WO2018110451A1 - Luminophore permettant de détecter un rayonnement ionisant, matériau luminophore contenant ledit luminophore, appareil d'inspection et appareil de diagnostic ayant ledit matériau luminophore - Google Patents

Luminophore permettant de détecter un rayonnement ionisant, matériau luminophore contenant ledit luminophore, appareil d'inspection et appareil de diagnostic ayant ledit matériau luminophore Download PDF

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WO2018110451A1
WO2018110451A1 PCT/JP2017/044190 JP2017044190W WO2018110451A1 WO 2018110451 A1 WO2018110451 A1 WO 2018110451A1 JP 2017044190 W JP2017044190 W JP 2017044190W WO 2018110451 A1 WO2018110451 A1 WO 2018110451A1
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phosphor
formula
group
tetrahedron
light emission
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PCT/JP2017/044190
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English (en)
Japanese (ja)
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博充 木村
山根　久典
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三菱ケミカル株式会社
国立大学法人東北大学
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Publication of WO2018110451A1 publication Critical patent/WO2018110451A1/fr

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01T—MEASUREMENT OF NUCLEAR OR X-RADIATION
    • G01T1/00—Measuring X-radiation, gamma radiation, corpuscular radiation, or cosmic radiation
    • G01T1/16—Measuring radiation intensity
    • G01T1/20—Measuring radiation intensity with scintillation detectors
    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21K—TECHNIQUES FOR HANDLING PARTICLES OR IONISING RADIATION NOT OTHERWISE PROVIDED FOR; IRRADIATION DEVICES; GAMMA RAY OR X-RAY MICROSCOPES
    • G21K4/00—Conversion screens for the conversion of the spatial distribution of X-rays or particle radiation into visible images, e.g. fluoroscopic screens

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  • the present invention relates to a phosphor for detecting ionizing radiation having a novel composition.
  • Typical phosphor materials for detecting radiation include Lu 2 SiO 5 , Ga 3 Al 5 O 12 , Gd 2 Si 2 O 7 and the like.
  • the scintillator characteristics were improved by replacing the base atom with a homologous atom or co-adding impurity atoms with different valences together with the luminescent center atom. Has been attempted (see Patent Documents 1 to 3).
  • An object of the present invention is to provide a novel phosphor material capable of greatly improving scintillator characteristics.
  • the present inventors diligently investigated a new search for phosphor materials. As a result, the present inventors came up with a new phosphor material having a composition and crystal structure different from those of conventional phosphors for radiation detection. Completed.
  • the present invention includes the following phosphors.
  • a phosphor for ionizing radiation detection represented by the formula (1).
  • Q includes one or more selected from the group consisting of alkaline earth metal elements
  • R includes one or more selected from the group consisting of rare earth metal elements
  • G and T are: Each of them includes one or more selected from the group consisting of Si, Ge and Sn
  • X and Z include at least O (oxygen)
  • p, s, u, and q are 0.9 ⁇ p ⁇ 1.1, 3.5 ⁇ s ⁇ 12.5, 0.8 ⁇ u ⁇ 5.2, 0.9 ⁇ q ⁇ 1.1.
  • the phosphor of the formula (1) is: Four X coordinated to G form a tetrahedron, and by sharing the apex of the tetrahedron, two tetrahedrons are connected to form a (G 2 X 7 ) unit, Z coordinated to T forms a tetrahedron, and by sharing the vertices of the tetrahedron, three tetrahedrons are connected to form a unit (T 3 Z 10 ), The phosphor according to any one of [1] to [3], wherein u and q satisfy u ⁇ q.
  • a phosphor for ionizing radiation detection represented by the formula (2).
  • Q includes one or more selected from the group consisting of alkaline earth metal elements, R includes one or more selected from the group consisting of rare earth metal elements, E is Si, Ge And at least one selected from the group consisting of Sn, J includes at least O (oxygen), and p, s, m, and n are 0.9 ⁇ p ⁇ 1.1 and 3.5 ⁇ , respectively.
  • the lattice constants a, b, c, ⁇ , and the lattice volume V satisfy the following. 5.19 ⁇ ⁇ a ⁇ 5.92 ⁇ 18.51mm ⁇ b ⁇ 55.00mm 6.45mm ⁇ c ⁇ 7.36mm 103.01 ° ⁇ ⁇ ⁇ 110.79 ° 661.40 ⁇ 3 ⁇ V ⁇ 2200.00 ⁇ 3 [9]
  • the phosphor according to any one of [1] to [8], which is a single crystal.
  • the present invention further includes the following.
  • a radiation detector comprising the phosphor material according to [10].
  • An inspection apparatus using radiation detection comprising the phosphor material according to [10].
  • a diagnostic device using radiation detection comprising the phosphor material according to [10].
  • the present invention provides a novel phosphor material for detecting radiation such as X-rays and ⁇ -rays.
  • FIG. 3 is a schematic diagram showing a crystal structure of a phosphor manufactured in Example 1.
  • FIG. 3 is a graph showing the emission attenuation characteristics of the phosphor manufactured in Example 1.
  • the XRD pattern simulated from the XRD measurement result of the fluorescent substance manufactured in Example 2, and the crystal structure analysis result of Example 1 is shown.
  • or 4 is shown.
  • or 9 is shown.
  • the XRD measurement result of the fluorescent substance manufactured in Example 2 and 10 is shown.
  • the UV excitation light emission spectrum of the fluorescent substance manufactured in Example 2 is shown.
  • FIG. 10 is a schematic diagram showing a crystal structure of a phosphor manufactured in Example 14. The XRD pattern simulated from the XRD measurement result of the fluorescent substance manufactured in Example 14 and the crystal structure analysis result of Example 14 is shown. The XRD measurement result of the fluorescent substance manufactured in Example 17 and 18 is shown.
  • the UV excitation light emission spectrum of the fluorescent substance manufactured in Example 14 is shown.
  • the UV excitation light emission spectrum of the fluorescent substance manufactured in Example 15 is shown.
  • the UV excitation light emission spectrum of the fluorescent substance manufactured in Example 16 is shown.
  • the UV excitation light emission spectrum of the fluorescent substance manufactured in Example 17 is shown.
  • the UV excitation light emission spectrum of the fluorescent substance manufactured in Example 19 is shown.
  • the UV excitation light emission spectrum of the fluorescent substance manufactured in Example 20 is shown.
  • the UV excitation light emission spectrum of the fluorescent substance manufactured in Example 21 is shown.
  • the phosphor according to the first embodiment of the present invention is a phosphor satisfying the following formula (1) (hereinafter also referred to as phosphor (1)).
  • Q includes one or more selected from the group consisting of alkaline earth metal elements
  • R includes one or more selected from the group consisting of rare earth metal elements
  • G and T are respectively Including at least one selected from the group consisting of Si, Ge and Sn independently
  • X and Z contain at least O (oxygen).
  • P, s, u, and q are 0.9 ⁇ p ⁇ 1.1, 3.5 ⁇ s ⁇ 12.5, 0.8 ⁇ u ⁇ 5.2, and 0.9 ⁇ q ⁇ 1.1, respectively. Satisfy.
  • the range of s is preferably 3.5 ⁇ s ⁇ 10.5, more preferably 3.5 ⁇ s ⁇ 8.5, still more preferably 3.5 ⁇ s ⁇ 6.5, and the range of u is Preferably 0.8 ⁇ u ⁇ 4.2, more preferably 0.8 ⁇ u ⁇ 3.2, and still more preferably 0.8 ⁇ u ⁇ 2.2.
  • the phosphor according to the second embodiment of the present invention is a phosphor satisfying the following formula (2) (hereinafter also referred to as phosphor (2)).
  • Q includes one or more selected from the group consisting of alkaline earth metal elements
  • R includes one or more selected from the group consisting of rare earth metal elements
  • E represents Si, Ge and One or more selected from the group consisting of Sn is included
  • J includes at least O (oxygen).
  • P, s, m, and n are 0.9 ⁇ p ⁇ 1.1, 3.5 ⁇ s ⁇ 12.5, 4.3 ⁇ m ⁇ 13.7, and 14.6 ⁇ n ⁇ 47.4, respectively. Satisfy.
  • the range of s is preferably 3.5 ⁇ s ⁇ 10.5, more preferably 3.5 ⁇ s ⁇ 8.5, still more preferably 3.5 ⁇ s ⁇ 6.5, and the range of m is Preferably 4.3 ⁇ m ⁇ 11.7, more preferably 4.3 ⁇ m ⁇ 9.7, still more preferably 4.3 ⁇ m ⁇ 7.7, and the range of n is preferably 14.6. ⁇ n ⁇ 40.4, more preferably 14.6 ⁇ n ⁇ 33.4, and further preferably 14.6 ⁇ n ⁇ 26.4.
  • the Q element are Mg, Ca, Sr, Ba, and the like, and preferably contain at least Ba.
  • the Ba site may be substituted with another metal, and the substitution ratio may be 90% or less with respect to the total amount of Ba.
  • the R element include Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, and Lu, and preferably include at least Lu.
  • the Lu site may be substituted with another metal, and the substitution ratio may be 90% or less with respect to the total amount of Lu.
  • the G element and the T element include one or more selected from the group consisting of Si, Ge, and Sn, and may be the same or different, but preferably include at least Si.
  • the Si site may be substituted with another metal, and the substitution ratio may be 90% or less with respect to the total amount of Si.
  • the element E includes one or more selected from the group consisting of Si, Ge, and Sn, and may be the same or different, but preferably includes at least Si.
  • the Si site when Si is included as the E element, the Si site may be replaced with another metal, and the replacement ratio may be 90% or less with respect to the total amount of Si. Moreover, it is preferable to contain 50% or more of Si with respect to the total amount of element E, and more preferably 60% or more.
  • the X element and the Z element include at least O (oxygen), and may include N, F, Cl, S, and the like. It is preferable to contain 80% or more of O with respect to the total amount of each of the X element and Z element, and more preferably 90% or more.
  • the J element includes at least O (oxygen), and may include N, F, Cl, S, and the like. It is preferable that 80% or more of O is contained with respect to the total amount of J element, and more preferably 90% or more.
  • the phosphor represented by the above formula (1) and / or (2) preferably contains one or more activators selected from the group consisting of Ce, Pr, Nd, Eu, Tb and Yb. Specifically, it is preferable that either or both of atoms Q and R contain the above activator.
  • the phosphor material for ionizing radiation detection preferably contains Ce, Pr, Nd, Eu, Tb, and more preferably contains Ce. Atoms other than the atoms exemplified as the above-mentioned activator such as alkaline earth metal can be added together with the activator from the viewpoint of controlling the light emission amount and the light emission lifetime.
  • X elements coordinated to the G element form a tetrahedron, and two tetrahedrons are connected by sharing the apex of the tetrahedron (G 2 X 7 ).
  • U indicating (G 2 X 7 ) unit satisfies 0.8 ⁇ u ⁇ 5.2
  • q indicating (T 3 Z 10 ) unit satisfies 0.9 ⁇ q ⁇ 1.1. That is, typically, the abundance ratio of (G 2 X 7 ) units to (T 3 Z 10 ) units is 1: 1, 2: 1, 3: 1, 4: 1, or 5: 1. Preferably it is 1: 1 or 2: 1, but due to stacking irregularities in the crystal structure, the typical ratio values of (G 2 X 7 ) units and (T 3 Z 10 ) units may shift. In addition to this, u and q preferably satisfy u ⁇ q.
  • the value of p indicating the Q element and the value of s indicating the R element in the phosphor satisfy 0.9 ⁇ p ⁇ 1.1 and 3.5 ⁇ s ⁇ 12.5, respectively. If it is the said range, the compound which has a structure represented by the said Formula (1) may be produced
  • the present inventors have analyzed the crystal structure of a crystal having a general formula of BaLu 6 (Si 2 O 7 ) 2 (Si 3 O 10 ).
  • the BaLu 6 (Si 2 O 7 ) 2 (Si 3 O 10 ) crystal was monoclinic.
  • the novel phosphor according to the present embodiment forms a tetrahedron with four Os coordinated to Si that is a G element, and shares the vertices of the tetrahedron.
  • Two tetrahedrons form a unit of (Si 2 O 7 )
  • O coordinated to Si as a T element forms a tetrahedron
  • three tetrahedrons are shared by sharing the apex of the tetrahedron.
  • the inventors have conceived that a crystal structure is formed by continuously forming (Si 3 O 10 ) units and adding Ba and Lu in addition to these units as appropriate.
  • FIG. 2 shows a schematic diagram of the crystal structure based on a 2: 1 abundance ratio of (G 2 X 7 ) units to (T 3 Z 10 ) units.
  • FIG. 15 shows a schematic diagram of the crystal structure based on the abundance ratio of (G 2 X 7 ) units to (T 3 Z 10 ) units of 1: 1.
  • BaYb 6 (Si 2 O 7 ) 2 (Si 3 O 10 ), BaY 4 (Si 2 O 7 ) (Si 3 O 10 ) and the like have been reported, The composition containing Lu has not been reported so far and corresponds to a novel compound. In addition, there has been no report on the use of compounds having these crystal structures as phosphors for radiation detection.
  • the crystal structure of the compound according to this embodiment can be identified by X-ray diffraction or the like.
  • the basic structure BaLu 6 (Si 2 O 7 ) 2 (Si 3 O 10 ) crystal and BaLu 4 (Si 2 O 7 ) (Si 3 O 10 ) crystal
  • BaLu 10 (Si 2 O 7 ) 4 (Si 3 O 10 ) crystal BaLu 12 (Si 2 O 7 ) 5 (Si 3 O 10 ) Crystals and those whose lattice constants are changed by substituting constituent atoms of the crystals with other atoms are also included in the present invention.
  • the lattice constant ranges are 5.19 ⁇ ⁇ a ⁇ 5.92 ⁇ , 18.51 ⁇ ⁇ b ⁇ 55.00 ⁇ , 6.45 ⁇ ⁇ c ⁇ 7.36 ⁇ , 103.01 ° ⁇ ⁇ ⁇ 110.79 °. It is preferable that The range of b is more preferably 18.51 ⁇ ⁇ b ⁇ 53.50 ⁇ , more preferably 18.51 ⁇ ⁇ b ⁇ 45.00 ⁇ , particularly preferably 18.51 ⁇ ⁇ b ⁇ 35.00 ⁇ , and 18.51 ⁇ ⁇ b ⁇ Most preferred is 29.23 cm.
  • the lattice volume V is preferably satisfies 661.40 ⁇ 3 ⁇ V ⁇ 2200.00 ⁇ 3, it is more preferable to satisfy the 661.40 ⁇ 3 ⁇ V ⁇ 1800.00 ⁇ 3, 661.40 ⁇ 3 ⁇ V ⁇ 1600. more preferably satisfying ⁇ 3, particularly preferably satisfies 661.40 ⁇ 3 ⁇ V ⁇ 1400.00 ⁇ 3, and most preferably satisfies the 661.40 ⁇ 3 ⁇ V ⁇ 1093.37 ⁇ 3. If it is the said range, the compound which has a structure represented by the said Formula (1) may be produced
  • the abundance ratio of (G 2 X 7 ) units to (T 3 Z 10 ) units is 1: 1, 2: 1, 3: 1, 4: 1, or 5: 1, preferably 1: 1 or 2: 1.
  • the lattice constant ranges are 5.19 ⁇ 5 ⁇ a ⁇ 5.92 ⁇ and 18.51 ⁇ ⁇ b. ⁇ 21.22 ⁇ , 6.45 ⁇ ⁇ c ⁇ 7.36 ⁇ , 103.01 ° ⁇ ⁇ ⁇ 110.79 ° are preferable.
  • the lattice volume V preferably satisfies 661.40 ⁇ 3 ⁇ V ⁇ 804.90 ⁇ 3 .
  • the range of lattice constants is 5.21 ⁇ 5 ⁇ a ⁇ 5.88 ⁇ , 25. It is preferable that 83 ⁇ ⁇ b ⁇ 29.23 ⁇ , 6.45 ⁇ ⁇ c ⁇ 7.32 ⁇ , and 103.25 ° ⁇ ⁇ ⁇ 109.93 °.
  • the lattice volume V derived from these lattice constants preferably satisfies 921.981 3 ⁇ V ⁇ 1093.37 ⁇ 3 .
  • the phosphor can function as a phosphor by activating atoms serving as emission centers.
  • the volume-based average primary particle diameter (D 50 ) is usually 0.1 ⁇ m or more, preferably 1 ⁇ m or more, and usually 500 ⁇ m or less, preferably 200 ⁇ m or less.
  • the phosphor for ionizing radiation detection used in a positron emission tomography (PET) apparatus or the like is preferably a single crystal.
  • the phosphor (2) may have a structure that the phosphor (1) can take, may have a lattice constant, or may be a single crystal.
  • the raw material an oxide of each constituent atom can be used.
  • a raw material with a purity of 3N or more because a small amount of impurity atoms may inhibit light emission from the emission center.
  • a raw material having a purity of 4N or higher Weighing the raw materials so that the desired composition can be obtained, thoroughly mixing them using a ball mill, etc., filling them in a crucible, firing them at a predetermined temperature and atmosphere, and grinding and washing the fired products.
  • the phosphor according to the embodiment can be obtained.
  • the method for mixing the raw materials is not particularly limited, and a commonly used method can be applied, and either a dry mixing method or a wet mixing method may be used.
  • Examples of the dry mixing method include mixing using a ball mill or the like.
  • As the wet mixing method for example, a solvent such as water or a dispersion medium is added to the raw material, mixed using a mortar and pestle to form a dispersion solution or slurry, and then spray drying, heat drying, natural drying, etc. The method of drying is mentioned.
  • the obtained mixture is filled in a heat-resistant container such as a crucible or a tray made of a material having low reactivity with each oxide raw material and fired.
  • a heat-resistant container such as a crucible or a tray made of a material having low reactivity with each oxide raw material and fired.
  • the material of the heat-resistant container used at the time of firing is not particularly limited as long as it is a material having low reactivity with each oxide raw material, and examples thereof include platinum-based containers such as Pt, Pt / Rh alloy, and Ir.
  • the atmosphere during firing may be firing in a reducing atmosphere. In this case, in addition to platinum-based containers, Mo and W-based containers can also be used.
  • Calcination temperature and time are not particularly limited as long as the phosphor according to the present embodiment is obtained, and it is preferable to set the temperature and time at which the mixed raw materials sufficiently react. However, if the temperature is too high, or if the firing time is too long, there is a risk of causing a composition shift due to evaporation of the raw material components. It is usually fired at 1000 ° C. or more and 2000 ° C. or less, and firing at 1400 ° C. or more and 1800 ° C. or less is preferable.
  • the pressure during firing is not particularly limited as long as the phosphor according to the present embodiment is obtained, but firing at normal pressure is preferable from the viewpoint of ease of implementation.
  • the atmosphere during firing is not particularly limited as long as the phosphor according to the present embodiment is obtained, but it is preferable to take a suitable atmosphere in consideration of the stability of the material and the fired member.
  • a suitable atmosphere for example, when a phosphor material having Ce 3+ as the emission center is used, a reducing atmosphere is preferable for the purpose of suppressing a valence change of Ce 3+ ⁇ ⁇ Ce 4+ .
  • an argon atmosphere, a nitrogen atmosphere, or a hydrogen-containing atmosphere thereof can be given.
  • the oxidizing atmosphere is preferable. Specifically, an argon atmosphere, a nitrogen atmosphere, an air atmosphere, or the like containing oxygen of several ppm or more can be given. Further, after firing in a reducing atmosphere, a technique such as annealing in an oxidizing atmosphere can also be used.
  • the fired body obtained by the above firing can be heated and melted to produce a single crystal from the melt.
  • the container and atmosphere at the time of producing the single crystal can be appropriately selected from the same viewpoint as the firing.
  • the method for growing a single crystal is not particularly limited, and general Czochralski method, Bridgman method, micro-pulling method, EFG method, zone melt method, and the like can be used.
  • a flux method or the like can also be used. From the viewpoint of growing large crystals, the Czochralski method and the Bridgeman method are preferred.
  • the phosphor represented by the above formula (1) and / or (2) is excited by the irradiation of ionizing radiation and emits light.
  • One embodiment of the present invention provides a scintillator including the phosphor described above.
  • one Embodiment of this invention provides the scintillator for the electromagnetic radiation detection containing said fluorescent substance.
  • One embodiment of the present invention is a phosphor that is excited by irradiation with ionizing radiation and has a maximum emission peak wavelength in a wavelength region of 160 nm to 700 nm. X-rays, ⁇ -rays, ⁇ -rays, and neutron rays are used as the ionizing radiation.
  • the phosphor according to the present embodiment can be used as a radiation detector when combined with a light receiver.
  • the light receiver used in the radiation detector include a position detection type photomultiplier tube (PS-PMT), a silicon photomultiplier (Si-PM) photodiode (PD), and an avalanche photodiode (APD). .
  • PS-PMT position detection type photomultiplier tube
  • Si-PM silicon photomultiplier
  • APD avalanche photodiode
  • the phosphor according to the present embodiment can be used as a radiation inspection apparatus including these radiation detectors.
  • the radiation inspection apparatus include nondestructive inspection detectors, resource exploration detectors, non-destructive inspection apparatuses such as high energy physics detectors, and diagnostic apparatuses such as medical image processing apparatuses.
  • the medical image processing apparatus include a positron emission tomography (PET) apparatus, an X-ray tomography (CT) apparatus, and a single photon emission tomography (SPECT) apparatus.
  • PET include two-dimensional PET, three-dimensional PET, time-of-flight (TOF) PET, and depth detection (DOI) PET. Moreover, these can be used in combination.
  • the phosphor according to this embodiment can synthesize a solid solution or a substitution product in which part or all of the constituent atoms are replaced with other atoms.
  • the atom can be selected according to the application and purpose.
  • Q as the main atom may include Ba, and R may include Lu. preferable.
  • R may include Lu. preferable.
  • substitution atoms are not limited to atoms of the same group as the constituent atoms, and substitution products can be generated even from atoms of different groups.
  • the phosphor according to this embodiment is used for a radiation detector, co-addition of impurities can be used for shortening the light emission amount and the light emission lifetime.
  • any of powder, a sintered compact (ceramics), and a single crystal may be sufficient, and the form according to each use and the objective is preferable.
  • a single crystal is preferable, and in an X-ray CT apparatus, when used as a single crystal, a block of a sintered body, or an X-ray detection film for nondestructive inspection, the powder is dispersed in a resinous sheet. It is preferable to use it as a film.
  • the sample was packed in a copper sample holder, and the excitation emission spectrum and emission spectrum were measured using a fluorescence spectrophotometer FP-6500 (manufactured by JASCO). During measurement, the slit width of the light source side spectroscope and the slit width of the light receiving side spectroscope were set to 1 nm.
  • ⁇ -rays were applied to a sample installed on a photomultiplier tube (Tektronix TDS2024C).
  • the output of the photomultiplier tube was detected with an oscilloscope (H7195 manufactured by Hamamatsu Photonics).
  • the applied voltage of the photomultiplier tube and the scale of the oscilloscope were appropriately set to values capable of detecting the light emission signal.
  • the emission lifetime was calculated by fitting the obtained attenuation waveform with a general single exponential function.
  • the raw material was taken out from the alumina crucible, and pulverized and mixed again until the sample became uniform.
  • the mixed raw material was put into a uniaxial press die of ⁇ 5 mm, pressed at a pressure of 10 MPa for 1 minute, and processed into a pellet form.
  • This pellet raw material is placed on a Pt-Rh (30%) plate laid in an alumina sagger, and is fired in an electric furnace similar to the above at 1800 ° C. for 1 hour in the atmosphere. Went. After furnace cooling to room temperature, a sample was taken out.
  • FIG. 1 A stereomicroscope photograph taken while irradiating the crystallized sample with 365 nm UV light is shown in FIG. From FIG. 1, it was found that single crystal grains having a particle size of more than 100 ⁇ m were crystallized from the melt. In addition, it was observed that the crystal grains were photoexcited by UV of 365 nm and emitted light. The crystal grains were taken out and subjected to single crystal X-ray structural analysis.
  • the obtained reflection point was examined based on the extinction rule, and the single crystal grain space group was analyzed as P21 / m.
  • the obtained crystal grains were found to be a compound represented by the composition formula BaLu 6 Si 7 O 24 and having the crystal structure shown in FIG. That is, it has been found that the structure has a structure represented by the following formula (1) as a general formula.
  • Q atom is Ba
  • R atom is Lu
  • G atom and T atom are Si
  • X atom and X atom are equivalent to O
  • this compound Since this compound has a large theoretical density of 6.0 and an effective atomic number of 63, it can be suitably used as a phosphor for ionizing radiation detectors similarly to scintillator crystals represented by Lu 2 SiO 5 .
  • Lu 2 SiO 5 has a high melting point of 2050 ° C., but the compound obtained in this example has an advantage that it is easy to grow a single crystal because it was melted by firing at 1800 ° C. Further, when an Ir crucible is used for single crystal growth, it is possible to grow at a temperature lower than 2000 ° C., which is the Ir softening point. That is, it can be expected that the cost of the member is reduced by extending the life of the crucible.
  • FIG. 3 shows the result of evaluating the attenuation characteristics of the light emission obtained by injecting a Cs-137 (662 keV) ⁇ -ray source into the sample melted and solidified in Example 1.
  • Luminescence derived from the 4f-5f transition of Ce 3+ inserted as the luminescence center was detected, and the lifetime was calculated to be 38 ns.
  • This compound has a life shorter than about 42 ns, which is the life of a general Lu 2 SiO 5 scintillator, and can be suitably used for a medical diagnostic device such as a PET device that requires light emission with a short life.
  • Example 2 to 10 Synthesis of BaLu 6 (Si 2 O 7 ) 2 (Si 3 O 10 ) Phase Substitutes and Solid Solutions>
  • the synthesis was performed in the same manner as in Example 1 in the procedure of weighing, mixing, pre-baking, pelletizing, and main baking. However, the temperature and time of pre-baking and main baking were appropriately changed in consideration of the volatility of the raw materials, the melting point, and the reactivity between the raw materials. Further, the main firing was performed in a mixed atmosphere of Ar / H 2 (3%). Table 2 shows each experimental condition.
  • FIG. 4 shows the XRD pattern simulated from the XRD measurement result of the sample obtained in Example 2 and the crystal structure analysis result of Example 1.
  • the peak patterns are in agreement, and it can be seen that in Example 2, single-phase BaLu 6 (Si 2 O 7 ) 2 (Si 3 O 10 ) was synthesized.
  • the XRD measurement results of Examples 2 to 10 are shown in FIG. 5, FIG. 6, and FIG. In both cases, the peak pattern is the same, and it can be seen that a substitution product and a solid solution are generated.
  • Table 3 shows the lattice constants calculated from the XRD measurement results.
  • Examples 11 to 13 Synthesis of Pr, Eu, Tb activator of BaLu 6 (Si 2 O 7 ) 2 (Si 3 O 10 )> BaLu 6 (Si 2 O 7 ) 2 (Si 3 O 10 ) to which Pr, Eu, and Tb were added as the emission center was synthesized. Pr 6 O 11 , Eu 2 O 3 , and Tb 2 O 3 were used as raw materials for each activator. The synthesis was performed in the same manner as in Example 1 in the procedure of weighing, mixing, pre-baking, pelletizing, and main baking. The main calcination of Example 11 was performed under a mixed atmosphere of Ar / H 2 (3%), and the main calcinations of Examples 12 and 13 were performed under air. Table 4 shows each experimental condition.
  • the count number when the sample is not filled in the cell in the same measurement system is also shown. As is apparent from Table 5, all the samples have a significantly larger detection count than the case of “no sample”, indicating that the sample is emitting light by X-ray excitation. As described above, the results of Examples 1 to 13 indicate that the phosphor of the present invention can be suitably used as a phosphor material for use in a radiation detector.
  • the obtained compound is a compound represented by the composition formula BaLu 4 Si 5 O 17 , which has the same structure as BaY 4 Si 5 O 17 which is a known compound.
  • FIG. 15 shows a schematic diagram of the crystal structure of BaLu 4 Si 5 O 17 .
  • This compound can be represented by the following general formula (1), similarly to the compound group synthesized in Examples 1 to 13.
  • the Q atom is Ba
  • the R atom is Lu
  • the G atom and the T atom are Si
  • the X atom and the X atom are O, and represented by BaLu 4 (Si 2 O 7 ) (Si 3 O 10 ). Is done.
  • Si which is an element G
  • two tetrahedrons are connected to form a unit (Si 2 O 7 ).
  • FIG. 16 shows the XRD measurement result of the sample synthesized in Example 14, and the XRD pattern simulated from the crystal structure of FIG. The peak patterns coincide with each other, indicating that single-phase BaLu 4 (Si 2 O 7 ) (Si 3 O 10 ) was synthesized in Example 14.
  • Example 15 to 18 Synthesis of BaLu 4 (Si 2 O 7 ) (Si 3 O 10 ) Substitutes and Solid Solutions>
  • the BaLu 4 (Si 2 O 7 ) (Si 3 O 10 ) phase obtained in Example 14 and the substitution product and solid solution Ce activator of this phase were synthesized.
  • the synthesis was performed in the same manner as in Example 14 in the procedure of weighing, mixing, pre-baking, pelletizing, and main baking. However, the temperature and time of pre-baking and main baking were appropriately changed in consideration of the volatility of the raw materials, the melting point, and the reactivity between the raw materials. Further, the main calcination was performed in a mixed atmosphere of Ar / H 2 (3%) in Examples 15 to 17, and in the air in Example 18. Table 7 shows each experimental condition.
  • the sample after the main firing was pulverized and mixed in a mortar, and XRD measurement was performed.
  • the XRD measurement result of a typical sample (Examples 17 and 18) is shown in FIG. Table 8 shows the lattice constants calculated from the XRD measurement results.
  • 18 to 21 show the UV excitation emission spectra of the samples prepared in Examples 14 to 17, respectively. In any sample, broad emission having a maximum emission peak intensity in the vicinity of 400 nm was observed. This is attributed to the light emission of the 5d-4f transition of Ce 3+ put as the emission center element. Ce 3+ light emission has a short light emission lifetime, and can be used for a diagnostic apparatus such as a PET apparatus in which the decay time is regarded as important.
  • the sample after the main firing was pulverized and mixed in a mortar, and the UV excitation emission spectrum was measured.
  • the results are shown in FIGS.
  • FIGS. As shown in FIG. 22, from the sample of Example 19 to which Pr was added, broad emission derived from the 5d-4f transition of Pr 3+ was observed from 250 nm to 340 nm.
  • the light emission of Pr 3+ is suitable for use in a diagnostic apparatus such as PET because it has a short light emission life like the light emission of Ce 3+ .
  • the light emission having a sharp peak at 315 nm in FIG. 22 is light emission derived from the ff transition of Gd 3+ mixed as an impurity from a member such as a mortar.
  • the count number when the sample is not filled in the cell in the same measurement system is also shown. As can be seen from Table 10, all the samples have a significantly larger detection count than the case of “no sample”, indicating that the samples are emitting light by X-ray excitation. As described above, the results of Examples 14 to 21 indicate that the phosphor of the present invention can be suitably used as a phosphor material for use in a radiation detector.

Abstract

La présente invention aborde le problème de la fourniture d'un matériau luminophore qui a une nouvelle composition et permet d'avoir des caractéristiques de scintillateur considérablement améliorées. Le problème est résolu par un luminophore qui est destiné à détecter un rayonnement ionisant et qui est représenté par la formule (1). (1) QpRs(G2X7)u(T3Z10)q (Dans la formule (1), Q comprend au moins un élément choisi dans le groupe constitué par les éléments du groupe des métaux alcalino-terreux, R comprend au moins un élément choisi dans le groupe constitué par les éléments du groupe des métaux des terres rares, G et T comprennent chacun indépendamment au moins un élément choisi dans le groupe constitué par le Si, le Ge et le Sn, et X et Z comprennent au moins l'O (oxygène). En outre, p, s, u et q satisfont 0,9 ≤ p ≤ 1,1, 3,5 ≤ s ≤ 12,5, 0,8 ≤ u ≤ 5,2, et 0,9 ≤ q ≤ 1,1, respectivement).
PCT/JP2017/044190 2016-12-16 2017-12-08 Luminophore permettant de détecter un rayonnement ionisant, matériau luminophore contenant ledit luminophore, appareil d'inspection et appareil de diagnostic ayant ledit matériau luminophore WO2018110451A1 (fr)

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JP2014169390A (ja) * 2013-03-04 2014-09-18 Niigata Univ テルビウムを賦活したケイ酸塩緑色蛍光体
JP5674385B2 (ja) * 2010-08-27 2015-02-25 古河機械金属株式会社 シンチレータ用ガーネット型結晶およびこれを用いる放射線検出器

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