSC| Publication of the preliminary search report|Effective date: 20201225 |
    2021-09-07| PLFP| Fee payment|Year of fee payment: 4 |
    优先权:
    申请号 | 申请日 | 专利标题
    JP2017-199343|2017-10-13|
    JP2017199343A|JP6985882B2|2017-10-13|2017-10-13|Scintillator material and radiation detector|
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