WO2020150344A1 - Scintillateurs en verre de chalcogénure et en vitrocéramique - Google Patents

Scintillateurs en verre de chalcogénure et en vitrocéramique Download PDF

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WO2020150344A1
WO2020150344A1 PCT/US2020/013670 US2020013670W WO2020150344A1 WO 2020150344 A1 WO2020150344 A1 WO 2020150344A1 US 2020013670 W US2020013670 W US 2020013670W WO 2020150344 A1 WO2020150344 A1 WO 2020150344A1
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scintillator
glass
previous
luminescent
chalcogenide
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Mark Davis
Joseph Hayden
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Schott Corporation
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/32—Non-oxide glass compositions, e.g. binary or ternary halides, sulfides or nitrides of germanium, selenium or tellurium
    • C03C3/321—Chalcogenide glasses, e.g. containing S, Se, Te
    • C03C3/323—Chalcogenide glasses, e.g. containing S, Se, Te containing halogen, e.g. chalcohalide glasses
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/32—Non-oxide glass compositions, e.g. binary or ternary halides, sulfides or nitrides of germanium, selenium or tellurium
    • C03C3/321—Chalcogenide glasses, e.g. containing S, Se, Te
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/12—Compositions for glass with special properties for luminescent glass; for fluorescent glass
    • C—CHEMISTRY; METALLURGY
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7701—Chalogenides
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7704—Halogenides
    • C09K11/7705—Halogenides with alkali or alkaline earth metals
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7714—Antimonates; Arsenates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7715—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing cerium
    • C09K11/7716—Chalcogenides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7715—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing cerium
    • C09K11/7719—Halogenides
    • C09K11/772—Halogenides with alkali or alkaline earth metals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
    • C09K11/7729—Chalcogenides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
    • C09K11/7732—Halogenides
    • C09K11/7733—Halogenides with alkali or alkaline earth metals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
    • C09K11/7742—Antimonates; Arsenates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C09K11/7767—Chalcogenides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
    • C09K11/7784—Chalcogenides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
    • C09K11/779—Halogenides
    • C09K11/7791—Halogenides with alkali or alkaline earth metals
    • 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

Definitions

  • the present disclosure describes chalcogenide glass and glass-ceramic compositions that can be used as scintillating materials.
  • the first refers to the case in which high- energy photons create electron-hole pairs in a material, typically a semiconductor, and a direct measure of the ensuing change in electrical properties of the semiconductor is made.
  • Direct detection systems offer superior energy resolution but do so at the cost of decreased stopping power (i.e. the ability to fully absorb high-energy photons and particles) as well as higher cost.
  • Indirect detection includes the broad class of scintillator materials, so-named due to their ability to produce photons of lower energies, commonly in the visible range, for which a wide range of sensitive detection methods already exist.
  • Non-single crystalline materials specifically glasses and glass ceramics, alleviate many of these constraints.
  • Glass is essentially a high-temperature solution whose atomic structure is largely frozen-in at the“glass transition”, a temperature region in which a high-temperate melt changes into an elastic solid owing to strong kinetic constraints.
  • Glass- ceramics are produced by crystallizing, in a controlled and deterministic manner, a precursor glass. Glass-ceramics typically contain a considerable fraction of residual, non-crystallized glass and, as such, are part crystalline and part glassy. Once cooled, both glasses and glass- ceramics behave in many ways like their fully crystalline counterparts with well-defined physical and optical properties.
  • the correspondence of the glass (or glassy portion of a glass-ceramic) to that of a solution, rather than that of a crystal means the accessible composition range of a glass or glass-ceramic far exceeds that of most crystals.
  • glass-forming techniques—relevant for glass-ceramics as well— are well known that permit very large formats (e.g., meter-class pieces, depending on the specific composition) and can do so at an expense far less than that of fully crystalline materials. Glasses and glass- ceramics are, typically, isotropic, meaning they do not possess directionally-specific properties. In general, these inherent advantages to a glass or glass-ceramic approach have to be weighed against performance that may be inferior to that of a crystal-based approach.
  • a so-called“extrinsic” scintillator relies on an added luminescent ion, or dopant, from which the scintillation photons arise ( Rodnyi , 1997).
  • Intrinsic scintillators including materials such as BaF2, do not rely on dopants but rather their inherent chemistry leads to visible light emission when illuminated with a high-energy photon.
  • the compositions described herein are largely, but not exclusively, extrinsic scintillators.
  • Scintillating materials must possess several key traits if they are to be truly useful; amongst the most important are the following ( Rodnyi , 1997; Lecoq, P. , Development of new scintillators for medical applications, Nuclear Instruments and Methods in Physics Research, Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, 809, 130-139, 2016):
  • Adequate light yield the ability with which a scintillator creates lower-energy photons based on an interaction with an X-ray or gamma ray; measured in units of created lower-energy photons per absorbed high-energy photon, usually normalized to 1 MeV (Ph/MeV).
  • Radiation hardness as scintillating materials will, by definition, be subjected to high-energy photons, the ability of these materials to withstand exposure to such photons without incurring significant damage over time is critical.
  • Chalcogenide glasses and glass-ceramics are well known in the field of infrared (IR) imaging owing to their enhanced optical transmission for wavelengths exceeding 3 microns. They have low band-gap energies, which is the difference in energy levels between the valence and conduction bands of the constituent atoms in the base glass. As has been recognized previously, fully crystalline materials with lower band-gap energies tend to have higher scintillator light outputs (e.g., Lecoq et al, 2017). Figure 1 shows the scintillation light yield plotted as a function of material band-gap energy ⁇ Lecoq, 2016).
  • the solid line is based on a theoretically -best type of behavior; the various data points correspond to that of known scintillating crystals. While such a correlation provides rough guidance on compositional families that might be of interest, they do not provide information necessary to design a glass or glass-ceramic composition which is (1) stable against un-controlled crystallization; (2) have specific scintillation properties of interest (e.g., fast decay time; sufficient stopping power for a gamma-ray); (3) have adequate chemical durability, and so on.
  • Figure 1 suggests that materials with band gap energies ⁇ 3.0 eV and, more commonly, ⁇ 2.5 eV should have high light yields.
  • chalcogenide crystals are well known and employed in the scintillation community (e.g., ZnS:Ag)
  • the use of chalcogenide glasses and glass-ceramics as an indirect scintillator is nearly absent from the technical and patent literature.
  • the present disclosure provides a scintillator comprising a luminescent chalcogenide glass or glass-ceramic composition that converts non-visible spectrum radiation into visible spectrum radiation with a light yield of 3,000 Ph/MeV or more, a decay time of 1,000 nanoseconds or less, a density of 3.0 g/cm3 or more, and/or an afterglow of 5% or less at 3 milliseconds.
  • the luminescent chalcogenide glass or glass-ceramic composition comprises a chalcogen base component, a luminescent component, and/or an additive that enhances solubility of the luminescent component.
  • the luminescent component comprises a lanthanide.
  • the present disclosure also provides a radiological image detector comprising the described scintillator(s) BRIEF DESCRIPTION OF THE FIGURES
  • Figure 1 is a graph showing scintillation light yield as a function of material band-gap energy.
  • Figure 2 is a schematic description of electron transitions in lanthanum compounds.
  • FIG. 2 is a schematic illustration of four different types of electronic transitions that can be observed in lanthanide-activated compounds ( Dorenbos , P., Electronic structure engineering of lanthanide activated materials, Journal of Materials Chemistry, 22 (42), 22344-22349, 2012a). Note the overlap of d-level electronic shells (broad horizontal lines just above“fd” energy transfer arrows) with the conduction band, implying the critical interplay between these two features.
  • chalcogenide glass and glass-ceramic compositions and compositional families specifically engineered so as to maximize the attributes noted above that are important for efficient and useful scintillation, and to minimize non-radiative pathways during the luminescence phase, thereby maximizing the scintillation yield.
  • chalcogenide glasses and glass-ceramics— far exceed that of oxygen (Z 8) leading to enhanced stopping power relative to oxide glasses.
  • Chalcogenide glass and glass-ceramic scintillators can be roughly subdivided in two main families with regard to the (desirable) solubility of positively charged, luminescent ions such as the lanthanides.
  • the spectroscopic redshift D tends to increase in this order: fluorides ⁇ chlorides ⁇ bromides ⁇ iodides ⁇ oxides ⁇ sulfides ⁇ selenides ⁇ tellurides ( Dorenbos , 2012b).
  • This combined with the classification system of Choi noted above, gives us degrees of freedom for compositional tuning. For example, we can shift the Ce emission to longer or shorter wavelengths to avoid thermal quenching of the emitting state to the conduction band, thereby avoiding host glass absorption, and placing emission within the sensitivity range of popular detectors.
  • Non-limiting examples of materials useful as scintillators include glass and glass- ceramic compositions having a chalcogen base component, a luminescent component and/or an additive.
  • the materials can be manufactured in manners known to those skilled in the chalcogenide glass and glass-ceramic arts.
  • compositional families useful for the scintillators of the disclosure include those with at least some degree of transmission in the visible part of the spectrum to have a luminescence matching the sensitivity ranges of conventional detectors (e.g., PMT, Si photodiodes, etc.).
  • glasses and glass-ceramics having a chalcogen base component based on S, Se, and Te but with band-gap energies in the range of, approximately, ⁇ 3.5 eV or 2.0 to 3.5 eV are included herein.
  • the chalcogen base component can include additional elements including but not limited to Al, Ga, In, Si, Ge, Sn, Pb, P, As, Sb, Sc, Y, La, Gd and Lu.
  • constituents may be added to the base component to act as nucleation sites for crystals, including but not limited to titanium and zirconium; to create desired phase separation, including but not limited to boron and aluminum; and as desirable components within the crystal phase or to adjust glass properties, such as alkali cations, including but not limited to Li, Na, K, Rb, Cs, and alkaline earth cations, including but not limited to Sr and Ba.
  • the combined amount of the chalcogen and other components of the base component can be present in about 75 to less than 100 mol% of the composition.
  • the base component includes no Ge, Ge from 10-30 mol%, 14-25 mol%, 24-25 mol%; no Ga, Ga from 4-30 mol%, 4-17 mol% or 10-17 mol%, no La or La from 10-15 mol%; no Sb, Sb from 5-25 mol%, 5-12 mol%, 5-10 mol%, 10-12 mol% or 12-22 mol%; no S, S from 50-75 mol%, 52-70 mol%, 54-65 mol%, 57-60 mol% or 64-70 mol%; and/or no Ba or Ba from 20- 25 mol%.
  • Scintillation may be produced by the base components themselves but is more commonly produced from a luminescent component which can be single luminescent ions or a luminescent ion system involving two or more dopants that interact energetically within the base component.
  • Luminescent ions are principally, but not exclusively, chosen from the lanthanides with partially filled 4f orbitals (e.g., Ce, Pr, Sm, Eu, Tb, Dy, Ho, Er, Tm and Yb), usually present in either or some combination of the 2+, 3+ and 4+ oxidation states after or during exposure to high energy radiation.
  • Additional luminescent ion systems considered are those with empty, partially or completely filled d orbitals; examples include but are not limited to chromium, manganese, vanadium, scandium, nickel, copper, titanium, niobium, silver, zirconium, molybdenum, tantalum, tungsten, gold, and hafnium in oxidation states from +1 to +6.
  • Specific examples include, but are not limited to, Cu 1+ , Ag 1+ , Au 1+ , V 2+ , Ti 2+ , Mn 1+ , Ni 2+ , Co 2+ , Mn2+, V 3+ , Fe 2+ , Fe 3+ , Ti 3+ , Ni 3+ , Cr 3+ , Cr4+, Mn 4+ , Mn 5+ , and Cr 5+ , depending on the number of d orbital electrons present, which in some embodiments are present from greater than 0 to 10 mol% or less.
  • luminescent ion systems also contain elements where s orbitals are involved in the generation of scintillation light; examples include but are not limited to thallium (Tl + ), lead (Pb2+), and bismuth (Bi 3+ ). These ion systems can combine elements from f, d and s orbital ions.
  • the luminescent component can be absent and when used can be present from 0.05-0.25 mol%.
  • Additives specifically chosen to enhance lanthanide solubility include Ga, In, halides, and oxygen (O).
  • Halides e.g., F, Cl, Br, I
  • band-gap level positions in particular, the bottom of the conduction band and top of the valence band— is known to be particularly effective at influencing d-shell electronic orbitals due to the relative lack of shielding that such orbitals experience in the lanthanide family.
  • radiative characteristics e.g., emission cross-section, lifetime
  • the additives can be absent and when used can be present from 3-15 mol%, 3.1-5 mol%, 5-15 mol% or 8-15 mol%.
  • chalcogenide glass-ceramics are also useful as scintillators.
  • oxide- or oxy-fluoride based glass-ceramic scintillators e.g., Kang, Z. T., R. Rosson, B. Barta, C. Han, J.H. Nadler, M. Dorn, B. Wagner, and B. Kahn, GdBr3:Ce in glass matrix as nuclear spectroscopy detector, Radiation Measurements, 48 (1), 7-11, 2013; Cao, J, W. Chen, L. Chen, X. Sun, andH.
  • Glass-ceramics are, in general, produced by crystallizing, in a controlled and deterministic manner, a precursor glass. In principle, glass-ceramics can combine the positive attributes of both crystals and glass— as described above— in one material (e.g., Holand, W., and G.H. Beall, Glass-Ceramic Technology, 2 Ed., 414 pp., The American Ceramic Society, Westerville, 2012).
  • the foregoing components can be present in an amount from greater than 0 to 15 mol% or less.
  • Non-limiting examples of glass and glass-ceramic compositions useful as scintillators are shown in Tables 1-7.
  • luminescent ion species may be present alone, or one or more can be present together to give scintillation light of desired properties.
  • the luminescent ions and the host glass, or crystals in the case of a glass-ceramic one or more specific functionalities are exploited within the scintillation process , including ( e.g., Dorenbos , 2012a):
  • MMCT Metal -to-metal charge transfer
  • Luminescent ion-to-luminescent ion energy transfer in which only energy is exchanged, leading to a rich variety of phenomena, including, but not restricted to, resonant transfer, phonon-assisted transfer, cross relaxation, and upconversion (e.g., Auzel, F, Upconversion and anti-Stokes processes with f and d Ions in solids, Chemical Reviews, 104 (1), 139-173, 2004; Kalisky, Y, The Physics and Engineering of Solid State Lasers, tutorial Texts in Optical Engineering, vol. TT71, 203 pp., SPIE Press, 2006).
  • upconversion e.g., Auzel, F, Upconversion and anti-Stokes processes with f and d Ions in solids, Chemical Reviews, 104 (1), 139-173, 2004; Kalisky, Y, The Physics and Engineering of Solid State Lasers, tutorial Texts in Optical Engineering, vol. TT71, 203 pp., SPIE Press, 2006.
  • a scintillator detection system is composed of a scintillating material, an apparatus to gather and focus the scintillation photons (visible to near-IR region) into a light detector (e.g., a photomultiplier tube), a means by which to transmit and amplify the generated electrical signals using appropriate electrical means, and, finally, an apparatus to perform any necessary counting statistics using, for example, a single- or multi-channel analyzer.
  • General configurations for the glasses and glass-ceramics considered herein include those as a bulk scintillator, but also fiber-based configurations, particularly— though not exclusively— as used in multi-channel plates. Specific applications include digital radiography, computed tomography (CT), PET imaging, baggage and cargo security screening, oil and gas exploration, and nuclear power plant monitoring.
  • CT computed tomography
  • PET imaging PET imaging
  • baggage and cargo security screening oil and gas exploration
  • nuclear power plant monitoring nuclear power plant monitoring.
  • Testing methods employ standard techniques used for characterization of transparent, luminescing materials, including optical transmission, luminescence emission and excitation, photoconductivity, optical reflectance and thermo-luminescence; the latter technique is particularly useful for identification of energy traps within the forbidden zone (between the VB and CB) which can seriously affect light output from a scintillator.
  • techniques specifically designed for characterization of scintillator materials can be used, including a photomultiplier tube (PMT), a low-activity radiation source, and a multi-channel analyzer to conduct pulse-height analysis thereby establishing the gamma-ray energy resolution and light output of the scintillator ⁇ Knoll, 2010).
  • the present disclosure describes scintillators including those that comprise a luminescent chalcogenide glass composition or a luminescent chalcogenide glass-ceramic composition, wherein the chalcogenide glass and glass-ceramic compositions convert high- energy, non- visible spectrum radiation into visible spectrum radiation with a light yield of 3,000 Ph/MeV or more, a decay time of 1,000 nanoseconds or less, a density of 3.0 g/cm 3 or more, and/or an afterglow of 5% or less at 3 milliseconds.
  • the disclosure also includes methods of converting high-energy non-visible spectrum radiation into visible spectrum radiation comprising the steps of exposing a luminescent chalcogenide glass composition or a luminescent chalcogenide glass-ceramic composition to the non-visible spectrum radiation, wherein the chalcogenide glass composition or chalcogenide glass-ceramic composition converts the high-energy non-visible spectrum radiation into visible spectrum radiation with a light yield of 3,000 Ph/MeV or more, a decay time of 1,000 nanoseconds or less, a density of 3.0 g/cm 3 or more, and an afterglow of 5% or less at 3 milliseconds.
  • the light yield is 10,000 Ph/MeV or more or 30,000 Ph/MeV or more; the decay time is 100 nanoseconds or less or 40 nanoseconds or less; the density is 3.5 g/cm 3 or more or 4.0 g/cm 3 or more; and/or the afterglow is 0.1% or less at 3 milliseconds or 0.01% or less at 3 milliseconds.
  • the luminescent material can be present in an amount from about 0.01 to about 5 mol% of the composition and can be a lanthanide, a transition metal, or a combination thereof.

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  • Measurement Of Radiation (AREA)

Abstract

La présente invention concerne des compositions de verre de chalcogénure et de vitrocéramique qui peuvent être utilisées comme matériaux scintillants.
PCT/US2020/013670 2019-01-16 2020-01-15 Scintillateurs en verre de chalcogénure et en vitrocéramique WO2020150344A1 (fr)

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CN112723749A (zh) * 2021-03-03 2021-04-30 哈尔滨工程大学 一种含有闪烁纳米晶体的高透明微晶玻璃及制备方法
CN115124238A (zh) * 2022-05-17 2022-09-30 北京工业大学 一种红外非线性硫系玻璃材料及其制备方法

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JP2012036230A (ja) * 2010-08-03 2012-02-23 Univ Of Miyazaki 蛍光体および電磁波検出装置
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112723749A (zh) * 2021-03-03 2021-04-30 哈尔滨工程大学 一种含有闪烁纳米晶体的高透明微晶玻璃及制备方法
CN115124238A (zh) * 2022-05-17 2022-09-30 北京工业大学 一种红外非线性硫系玻璃材料及其制备方法
CN115124238B (zh) * 2022-05-17 2023-12-01 北京工业大学 一种红外非线性硫系玻璃材料及其制备方法

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