EP4263747A1 - Kunststoffszintillatoren mit durch purcell-effekt verstärkter intrinsischer emission - Google Patents

Kunststoffszintillatoren mit durch purcell-effekt verstärkter intrinsischer emission

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Publication number
EP4263747A1
EP4263747A1 EP21839525.9A EP21839525A EP4263747A1 EP 4263747 A1 EP4263747 A1 EP 4263747A1 EP 21839525 A EP21839525 A EP 21839525A EP 4263747 A1 EP4263747 A1 EP 4263747A1
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EP
European Patent Office
Prior art keywords
plastic scintillator
fluorophore
plastic
objects
dpa
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP21839525.9A
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English (en)
French (fr)
Inventor
Djadidi TOYBOU
Vesna Simic
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Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
Original Assignee
Commissariat a lEnergie Atomique CEA
Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
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Publication of EP4263747A1 publication Critical patent/EP4263747A1/de
Withdrawn legal-status Critical Current

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    • 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
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials

Definitions

  • the present invention relates to the field of plastic scintillators for the detection of ionizing radiation. It relates, more particularly, to new plastic scintillators whose chemical composition has been optimized to improve their intrinsic emission properties by PURCELL effect.
  • the PURCELL effect makes it possible to amplify the number of photons emitted, to orient their propagation towards privileged axes (improve collection) and to reduce their decay time (faster response) in order to make these detectors more efficient (better signal at noise, increased sensitivity to low energies, better temporal resolution, discrimination between different radiations).
  • the plastic scintillators of the invention can be used for applications in the field of the nuclear power industry, research in nuclear physics, medical physics (medical imaging and radiotherapy), and in general for security and surveillance. nuclear and radiological risks.
  • Scintillation detectors are devices comprising an optically coupled scintillator and photodetector.
  • a scintillator receives ionizing radiation on one of its faces and emits scintillation photon radiation due to the interaction between the ionizing radiation and the constituent material of the scintillator.
  • the scintillation photon radiation emitted in the isotropically scintillating material is collected by the photodetector from one side of the scintillator, and converted into an electrical signal that is more easily usable.
  • scintillators can be organic, inorganic or hybrid organic-inorganic in nature.
  • organic scintillators there are plastic scintillators, which are composed of a polymer matrix, typically polystyrene or its derivatives, incorporating one or more fluorescent molecules (usually two) also called fluorophores in low proportions with respect to the matrix polymer.
  • the fluorescent molecules are chosen so that their absorption and emission spectra are complementary and make it possible to shift, by energy transfer, the emission of the matrix towards the maximum sensitivity of the photodetector and in a spectral range corresponding to an area of transparency of the material.
  • Plastic scintillators have many advantages from the point of view of the material, in particular because of their low manufacturing costs, their availability, their ease of shaping and machining, their large size, their robustness, their non-hygroscopic nature or else their low sensitivity to heat (the range of use, where the operation of said scintillators is independent of temperature, extends from -60° C. to +20° C.). They also have advantages from the point of view of detection, due to their very short response time (radiative lifetime of 1 to 4 nanoseconds) and their high hydrogen content (suitable for neutron detection). However, plastic scintillators are less efficient in terms of detection than organic crystalline scintillators (anthracene, stilbene) or inorganic crystal scintillators.
  • the proposed solutions consist in modifying the chemical composition of the scintillator to improve the absorption of the ionizing radiation (by increasing the effective atomic number of the material) or the quality of the energy transfer between fluorophores or fluorescent molecules.
  • J. Liu et al. Enhanced light extraction efficiency of plastic scintillator by photonic crystal prepared with a self-assembly method.
  • J. Liu et al. Nuclear Instruments and Methods in Physics Research A 795 (2015) 305–308 describe the incorporation of an assembly compact polystyrene beads of nanometric dimensions on the surface of a plastic scintillator to form an anti-reflective photonic structure on the exit face of the scintillator.
  • the aim of the invention is not only to improve the extraction of scintillation photon radiation in the direction of the photodetector but also to increase the spontaneous emission rate of the plastic scintillator and to reduce the emission time of these photons by exploiting the PURCELL effect.
  • This effect can be obtained by modifying the electromagnetic environment of the transmitter by nanostructuring the emissive material by means of microcavities of low volume and high quality factor as described in EP3 502 750.
  • This approach requires materials of higher optical index than standard plastic scintillators to maximize the effects.
  • the second approach consists in amplifying the spontaneous emission of the emitter by coupling it to surface plasmons using metallic nano-objects.
  • R 1 and R 2 identical or different, represent a hydrogen atom, a mono or polycyclic aryl radical comprising from 6 to 18 carbon atoms, said mono or polycyclic aryl radical being optionally substituted,
  • either is in the form of a nanostructured layer having a thickness of between 1 ⁇ m and 10 mm, in which holes and protrusions or spikes are made, with a diameter of between 70 nm and 250 nm, and a height of between 1 ⁇ m and 10mm;
  • . either comprises one or more metallic nano-objects.
  • the plastic scintillator of the invention can therefore comprise metallic nano-objects, in particular metallic nanowires, preferably in the form of silver nanowires having a cross-section between 1 and 150 nm 2 and whose length/diameter ratio is greater than 10.
  • the plastic scintillator when it does not include metallic nano-objects, is in the form of a nanostructured layer having a thickness of between 1 ⁇ m and 10 mm, in which holes and protuberances or spikes, also called “pillars", with a diameter between 70 nm and 250 nm and a height between 1 ⁇ m and 10 mm.
  • the distance between the holes and the pillars is less than ⁇ /2.n eff .
  • lambda ( ⁇ ) represents the wavelength of scintillation photon radiation and n eff the effective refractive index of the polymer.
  • plastic scintillators of the invention allow an improvement in the extraction of scintillation photon radiation in the direction of the photodetector and also an increase in the spontaneous emission rate of the plastic scintillator and a reduction in the emission time of these photons by exploiting the PURCELL effect, and this without using organometallic complexes based on iridium and bismuth as described in the state of the art.
  • the invention also relates to an ionizing radiation detector comprising a plastic scintillator according to the invention and a photodetector.
  • Another object of the invention is the use of a plastic scintillator according to the invention, in nuclear instrumentation for measuring the intensity of gamma, electron or neutron radiation, in nuclear medicine, in radiation protection of people in their workplaces or in the environment, for the inspection of goods, for the monitoring and control of cosmic radiation.
  • TEOS tetraethyl orthosilicate
  • PTES triethoxy(phenyl)silane
  • R 1 and R 2 identical or different, represent a hydrogen atom, a mono or polycyclic aryl radical comprising from 6 to 18 carbon atoms, said mono or polycyclic aryl radical being optionally substituted,
  • either is in the form of a nanostructured layer having a thickness of between 1 ⁇ m and 10 mm, in which holes and protrusions or spikes are made, with a diameter of between 70 nm and 250 nm, and a height of between 1 ⁇ m and 10mm;
  • . either comprises one or more metallic nano-objects.
  • the plastic scintillator of the invention can therefore comprise metallic nano-objects, in particular metallic nanowires, preferably in the form of silver nanowires having a section between 1 and 150 nm 2 and whose length/diameter ratio is greater at 10.
  • the plastic scintillator when it does not comprise metallic nano-objects, may be in the form of a nanostructured layer having a thickness of between 1 ⁇ m and 10 mm, in which holes and protrusions or spikes are made, also called "pillars", with a diameter between 70 nm and 250 nm and a height between 1 ⁇ m and 10 mm.
  • the distance between the holes and the pillars is less than ⁇ /2.n eff .
  • lambda ( ⁇ ) represents the wavelength of scintillation photon radiation and n eff the effective refractive index of the polymer. Examples of such nanostructures with nanopillars and nanoholes are described in application EP3 502 750 and represented, respectively, in FIGS. 3 and 4 of this application.
  • plasticizer is meant a liquid substance of low volatility (a low saturated vapor pressure) or solid, incorporated into a matrix of polymer(s), which modifies the rheological properties of the polymer or mixture. of polymers, improves the implementation of the polymer or mixture of polymers, makes it possible to improve the flexibility of the finished product, its resistance to shocks and to low temperatures.
  • the plasticizers can be polymerized or not, of low molar mass (200 to 400 g/mol).
  • plasticizer By way of example of a plasticizer, mention may be made of phthalates, phosphates, epoxides (adipates, azelates, sebacates, in particular polyadipate and polysebacate of ethylene glycol, polysuccinate).
  • polymerization initiator is meant a compound allowing the initiation and progress of the polymer formation reaction.
  • the polymerization initiators are preferably radical or cationic.
  • radical polymerization initiator the generation of radicals can take place by thermal decomposition (thermal initiators), under the action of light or UV radiation (photochemical initiators) or by an oxidation-reduction reaction (initiators redox).
  • thermal initiators such as, for example, azo compounds such as azo-bis(isobutyronitrile or AIBN, peroxides such as benzoyl peroxide or lauroyl peroxide; redox initiators such as peroxyesters such as tert -Bu 2-ethylhexane peroxoate or tert -Bu peroxy -2-ethylhexane; photochemical initiators such as benzil, benzophenone, 2,2-dimethoxy-2-phenylacetophenone (DMAP or Irgacure 651), for example.
  • azo compounds such as azo-bis(isobutyronitrile or AIBN, peroxides such as benzoyl peroxide or lauroyl peroxide
  • redox initiators such as peroxyesters such as tert -Bu 2-ethylhexane peroxoate or tert -Bu peroxy -2-ethylhexane
  • photochemical initiators
  • the initiation is done with an acid.
  • Br ⁇ nsted acids such as sulfuric or triflic acid can be used, as well as Lewis acids such as AlCl 3 , TiCl 4 , BF 3 , HClO 4 , optionally in the presence of a co-initiator.
  • the term “nanostructured” is used in the sense described above with a diameter of the holes and/or pillars which is between 70 nm and 250 nm and a height of the holes and/or pillars which is between 1 ⁇ m and 10 mm.
  • the distance between the holes and the pillars is less than ⁇ /2.n eff .
  • lambda ( ⁇ ) represents the wavelength of scintillation photon radiation and n eff the effective refractive index of the polymer.
  • fluorophore is meant a chemical molecule capable of emitting fluorescence light upon excitation, usually by absorption of a photon immediately followed by spontaneous emission.
  • fluorophore and fluorescent molecule may be used interchangeably.
  • metallic nano-objects we mean metallic materials made of aluminum (Al), silver (Ag), gold (Au), copper (Cu), lithium (Li), platinum (Pt) or palladium (Pd), having one, two or three dimensions located between 1 and 100 nm.
  • Metallic nano-objects can be in the form of . nanoparticles whose three dimensions are between 1 and 100 nm, . nanowires, nanofibers, or nanotubes, which are slender nano-objects with a section between 1 and 150 nm 2 and whose length/diameter ratio is greater than 10.
  • aryl generally designates a mono- or poly-cyclic aromatic hydrocarbon comprising from 6 to 18 carbon atoms.
  • aryl radical can be optionally substituted by .
  • alkyl within the meaning of the present invention, means a linear, branched or cyclic, saturated, optionally substituted carbon radical comprising 1 to 12 carbon atoms, for example 1 to 8 carbon atoms, for example 1 to 6 carbon atoms.
  • saturated, linear or branched alkyl mention may be made, for example, of the methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecanyl radicals and their branched isomers.
  • cyclic alkyl within the meaning of the present invention, means a cyclic carbon radical, saturated, optionally substituted, comprising 3 to 12 carbon atoms, for example 3 to 10 carbon atoms, for example 3 to 8 carbon atoms.
  • cyclic alkyl mention may be made of the cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, bicyclo[2,1,1]hexyl, bicyclo[2,2,1]heptyl, adamantyl radicals.
  • the alkyl radical may optionally be substituted by . one or more groups –NH 2 , -NHR 5 , -NR 5 R 6 with R 5 and R 6 , identical or different, representing a phenyl, an alkyl radical containing 1 to 12 carbon atoms, . one or more hydroxyl, . one or more halogen atoms chosen from fluorine, chlorine, bromine and iodine atoms, . one or more nitro groups (-NO 2 ), . one or more nitrile groups (-CN).
  • amine is meant a group of formula -NR 7 R 8 , in which R 7 and R 8 , which are identical or different, represent a hydrogen atom, an alkyl comprising 1 to 12 carbon atoms as defined in the context of the invention, an aryl comprising 6 to 18 carbon atoms as defined in the context of the invention, the alkyl and the aryl being optionally substituted as defined above.
  • thiol is meant a group of formula –SR 9 , in which R 9 is a hydrogen atom, an alkyl comprising 1 to 12 carbon atoms as defined in the context of the invention, an aryl comprising 6 with 18 carbon atoms as defined in the context of the invention, the alkyl and the aryl being optionally substituted as defined above.
  • epoxy is meant a group of the formula
  • R 10 R 11 and R 12 which are identical or different, represent a hydrogen atom, an alkyl comprising 1 to 12 carbon atoms as defined in the context of the invention, an aryl comprising 6 to 18 carbon atoms as defined in the context of the invention, the alkyl and the aryl being optionally substituted as defined above.
  • the polymer can be chosen from polystyrene, the isomers of polymethylstyrene (alpha-, ortho-meta-, para-methylstyrene), poly-vinyltoluene, polyvinyltriphenylamine, polyfluorene, polyvinylfuran and poly(N-vinylcarbazole) (PVK).
  • the polymer is chosen from polystyrene, polymethylstyrene isomers (alpha-, ortho-meta-, para-methylstyrene), polyvinyltoluene, and polyvinylcarbazole (PVK).
  • the plastic scintillator of the invention may comprise one or more fluorescent molecules or fluorophore(s) of formula (I).
  • it consists of a polymer matrix as defined above incorporating two fluorescent molecules or fluorophores.
  • it may be advantageous to incorporate more than two fluorescent molecules or fluorophores.
  • the fluorophores can be the same or different.
  • the fluorophore(s) are present in an amount of between 0.01% and 3% by weight, preferably between 0.01 and 1.5% by weight. mass, relative to the total mass of the plastic scintillator. In the case where several fluorophore(s) are present, it is indeed the total quantity of fluorophores which is between 0.01% and 3% by mass, preferably between 0.01 and 1.5% by mass, by relative to the total mass of the plastic scintillator.
  • the plastic scintillator of the invention when it does not comprise metallic nano-objects, in particular metallic nanowires, preferably silver nanowires (AgNWs), is in the form of a nanostructured layer having a thickness between 1 ⁇ m and 10 mm, in which holes and protuberances or spikes, also called “pillars", are made with a diameter between 70 nm and 250 nm and a height between 1 ⁇ m and 10 mm.
  • the distance between the holes and the pillars is less than ⁇ /2.n eff .
  • lambda ( ⁇ ) represents the wavelength of scintillation photon radiation and n eff the effective refractive index of the polymer. Examples of such nanostructures with nanopillars and nanoholes are described in application EP3 502 750 and represented respectively in FIGS. 3 and 4 of this application.
  • the nanostructuring of the plastic scintillators of the invention by means of holes and pillars as defined above modifies the electromagnetic environment of the scintillator.
  • Said nanostructures are 2D arrays of nano-pillars and nano-holes, with pitch and diameter between 70 nm and 250 nm.
  • the nanostructuring of the scintillators is done using recent structuring processes known to those skilled in the art, namely the NIL (Nano-Imprint Lithography) process as described by S.Y. Chou, P.R. Krauss, P.J. Renstrom, 1996, Imprint lithography with 25-nanometer resolution, Science, 272, 5258, 85 87; the NEP (NanoEmbossing of Polymers) process as described by M.
  • NIL Nano-Imprint Lithography
  • nanostructuring gives the photons emitted in the cavity a directional character, which makes their collection easier. They also have the particularity of being emitted faster (shorter decay time) than in a free environment, which can be advantageously used to differentiate between several radiations by separating the signal from the nanostructured volume from that of the rest of the scintillator. .
  • Nanostructuring can also improve the temporal resolution of large scintillators which suffer from insufficient resolution for applications such as PET (Positron Emission Tomography) for example.
  • the plastic scintillator of the invention comprises one or more metallic nano-objects made of aluminum (Al), silver (Ag), gold (Au), copper ( Cu), lithium (Li), platinum (Pt) or palladium (Pd), in the form of nanoparticles, nanowires, nanofibers, or nanotubes, as defined above.
  • the metallic nano-objects are in the form of metallic nanowires having a section between 1 and 150 nm 2 and whose length/diameter ratio is greater than 10.
  • Nanowires of different metals, chosen from those mentioned above, can be used.
  • the metallic nano-objects are made of silver and in the form of nanowires (in English, Silver NanoWires or AgNWs) having a section between 1 and 150 nm 2 and whose length/diameter ratio is greater than 10.
  • the presence of metallic nano-objects as defined above, in particular in the form of nanowires, makes it possible to enhance the luminescence of the polymer matrix which can then transfer more light to the fluorophore(s).
  • the light response is thus amplified by the phenomenon of plasmonic enhancement of fluorescence.
  • the phenomenon of plasmonic enhancement of fluorescence makes it possible to improve the efficiency, the transfer rate and the range of energy transfer by Förster type resonance (in English, Förster resonance energy transfer or FRET) within a Donor (the polymer matrix) – Acceptor (the fluorophore) couple by increasing the strength of the interactions between them. This can lead to a single Donor exciting multiple Acceptors over distances beyond the normal FRET range.
  • nanowires have at least one dimension approaching the wavelength of light and one dimension much larger than it.
  • the light coupled to the nanowire will excite the free electrons to create a surface plasmon that can run back and forth along the surface on the metallic nanowire: this is propagating surface plasmon.
  • these nanowires When these nanowires are sufficiently concentrated in the matrix to form a branched network of chains like a percolating network, their individual plasmon absorbance modes are modified and reveal a stronger common mode than those obtained with isolated nanowires. The appearance of these new plasmonic modes can be visualized on the UV-visible absorption spectra .
  • percolating network is meant an organization of nanowires creating a plasmonic coupling between two or more nanowires.
  • the concentration of nanowires in the matrix must be high enough to obtain chain percolation and low enough to maintain the transparency of the polymer matrix.
  • the concentration of nanowires in the matrix can be such that the transmittance of the material at the emission wavelength of the scintillator is not less than 80%.
  • Metallic nano-objects in particular metallic nanowires, and preferably silver nanowires (AgNWs), can be covered/encapsulated by a shell or a dielectric layer such as a layer of silica in order to reduce the quenching or quenching of fluorescence in direct contact with metal surfaces.
  • a shell or a dielectric layer such as a layer of silica
  • the method used for the production of the silica shell coating the metallic nanowires is the Stöber method as described by CY Li, M. Meng, SC Huang, L. Li, SR Huang, S. Chen, LY Meng, R. Panneerselvam , SJ Zhang, B. Ren, ZL Yang, JF Li, ZQ Tian, J. Am. Chem. Soc. 2015, 137, 13784–13787.
  • TEOS tetraethoxysilane
  • TMOS tetramethoxysilane
  • PTES triethoxy(phenyl)silane
  • APTS n-butyltrimethoxysilane
  • APTS 3-aminopropyl)-triethoxysilane
  • GPMES 3-glycidoxypropyl)-dimethyl-ethoxysilane
  • MPTMS 3-mercaptopropyl)-trimethoxysilane
  • the silica may carry on its surface a group allowing the grafting of the fluorescent molecule on the nano-object.
  • the groups on the surface of the silica can be chosen from hydroxyl (-OH with TEOS or TMOS), phenyl (-Ph with PTES), an alkyl as defined above, or an amine, an epoxy, a thiol as defined above. These groupings are cited by way of example and are in no way limiting.
  • the scintillator comprises metallic nano-objects, in particular metallic nanowires, preferably silver nanowires (AgNWs), covered by a shell or a layer of silica
  • the silica carries in its surface a group chosen from hydroxyl or phenyl.
  • the thickness of the silica layer can be between 5 to 50 nm.
  • the plastic scintillator comprises - a polymer as defined above,
  • R 1 and R 2 identical or different, represent a hydrogen atom, a mono or polycyclic aryl radical comprising from 6 to 18 carbon atoms chosen from phenyl, naphthyl, anthracenyl, fluorenyl, phenanthrenyl, acenaphthylenyl, fluoranthenyl, benzanthracenyl, chrysenyl, pyrenyl, said aryl radical being optionally substituted by .
  • one or more groups –NH 2 , -NHR 3 , -NR 3 R 4 with R 3 and R 4 identical or different, representing a phenyl; an alkyl radical containing 1 to 12 carbon atoms, .
  • the plastic scintillator comprises - a polymer as defined above, - one or more fluorophore(s) of formula (I)
  • R 1 and R 2 identical and different, represent a hydrogen atom, a mono or polycyclic aryl radical chosen from phenyl, naphthyl, anthracenyl, fluorenyl,
  • aryl radical being optionally substituted by .
  • alkyl radical being optionally substituted by .
  • the plastic scintillator comprises - a polymer as defined above, - one or more fluorophore(s) of formula (I)
  • R 1 and R 2 identical and different, represent a hydrogen atom, a mono or polycyclic aryl radical chosen from phenyl, fluorenyl,
  • aryl radical being optionally substituted by .
  • alkyl radical being optionally substituted by .
  • the plastic scintillator comprises - a polymer chosen from polystyrene, polymethylstyrenes (alpha-, ortho-, meta, para-), poly-vinyltoluene, and polyvinylcarbazole (PVK), - one or more fluorophore(s) of formula (I)
  • R 1 and R 2 identical and different, represent a hydrogen atom, a mono or polycyclic aryl radical chosen from phenyl, fluorenyl, said aryl radical being optionally substituted by .
  • R 3 and R 4 groups with R 3 and R 4 , which are identical or different, representing a phenyl, an alkyl radical containing 1 to 12 carbon atoms, . one or more alkyl groups having 1 to 12 carbon atoms.
  • the plastic scintillator in the first , second , third and fourth embodiments is in the form of a nanostructured layer having a thickness of between 1 ⁇ m and 10 mm, in which holes and protrusions or spikes, also called “pillars", with a diameter between 70 nm and 250 nm and a height between 1 ⁇ m and 10 mm.
  • the distance between the holes and the pillars is less than ⁇ /2.n eff .
  • lambda ( ⁇ ) represents the wavelength of scintillation photon radiation and n eff the effective refractive index of the polymer.
  • the plastic scintillator comprises - a polymer as defined above,
  • R 1 and R 2 identical or different, represent a hydrogen atom, a mono or polycyclic aryl radical comprising from 6 to 18 carbon atoms chosen from phenyl, naphthyl, anthracenyl, fluorenyl, phenanthrenyl, acenaphthylenyl, fluoranthenyl, benzanthracenyl, chrysenyl, pyrenyl, said aryl radical being optionally substituted by .
  • one or more –NH 2 , -NHR 3 , -NR 3 R 4 groups with R 3 and R 4 which are identical or different, representing a phenyl, an alkyl radical containing 1 to 12 carbon atoms, .
  • silver nanowires AgNWs
  • silica shell having a thickness of 5 to 50 nm
  • the plastic scintillator comprises - a polymer as defined above, - one or more fluorophore(s) of formula (I)
  • R 1 and R 2 identical and different, represent a hydrogen atom, a mono or polycyclic aryl radical chosen from phenyl, naphthyl, anthracenyl, fluorenyl,
  • aryl radical being optionally substituted by .
  • alkyl radical being optionally substituted by .
  • silver nanowires AgNWs
  • silica shell having a thickness of 5 to 50 nm
  • the plastic scintillator comprises - a polymer as defined above, - one or more fluorophore(s) of formula (I)
  • R 1 and R 2 identical and different, represent a hydrogen atom, a mono or polycyclic aryl radical chosen from phenyl, fluorenyl,
  • aryl radical being optionally substituted by .
  • alkyl radical being optionally substituted by .
  • silver nanowires AgNWs
  • silica shell having a thickness of 5 to 50 nm
  • the plastic scintillator comprises - a polymer chosen from polystyrene, one of the alpha-, ortho-, meta-, para-isomers of polymethylstyrene, poly-vinyltoluene, and polyvinylcarbazole (PVK), - one or more fluorophore(s) of formula (I)
  • R 1 and R 2 identical and different, represent a hydrogen atom, a mono or polycyclic aryl radical chosen from phenyl, fluorenyl, said aryl radical being optionally substituted by .
  • R 3 and R 4 groups with R 3 and R 4 , which are identical or different, representing a phenyl, an alkyl radical containing 1 to 12 carbon atoms, . one or more alkyl groups having 1 to 12 carbon atoms, and
  • silver nanowires AgNWs
  • silica shell having a thickness of 5 to 50 nm
  • the plastic scintillator in the fifth , sixth , seventh and eighth embodiments is not nanostructured within the meaning of the invention.
  • the plastic scintillator comprises metallic nano-objects, in particular metallic nanowires, and more particularly silver nanowires (AgNWs), optionally covered with a silica shell, they are present in an amount sufficient to obtain a transmission coefficient of 80% of visible light at the emission wavelength of the scintillator.
  • metallic nano-objects in particular metallic nanowires, and more particularly silver nanowires (AgNWs), optionally covered with a silica shell
  • the fluorophore can be chosen, for example, from DPA, TPA-DPA, FI-DPA, or a mixture of at least two of these fluorophores:
  • the scintillator may further comprise a plasticizer to modulate the mechanical and thermal properties of the material.
  • the plasticizer can be chosen from N-methylcarbazole, N-ethylcarbazole, N-butylcarbazole, N-phenylcarbazole, triphenylamine, diphenylphthalate or tricresylphthalate, tricresylphthalate.
  • the plasticizer is generally present in an amount of between 0.005 and 10% by mass, preferably between 0.005 and 5% by mass, relative to the total mass of the plastic scintillator.
  • US Patent 3,445,439 describes a room temperature PVK synthesis process that uses a plasticizer such as triethyl phenyl phosphate, tri(tolyl)phosphate, trixylenyl phosphate, triphenyl phosphite and tris nonyl phenyl phosphite.
  • a plasticizer such as triethyl phenyl phosphate, tri(tolyl)phosphate, trixylenyl phosphate, triphenyl phosphite and tris nonyl phenyl phosphite.
  • the plastic scintillator is nanostructured, i.e. say that it is in the form of a nanostructured layer having a thickness of between 1 ⁇ m and 10 mm, in which holes and protrusions or spikes, also called “pillars", are made with a diameter of between 70 nm and 250 nm and a height between 1 ⁇ m and 10 mm.
  • the distance between the holes and the pillars is less than ⁇ /2.n eff , with lambda ( ⁇ ) representing the wavelength of scintillation photon radiation and n eff the effective refractive index of the polymer.
  • nanostructures with nanopillars and nanoholes are described in application EP3 502 750 and represented respectively in FIGS. 3 and 4 of this application.
  • These nanostructures can be formed during synthesis using a nanostructured mold or, a posteriori, using nano-injection techniques (J. Vera et al., Matériaux & Techniques 105, 303 (2017)), embossing (NEP) or lithography (NIL) defined above.
  • the fluorophores that can be used in the scintillators of the invention are, in general, commercial compounds or can be synthesized according to the methods described below in the examples. They can also be synthesized by methods known to those skilled in the art, such as the method described by V. N. Bliznyuk et al. (New Efficient Organic Scintillators Derived from Pyrazoline, ACS Appl. Mater. Interfaces 2016, 8, 20, 12843–12851).
  • the plastic scintillators of the invention can be prepared under an inert atmosphere (argon or nitrogen) by a process depending on the chosen monomer.
  • At least one monomer styrene, vinyltoluene, vinylcarbazole etc. is mixed. to polymerize into a polymer as defined above, with at least one fluorophore and optionally a plasticizer and a radical or cationic polymerization initiator as defined above, under conditions leading to a polymer or polymer matrix comprising at least a fluorophore, and optionally a plasticizer.
  • the quantity of monomer present in the mixture can be from 50 to 99.5% by mass, preferably from 70 to 99.5% by mass, relative to the total mass of the mixture.
  • the mixture comprises a plasticizer
  • a plasticizer it is generally present in an amount of between 0.005 and 10% by mass, preferably between 0.005 and 5% by mass, relative to the total mass of the mixture.
  • Plasticizers are, in general, commercial compounds.
  • a polymerization initiator When a polymerization initiator is used, it is generally present in an amount between 0.01 and 2% by mass, preferably between 0.01 and 1% by mass, relative to the total mass of the plastic scintillator.
  • the fluorophore(s) are present in an amount of between 0.01% and 3% by mass, preferably between 0.01 and 1.5% by mass, relative to the total mass of the mixture.
  • the mixture can be heated to a temperature where all components remain soluble and well mixed during polymerization.
  • the temperature will therefore depend on the nature of the monomer and the other components of the mixture. It is generally at least 80°C, for example at least 100°C, for example between 100 and 160°C. Heating is maintained until polymerization is complete. Thus the duration of the heating will depend on the duration of polymerization. It can range from an hour to a week, for example.
  • the polymer (or the polymer matrix) comprising the fluorophore(s), and optionally the plasticizer, is subjected to a nanostructuring process known to those skilled in the art, namely, the NIL process. , the CIP process, and the nano-injection process.
  • the scintillator contains metallic nano-objects as described above, they can be added to the starting mixture. They will be present in the mixture in an amount between 0.01% and 10% by mass, relative to the mass of the mixture.
  • These metallic nano-objects can be prepared beforehand according to the polyol process as described by F. Fiévet et al in Chem. Soc. Rev., 2018, 47, 5187. In this case, once the polymerization is complete, the polymer (or the polymer matrix) comprises the fluorophore(s), the metallic nano-objects as described above, and possibly the plasticizer. No nanostructuring process is then necessary.
  • the amplification of the spontaneous/intrinsic emission by Purcell effect of the plastic scintillators of the invention thus allows: - to make these detectors more sensitive to low-energy and/or weakly penetrating ionizing radiation ( ⁇ and ⁇ ); - to improve their particularly degraded temporal resolution in the case of large-sized scintillators (ie beacons or detection portals).
  • This makes it possible to envisage new applications for these materials such as Positron Emission Tomography (or PET) where inorganic scintillators (LaBr 3 or Lu 2 SiO 5 ) are generally preferred, although much more expensive but with better temporal resolution. ; - to improve their performance in discriminating between different ionizing radiations.
  • the plastic scintillators of the invention constitute a promising alternative to known state-of-the-art solutions. It is possible to modulate the composition so as to maximize the light yields, the emission wavelength and the temporal response according to the detection constraints. Another advantage of the plastic scintillators of the invention lies in their thermal stability.
  • Another object of the invention relates to the use of a plastic scintillator according to the invention, in nuclear instrumentation for measuring the intensity of gamma, electron or neutron radiation, in nuclear medicine, in radiation protection of people in their workplaces or in the environment, for the inspection of goods, for the monitoring and control of cosmic radiation.
  • inorganic scintillators of the LaBr3 type are used to image the inside of the human body.
  • the improvement of the temporal resolution of the plastic detectors according to the invention makes it possible to consider their use in these devices where they are not currently used because of their weak performances although less expensive than the inorganic crystals.
  • plastic scintillators of the invention can also be used in detection portals by improving the resolution and the sensitivity of these detectors.
  • the invention further relates to an ionizing radiation detector comprising a plastic scintillator according to the invention and a photodetector.
  • the ionizing radiation detectors also called scintillation detectors according to the invention therefore comprise a plastic scintillator according to the invention and an optically coupled photodetector.
  • the plastic scintillator receives ionizing radiation on one of its faces, called the input face, and emits scintillation photon radiation due to the interaction between the ionizing radiation and the plastic scintillator of the invention.
  • the scintillation photon radiation is collected by the photodetector from one of the faces of the scintillator, called the output face, and converted into an electrical signal.
  • the of application EP 3502750 schematically represents an example of an ionizing radiation detector to which a plastic scintillator according to the invention is capable of being applied.
  • 2,6-dibromoanthracene-9,10-dione (4 g; 10.9 mmol) (from the company abcr GMBH, 95%) is introduced into a 500 ml Schlenk tube together with the acid (4-( diphenylamino)phenyl)boronic (2.4 eq.; 26.2 mmol, 7.6 g) (Sigma-Aldrich, 95%).
  • the tube is degassed under argon twice.
  • Toluene (96 ml), ethanol (32 ml) and 2M sodium carbonate (6 eq.; 65 mmol, 32 ml) are then added.
  • the mixture thus obtained is degassed (argon) for 10 minutes before the addition of Pd(PPh 3 ) 4 (0.025 eq.; 0.15 mmol; 0.32 g) (Sigma-Aldrich, 99%).
  • the reaction is stirred at 90°C for 3 hours until the reaction is complete, followed by TLC analysis.
  • the crude mixture is filtered through Celite®, the aqueous phase is eliminated and the filtrates are washed with CH 2 Cl 2 until the major part of the colored product (red) is eluted (500 ml).
  • 2,6-bis(4-(diphenylamino)phenyl)anthracene-9,10-dione (11.2 g; 16.1 mmol) as well as anhydrous THF (200 ml) are introduced into a 500 ml bineck equipped of an arrival of argon.
  • the glassware is first carefully dried in the oven at 120°C and cooled under vacuum then under argon using a vacuum ramp.
  • the suspension thus formed is cooled to -78° C. (dry ice bath) before the addition, drop by drop, of a solution of phenyl lithium (1.9 M in dibutyl ether; 2.2 eq.; 35, 4 mmol; 18.7 ml) for 10 minutes.
  • 2,6-bis(4-(diphenylamino)phenyl)-9,10-diphenyl-9,10-dihydroanthracene-9,10-diol (8.5 g; 10 mmol) are introduced into a 250 ml flask.
  • disodium hydrogen phosphite (5.5 eq.; 4.85 g; 55 mmol) and potassium iodide (2 eq.; 3.33 g; 20 mmol).
  • the solids are dissolved with acetic acid (150ml) and heated at 120°C for 3 hours, after which a precipitate is formed. After hot filtration, a light yellow solid is recovered.
  • 2,6-dibromoanthracene-9,10-dione (5 g; 13.6 mmol) (from the company abcr GMBH, 95%) is introduced into a 500 ml Schlenk tube with 2-(9,9- diethyl-9H-fluoren-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2.2 eq.; 30 mmol; 10.4 g).
  • the tube is degassed and then filled with argon twice.
  • 2,6-bis(9,9-diethyl-9H-fluoren-2-yl)anthracene-9,10-dione (7.7 g; 11.9 mmol) is introduced into a 500 ml two-necked bottle equipped with an argon inlet (the glassware was first dried at 120°C, cooled under vacuum and finally purged with argon).
  • Anhydrous THF 150 ml is added which forms a suspension which is cooled to ⁇ 78° C. (in a dry ice bath).
  • a phenyllithium solution (1.9 M in dibutyl ether; 2.2 eq.; 26.1 mmol; 13.7 ml) is added dropwise for 10 min. The reaction mixture is stirred for 2 hours.
  • the TLC analyzes show the presence of the starting products.
  • An additional 7 mL of phenyllithium are added (13.3 mmol; 7 mL) the mixture is stirred for 1 hour at -78° C., which makes it possible to complete the reaction.
  • the catalyst is deactivated at 0° C. with a saturated solution of NH 4 Cl. The whole is concentrated to eliminate a large part of the THF.
  • Ethyl acetate (600 ml) is added to the residue (not all the solid is dissolved, producing a suspension), the aqueous phase is separated from the organic phase.
  • the organic phase is washed with brine, then transferred to an Erlenmeyer flask to be dried over MgSO 4 .
  • the suspension is heated to 60° C.
  • 2,6-bis(9,9-diethyl-9H-fluoren-2-yl)-9,10-diphenyl-9,10-dihydroanthracene-9,10-diol (6.5 g; 8.07 mmol) is introduced into a 250 ml flask along with disodium hydrogen phosphite (5.5 eq.; 3.9 g; 44.4 mmol) then potassium iodide (2 eq.; 2.67 g; 16, 1 mmol).
  • the solids are dissolved in acetic acid (150ml) and heated at 120°C for 3 hours, after which a large amount of precipitate is formed.
  • Hot filtration makes it possible to recover a light yellow solid which is washed with water, then a saturated solution of NaHCO 3 , again with water, methanol, ethyl acetate and finally with dichloromethane (200 ml for each wash). Further purification is carried out hot (80° C.) by suspending the crude product in 1,1,2,2-tetrachloroethane (50 ml) and then filtering this suspension. The product thus obtained is dried under vacuum (70° C., 1 mbar) and makes it possible to obtain a light yellow solid (5.85 g; 94%).
  • the spectra in liquid are carried out with solvents of spectroscopic quality. Absorption spectra are recorded on an Agilent Cary-60 UV-Vis single beam spectrophotometer . The fluorescence spectra are carried out on a Horiba Jobin-Yvon Fluoromax 4P spectrofluorimeter (150 W Xe lamp, simple monochromators).
  • Compounds 3 and 6 have well-separated absorption and emission bands (high stock shift) which makes it possible to limit losses by self-absorption.
  • triphenyl phosphate (TPhP, 75mg)
  • Vinylcabazole (VK) (sigma-aldrich, 98%) is purified by vacuum sublimation before use.
  • the monomer (15 g) and the fluorophore compound 3 TPA-DPA (18 mg) are weighed then introduced into a vial to be crimped.
  • the bottle is degassed 3 times before being placed in an oven at 120° C. in order to trigger radical polymerization.
  • the use of an initiator is not necessary because the monomer itself can act as an initiator.
  • a primer can be used.
  • the duration of the polymerization is fixed at 4 days.
  • the material is unmolded by breaking the crimp bottle.
  • the sample is finally polished on both sides to obtain the smoothest possible material.
  • TPA-DPA 0.12% by mass relative to the total mass of the plastic scintillator.
  • triphenyl phosphate (TPhP, 75mg)
  • Vinylcarbazole (VK) (sigma-aldrich, 98%) is purified by vacuum sublimation before use.
  • the quantity of FI-DPA is 0.05% by mass relative to the total mass of the plastic scintillator.
  • triphenyl phosphate (TPhP, 76mg)
  • Vinylcarbazole (VK) (sigma-aldrich, 98%) is purified by vacuum sublimation before use.
  • the amount of 9,10-DPA is 0.5% by mass relative to the total mass of the plastic scintillator.
  • the light output can be evaluated by plotting the histogram of the amplitudes of the measured pulses as a function of their frequency of occurrence, in the presence of a gamma source (137Cs). The larger the amplitudes, the more the spectrum will be extended towards the higher channel numbers.
  • a gamma source 137Cs.
  • the optimal 9,10-DPA composition is between 0.5 and 0.55% by mass of DPA, relative to the total mass of the plastic scintillator. Below and above this concentration, the light yields are lower (smaller pulse amplitudes).
  • styrene (Sigma-Aldrich) is purified by distillation to remove the polymerization inhibitor.
  • TPA-DPA The amount of TPA-DPA is 0.02% by mass relative to the total mass of the plastic scintillator.
  • Gains in detection efficiency are evaluated using a characterization bench comprising a light-tight enclosure inside which a photomultiplier (PMT) is placed.
  • the PMT is selected so that its spectral response is matched to the emission spectrum of the radioluminescent polymer. It is powered by a high voltage generator (CAEN, model N1470).
  • CAEN high voltage generator
  • the scintillator is placed on the window of the PMT.
  • the optical coupling between the plastic scintillator ( ) and the entry window of the PMT can be improved by using a medium with an intermediate refractive index which limits photon losses by reflection at the interface.
  • a viscous polysiloxane-based oil (Dow Corning, SR-7010, ) or (Cargille, OC-459, ) can be used for this purpose.
  • the source is placed on the plastic scintillator.
  • Signal acquisition is provided by a CAEN DT5730 digitizer.
  • the amplitudes of the collected pulses are classified in a histogram which constitutes the amplitude spectrum of the photons emitted, after interaction of the ionizing radiation in the plastic scintillator.
  • the spectra are obtained from the response of 30,000 traces.
  • the optimal composition in 9,10-DPA for a scintillator based on 9,10-DPA/PVK is between 0.5 and 0.55% by mass, relative to the total mass of the plastic scintillator. Below and above this concentration, the light yields are lower (smaller pulse amplitudes).
  • the nanowires are purified by flocculation, per 25 ml portion of solution.
  • acetone is added until the particles aggregate (2 to 4x the volume), then the solution is stirred and then left to stand for 5 minutes for decantation. The supernatant is discarded, the decant redispersed in the initial volume with water (or smaller volume if one wishes to concentrate). As long as the supernatant is not clear, the acetone flocculation operation can be repeated several times.
  • this purification step is not sufficient to eliminate the particles lighter than the nanowires, another step of decantation in methanol may be necessary.
  • the redispersion will be done in methanol.
  • the solution is then left to settle for 18-24 hours and recover the supernatant.
  • the decantate contains only large particles of several hundred nanometers in diameter characterized by a brick-red to violet color.
  • the purified nanowires are then transferred into dimethylacetamide (DMAc) via centrifugation (1 hour at 4500 rpm), before being incorporated into the polymer matrices.
  • DMAc dimethylacetamide
  • the silver nanowires were characterized using SEM (Carl Zeiss AG - SUPRA 40). They have an average diameter of 40 nm for lengths of the order of 3 ⁇ m.
  • TEOS can be replaced by triethoxy(phenyl)silane (PTES).
  • PTES triethoxy(phenyl)silane
  • the schematically shows the silver nanowires coated with a functionalized silica shell with the surface groups from TEOS (Si-OH) and PTES (Si-Ph) which will be exposed.
  • Vinylcarbazole (VK) (Sigma-Aldrich, 98%) is purified by vacuum sublimation before use.
  • the monomer (15 g) and the fluorophore 3 TPA-DPA (18 mg) are weighed then introduced into a vial to be crimped. 750 ⁇ L (10 mg/mL solution) of the solution of functionalized Si-Ph nanowires are added to the bottle. The solvent is evaporated under primary vacuum, then degassed with argon 3 times before being crimped and placed in an oven at 120°C.
  • a polymerization initiator can be used. However, in this example, the use of an initiator is not necessary to initiate the polymerization because the monomer itself can act as an initiator. The duration of the polymerization is fixed at 4 days.
  • the material is unmolded by breaking the crimp bottle.
  • the sample is finally polished on both sides to obtain the smoothest possible material.
  • TPA-DPA 0.12% by mass relative to the total mass of the plastic scintillator.
  • the amount of Si-Ph functionalized silver nanowires is 0.05% by mass relative to the total mass of the plastic scintillator.
  • TPA-DPA The amount of TPA-DPA is 0.02% by mass relative to the total mass of the plastic scintillator.
  • the amount of Si-Ph functionalized silver nanowires is 0.1% by mass relative to the total mass of the plastic scintillator.
  • the silver nanowires will have the role of enhancing the luminescence of the polymer matrix which can then transfer more light to the fluorophore(s) thus amplifying the light response.

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Measurement Of Radiation (AREA)
EP21839525.9A 2020-12-21 2021-12-17 Kunststoffszintillatoren mit durch purcell-effekt verstärkter intrinsischer emission Withdrawn EP4263747A1 (de)

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FR2013785A FR3118055B1 (fr) 2020-12-21 2020-12-21 Scintillateurs plastiques permettant une emission intrinseque amplifiee par effet purcell.
PCT/EP2021/086405 WO2022136145A1 (fr) 2020-12-21 2021-12-17 Scintillateurs plastiques permettant une emission intrinseque amplifiee par effet purcell

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US3445439A (en) 1967-04-13 1969-05-20 Int Standard Electric Corp Process for producing polyvinyl carbazole
US8698086B2 (en) 2010-06-23 2014-04-15 Lawrence Livermore National Security, Llc High effective atomic number polymer scintillators for gamma ray spectroscopy
WO2013003802A1 (en) * 2011-06-29 2013-01-03 Nanoptics, Incorporated Scintillating organic materials and methods for detecting neutron and gamma radiation
US9309456B2 (en) * 2011-04-15 2016-04-12 Lawrence Livermore National Security, Llc Plastic scintillator with effective pulse shape discrimination for neutron and gamma detection
ITMI20112402A1 (it) * 2011-12-28 2013-06-29 Eni Spa Convertitore di lunghezza d'onda e composizioni luminescenti
EP2919037A1 (de) 2014-03-13 2015-09-16 Université de Technologie de Troyes Optimierungsverfahren der Sammlung von Photonen in Szintillationskristallen, entsprechender Kristall und entsprechende Anwendungen
US10024983B1 (en) * 2015-12-01 2018-07-17 National Technology & Engineering Solutions Of Sandia, Llc Metal-loaded plastic scintillators for gamma-ray spectroscopy
CN106084103B (zh) * 2016-06-17 2019-03-01 同济大学 一种利用模板制备光子晶体塑料闪烁体的方法
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