Radiation Detection Materials

Abstract

A radiation detection material is disclosed. The radiation detection material is represented by the following formula (I): (M1' 8-2a M2' a )(M'' 14-(4b / 3) M'' b )O 24 (X 2-dc dX' n c- ):M'''' Formula (I): Further disclosed are devices and uses of the radiation-sensing material represented by formula (I).

Description

[Technical field]

[0001] The present disclosure relates to radiation sensing materials. The present disclosure further relates to devices, materials, and uses of the radiation sensing materials. [Background technology]

[0002] Photochromism is considered the reversible transformation of a chemical species between two forms by absorption of electromagnetic radiation, the two forms having different absorption spectra. That is, photochromism can be described as a reversible change in color upon exposure to radiation. Photochromism is usually used to describe compounds that undergo a reversible photochemical reaction in which an absorption band in the visible part of the electromagnetic spectrum changes dramatically in intensity or wavelength. Reversible photochromic materials can be found in applications such as toys, cosmetics, clothing, and industrial applications. In addition to this, or alternatively to a material being photochromic, it may be a luminescent material. "Luminescence" refers to the property of a material that can emit light without being heated. Luminescent materials can be used, for example, in lighting applications. Summary of the Invention

[0003] A radiation detection material is disclosed. The radiation detection material is represented by the following formula (I): (M1' 8-2a M2' a )(M'' 14-(4b / 3) M'' b )O 24 (X 2-dc dX' n c- ):M'''' Formula (I)

[0004] During the ceremony, M1' represents a monovalent monoatomic cation of an alkali metal selected from Group 1 of the IUPAC Periodic Table of the Elements, or any combination of such cations; M2' represents a divalent monoatomic cation of an alkaline earth metal selected from Group 2 of the IUPAC Periodic Table of the Elements, or any combination of such cations; M″ represents a trivalent monoatomic cation of an element selected from Group 13 of the IUPAC Periodic Table of the Elements, or any combination of such cations; M''' represents a monoatomic cation of an element selected from Group 14 of the IUPAC Periodic Table of the Elements, or any combination of such cations; X represents an anion of an element selected from the halogens of Group 17 of the IUPAC Periodic Table of the Elements, or any combination of such anions; X' represents an anion of one or more elements selected from the chalcogenides of Group 16 of the IUPAC Periodic Table of the Elements, or any combination of such anions; M'''' represents a dopant cation of an element selected from the rare earth metals of the IUPAC Periodic Table of the Elements, or from the transition metals of the IUPAC Periodic Table of the Elements, or a dopant cation of Ba, Sr, Tl, Pb, or Bi, or any combination of such cations, or M'''' is absent; a is a value between 0.05 and 4; b is a value between 1 and 10; c is a value of 1, 2, 3, or 4; d is a value greater than 0 and less than or equal to 2; n is a value of 1, 2, 3, or 4.

[0005] Further disclosed are devices comprising the radiation sensing materials disclosed herein.

[0006] Further disclosed are materials derived from the radiation sensing materials disclosed herein.

[0007] Further disclosed is the use of the radiation sensing materials disclosed herein to indicate the presence and / or intensity of ultraviolet, x-ray, gamma ray, infrared, near infrared, and / or particle radiation.

[0008] Further disclosed is the use of the radiation sensing materials disclosed herein as light sources in consumer products; security devices; detection; imaging; image acquisition; display, screen, window, or touch screen solutions; medicine; drug development; and / or diagnostics.

[0009] Further disclosed is the use of the radiation detection materials disclosed herein to detect disease in combination with antibodies or staining entities, in biomarker test kits, in screening platforms, and / or with additional materials.

[0010] The accompanying drawings, which provide a further understanding of the embodiments and are included in and constitute a part of this specification, illustrate embodiments and, together with the description, serve to explain the principles presented above. [Brief description of the drawings]

[0011] [Figure 1a] FIG. 1a shows the results of powder X-ray diffraction (XRD) measurements. [Figure 1b] FIG. 1b shows the results of powder X-ray diffraction (XRD) measurements. [Figure 2a] FIG. 2a shows the results of the reflectance measurement. [Figure 2b] FIG. 2b shows the results of the reflectance measurement. [Figure 2c] FIG. 2c shows the results of the reflectance measurement. [Figure 3a] FIG. 3a shows the results of a tenebresence color development measurement. [Figure 3b] FIG. 3b shows the results of the tenebrescence color development measurement. [Figure 3c] FIG. 3c shows the results of the tenebresence color development measurement. [Figure 4a] FIG. 4a shows the results of the photoluminescence measurement. [Figure 4b] FIG. 4b shows the results of the photoluminescence measurement. [Figure 5a] FIG. 5a shows the results of persistent luminescence measurements. [Figure 5b]FIG. 5b shows the results of persistent luminescence measurements. [Figure 6] FIG. 6 shows the results of the thermoluminescence measurements. [Figure 7] FIG. 7 shows a photograph of yellow photochromism. [Figure 8] FIG. 8 shows a photograph of near-infrared photochromism. [Figure 9a] FIG. 9a shows the results of a dual excitation emission simulation test. [Figure 9b] FIG. 9b shows the results of a dual excitation emission simulation test. [Figure 10] FIG. 10 shows the results of a dual excitation emission simulation test. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] The present disclosure relates to a radiation detecting material represented by the following formula (I): (M1' 8-2a M2' a )(M'' 14-(4b / 3) M'' b )O 24 (X 2-dc dX' n c- ):M'''' Formula (I)

[0013] During the ceremony, M1' represents a monovalent monoatomic cation of an alkali metal selected from Group 1 of the IUPAC Periodic Table of the Elements, or any combination of such cations; M2' represents a divalent monoatomic cation of an alkaline earth metal selected from Group 2 of the IUPAC Periodic Table of the Elements, or any combination of such cations; M″ represents a trivalent monoatomic cation of an element selected from Group 13 of the IUPAC Periodic Table of the Elements, or any combination of such cations; M''' represents a monoatomic cation of an element selected from Group 14 of the IUPAC Periodic Table of the Elements, or any combination of such cations; X represents an anion of an element selected from the halogens of Group 17 of the IUPAC Periodic Table of the Elements, or any combination of such anions; X' represents an anion of one or more elements selected from the chalcogenides of Group 16 of the IUPAC Periodic Table of the Elements, or any combination of such anions; M'''' represents a dopant cation of an element selected from the rare earth metals of the IUPAC Periodic Table of the Elements, or from the transition metals of the IUPAC Periodic Table of the Elements, or a dopant cation of Ba, Sr, Tl, Pb, or Bi, or any combination of such cations, or M'''' is absent; a is a value between 0.05 and 4; b is a value between 1 and 10; c is a value of 1, 2, 3, or 4; d is a value greater than 0 and less than or equal to 2; n is a value of 1, 2, 3, or 4.

[0014] In one embodiment, a is a value of 0.05 to 4, or 0.1 to 4, or 0.2 to 4, or 0.3 to 4, or 0.4 to 3, 0.5 to 2, or 0.6 to 1. In one embodiment, a is a value of 0.2 to 2, or 0.28 to 1.5, or 0.28 to 1, or 0.3 to 1, or 0.32 to 0.8. In one embodiment, a is a value of 1 to 4, or 1.3 to 3, or 1.5 to 2.

[0015] In one embodiment, b is a value from 1 to 10, or from 2 to 9, or from 3 to 8, or from 4 to 7, or from 5 to 6, or 6.

[0016] In one embodiment, c is a value of 1, 2, 3, or 4, or 1, 2, or 3, or 1 or 2.

[0017] In one embodiment, d has a value of greater than 0 and equal to or less than 2, or from 0.05 to 2, or from 0.1 to 2.

[0018] In one embodiment, n is a value of 1, 2, 3, or 4.

[0019] In one embodiment, in formula (I), "dc" is at most 2. That is, the value of "dc" must not exceed 2.

[0020] In one embodiment, The charge of M1' is 1+, The charge of M2' is 2+, The charge of M'' is 3+, The charge of M'' is 4+, The charge of X is 1- The charge of X' is 0.5- to 3.5-.

[0021] In one embodiment, the charge of X' is 1- to 3-. In one embodiment, the charge of X' is 1-, 2-, or 3-.

[0022] The radiation sensing material may be ultraviolet, x-ray, gamma ray, infrared, near infrared, and / or particulate radiation sensing material.

[0023] In one embodiment, the particle radiation is alpha radiation, beta radiation, neutron radiation, proton radiation, or any combination thereof.

[0024] Ultraviolet radiation is electromagnetic radiation with wavelengths between 10 nm (30 PHz) and 400 nm (750 THz). The electromagnetic spectrum of ultraviolet radiation (UVR) can be subdivided into several ranges recommended by the ISO standard ISO-21348, including ultraviolet A (UVA), ultraviolet B (UVB), and ultraviolet C (UVC). UVA wavelengths are generally considered to be between 315 nm and 400 nm, UVB wavelengths are generally considered to be between 280 and 320, and UVC wavelengths are generally considered to be between 100 nm and 290 nm. X-rays are electromagnetic radiation with wavelengths between 0.01 nm and 10 nm. Gamma rays are electromagnetic radiation with wavelengths between 0.000001 nm and 0.01 nm. Infrared radiation is electromagnetic radiation with wavelengths between 700 nm and 2500 nm. Near infrared radiation is electromagnetic radiation with wavelengths between 750 and 2500 nm. The radiation detection material may be 1zm to 2500nm, or 1zm to 2000nm, or 1zm to 5μm, or 1zm to 3μm, or 1zm to 8μm, or 1zm to 15μm, or 1zm to 1mm, or 1fm to 2500nm, or 1fm to 2000nm, or 1fm to 5μm, or 1fm to 3μm, or 1fm to 8μm, or 1fm to 15μm, or 1fm to 1mm, or 1pm to 2 It can detect radiation having a wavelength of 500 nm, or 1 pm to 2000 nm, or 1 pm to 5 μm, or 1 pm to 3 μm, or 1 pm to 8 μm, or 1 pm to 15 μm, or 1 pm to 1 mm, or 0.01 nm to 2500 nm, or 1 nm to 2000 nm, or 10 nm to 5 μm, or 100 nm to 3 μm, or 1 μm to 8 μm, or 2 μm to 15 μm, or 5 μm to 1 mm.

[0025] In one embodiment, the radiation sensitive material is a photochromic material that changes its color from white to yellow upon exposure to radiation.

[0026] The inventors have surprisingly found that it is possible to form a radiation sensing material that is capable of changing color from white to yellow when exposed to radiation. The yellow color can be attributed to absorption from the UVA-green region of the electromagnetic spectrum, i.e., from 350 to 580 nm.

[0027] The present inventors have surprisingly found that the absorption of the F center in a radiation-sensing material prepared by using a relatively large amount of, for example, calcium, is not where it is expected. 2+ is Na + and can at least partially replace it in the structure of the radiation-sensing material. 2+ The absorption band of the F center in radiation detection materials containing Na + It would be expected that the presence of calcium would be in the same region as that in which only F is present, i.e. in the green region of the electromagnetic spectrum, resulting in the material exhibiting a purple color. Surprisingly, however, the presence of calcium can result in absorption by the F center in the blue region of the spectrum, causing the material to exhibit a yellow color when exposed to radiation.

[0028] The inventors have further surprisingly found that a second absorption band can be observed in the near infrared region (NIR) corresponding to a photochromic change in absorption of NIR radiation after the radiation sensing material is exposed to, for example, ultraviolet light. In one embodiment, the radiation sensing material is a material that changes color from non-absorbing to absorbing in the near infrared region of the electromagnetic spectrum upon exposure to radiation, for example ultraviolet light. In one embodiment, the radiation sensing material is a material that absorbs radiation in the near infrared region of the electromagnetic spectrum.

[0029] The near infrared (NIR) region of the electromagnetic spectrum can be considered to be the range from 750 nm to 2500 nm. The present inventors have surprisingly found that it is possible to prepare radiation detecting materials which absorb radiation within the near infrared region of the electromagnetic spectrum, i.e. the radiation detecting materials exhibit absorption bands within the near infrared region.

[0030] In one embodiment, the radiation sensing material is a luminescent material, a material that exhibits persistent luminescence, and / or a material that exhibits afterglow.

[0031] In one embodiment, the radiation sensing material is a synthetic material.In one embodiment, the radiation sensing material is synthetically prepared.

[0032] In this specification, unless otherwise specified, the expression "monoatomic ion" should be understood as an ion consisting of a single atom. If an ion contains two or more atoms, even if these atoms are of the same element, it should be understood as a polyatomic ion. Therefore, in this specification, unless otherwise specified, the expression "monoatomic cation" should be understood as a cation consisting of a single atom.

[0033] The radiation sensing material of formula (I) has the additional utility of changing its color from white to yellow upon exposure to radiation.

[0034] In one embodiment, M1' represents a monovalent monatomic cation of Li, Na, K, Rb, Cs, or Fr. In one embodiment, M1' represents a monovalent monatomic cation of Li, Na, K, Rb, Cs, or Fr, or any combination of such cations. In one embodiment, M1' represents a monovalent monatomic cation of an alkali metal selected from the group consisting of Na, Li, K, Rb, Cs, and Fr. In one embodiment, M1' represents a monovalent monatomic cation of an alkali metal selected from the group consisting of Na, Li, K, Rb, and Cs. In one embodiment, M1' represents a monovalent monatomic cation of an alkali metal selected from the group consisting of Li, K, Rb, Cs, and Fr. In one embodiment, M1' represents a monovalent monatomic cation of an alkali metal selected from the group consisting of Li, K, Rb, and Cs. In one embodiment, M1' represents a monovalent monatomic cation of an alkali metal selected from the group consisting of Li, K, Rb, and Cs. In one embodiment, M1' represents a monovalent monatomic cation of Na.

[0035] In one embodiment, M1' represents a monovalent monatomic cation of Na, or a monovalent monatomic cation of Li, a monovalent monatomic cation of K, a monovalent monatomic cation of Rb, a monovalent monatomic cation of Cs, or a monovalent monatomic cation of Fr. In one embodiment, M1' represents a monovalent monatomic cation of Na.

[0036] In one embodiment, M represents a monovalent monatomic cation of Na in combination with a monovalent monatomic cation of Li, a monovalent monatomic cation of K, a monovalent monatomic cation of Rb, or a monovalent monatomic cation of Cs. In one embodiment, M represents a monovalent monatomic cation of Na in combination with a monovalent monatomic cation of K.

[0037] In one embodiment, M2' represents a divalent monoatomic cation of Be, Mg, Ca, Sr, Ba, or Ra. In one embodiment, M2' represents a divalent monoatomic cation of Be, Mg, Ca, Sr, Ba, or Ra, or any combination of such cations. In one embodiment, M2' represents a divalent monoatomic cation of an alkaline earth metal selected from the group consisting of Be, Mg, Ca, Sr, Ba, and Ra. In one embodiment, M2' represents a divalent monoatomic cation of an alkaline earth metal selected from the group consisting of Be, Mg, Ca, Sr, Ba, and Ra, or any combination of such cations.

[0038] In one embodiment, M2' represents a divalent monoatomic cation of Be, or a divalent monoatomic cation of Mg, or a divalent monoatomic cation of Ca, or a divalent monoatomic cation of Sr, or a divalent monoatomic cation of Ba, or a divalent monoatomic cation of Ra. In one embodiment, M2' represents a divalent monoatomic cation of Ca.

[0039] In one embodiment, M1' represents a monovalent monatomic cation of Na and M2' represents a divalent monatomic cation of Ca. In one embodiment, M1' represents a combination of a monovalent monatomic cation of Na and a monovalent monatomic cation of K and M2' represents a divalent monatomic cation of Ca.

[0040] In one embodiment, the radiation sensing material comprises 16-31 mol %, or 24-29 mol % of M1'.

[0041] In one embodiment, the radiation sensing material comprises 0.7-14 mol %, or 2-7 mol % of M2'.

[0042] In one embodiment, (M 8-2a M2' a ) contains 0 to 99.4 wt%, or 1 to 98 mol%, or 5 to 97 mol%, or 10 to 96 mol%, or 20 to 95 mol%, or 30 to 90 mol%, or 40 to 85 mol%, or 50 to 80 mol%, or 60 to 70 mol% of a single atomic cation of Na. 8-2a M2' a ) contains 75 to 99 mol %, or 78 to 98 mol %, or 80 to 97.5 mol %, or 83 to 97 mol %, or 85 to 96 mol %, or 87 to 94 mol % of Na monoatomic cations.

[0043] In one embodiment, M″ represents a trivalent monoatomic cation of a metal selected from the group consisting of Al and Ga, or a trivalent monoatomic cation of B, or any combination of such cations. In one embodiment, M″ represents a trivalent monoatomic cation of a metal selected from the group consisting of Al and Ga, or a combination of such cations. In one embodiment, M″ represents a trivalent monoatomic cation of B.

[0044] In one embodiment, M''' represents a monoatomic cation of an element selected from the group consisting of Si and Ge, or a combination of such cations.

[0045] In one embodiment, X represents an anion of an element selected from the group consisting of F, Cl, Br, I, and At, or any combination of such anions. In one embodiment, X represents an anion of an element selected from the group consisting of F, Cl, Br, and I, or any combination of such anions. In one embodiment, X is absent.

[0046] In one embodiment, X' represents an anion of an element selected from the group consisting of O, S, Se, and Te, or any combination of such anions. In one embodiment, X' represents an anion of one or more elements selected from the group consisting of O, S, Se, and Te, or any combination of such anions. In one embodiment, X' represents a monoatomic or polyatomic anion of one or more elements selected from the group consisting of O, S, Se, and Te, or any combination of such anions. In one embodiment, X' represents an anion of S. In one embodiment, X' represents an anion of (SO 4 ) 2- In one embodiment, X' is absent.

[0047] In one embodiment, either X or X' is present, or both X and X' are present. In one embodiment, at least X' is present.

[0048] In one embodiment, the radiation sensing material is doped with at least one transition metal ion. In one embodiment, the radiation sensing material is represented by formula (I), where M'''' represents a cation of an element selected from the transition metals of the IUPAC Periodic Table of Elements, or a cation of Ba, Sr, Tl, Pb, or Bi, or any combination of such cations. In one embodiment, M'''' represents a cation of an element selected from the group consisting of Yb, Er, Tb, and Eu, or a cation of an element selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Ag, W, and Zn, or any combination of such cations. In one embodiment, M'''' represents a cation of an element selected from the f-block transition metals of the IUPAC Periodic Table of Elements. In one embodiment, M'''' represents a cation of an element selected from the d-block transition metals of the IUPAC Periodic Table of Elements. In one embodiment, M'''' represents a cation of an element selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Ag, W, and Zn, or any combination of such cations. In one embodiment, M'''' represents a cation of Ti. In one embodiment, M'''' represents a dopant cation of an element selected from the rare earth metals of the IUPAC Periodic Table of the Elements. In one embodiment, M'''' represents a cation of an element selected from the group consisting of Yb, Er, Tb, and Eu, or any combination of such cations. In one embodiment, M'''' represents a combination of two or more dopant cations.

[0049] In one embodiment, the radiation sensing material is represented by Formula (I), where M'''' is absent. In this embodiment, the radiation sensing material is undoped.

[0050] In one embodiment, the radiation sensing material represented by formula (I) includes M'''' in an amount of 0.001-10 mol %, or 0.001-5 mol %, or 0.1-5 mol %, based on the total amount of the radiation sensing material.

[0051] The radiation sensing material was developed by Norrbo et al (Norrbo, I.; Gluchowski, P.; Paturi, P.; Sinkkonen, J.; Lastusaari, M., Persistent Luminescence of Tenebrescent Na 8 Al 6 S 6 O 24 (Cl,S) 2 : Multifunctional Optical Markers. Inorg. Chem. 2015, 54, 7717-7724), the reference of which is based on Armstrong and Weller (Armstrong, JA; Weller, JA Structural Observation of Photochromism. Chem. Commun. 2006, 1094-1096), but varying the amount of starting materials used. As examples, 3 Å or 4 Å molecular sieves or zeolite A; Na 2 SO 4 And / or Na 2 SeO 3 Sulfates such as CaCl 2 Salts such as LiCl, NaCl, KCl, CsCl, and / or RbCl can be used as starting materials. Other examples of salts that can be used are NaBr, NaI, CaBr 2 , CaI 2 , LiBr, LiI, KBr, KI, RbBr, RbI, CsBr and CsI. By way of example only, the starting materials may be 52.1 mol% 3 Å or 4 Å molecular sieves, 0.0-41.2 mol% NaCl, 2.2-43.4 mol% CaCl 2 6H 2 O, and 4.5 mol% Na 2 SO 4 At least one dopant may include an oxide, such as TiO 2The cations may be added as salts, chlorides, sulfides, bromides, phosphates, or nitrates. The material may be prepared as follows: 3 Å or 4 Å molecular sieves or zeolite A may first be dried at 500° C. for 1 hour. The initial mixture may then be heated in air at 850° C. for, for example, 2 hours, 5 hours, 12 hours, 24 hours, 36 hours, 48 ​​hours, or 72 hours. The product may then be allowed to cool freely to room temperature and crushed. Finally, the product may be washed with 12% H 2 O to form a fluid. 2 and 88% N 2 It can be reheated at 850 °C for 2 hours under atmosphere. If necessary, the prepared material can be washed with water to remove excess impurities. Purity can be confirmed by powder X-ray diffraction measurement.

[0052] A molecular sieve is a material with uniformly sized pores or small holes. These pores are similar in size to small molecules, so larger molecules cannot enter or be adsorbed, but small molecules can be adsorbed. The diameter of a molecular sieve is measured in angstroms (Å) or nanometers (nm). A 3 Å molecular sieve has a diameter of ((K 2 O) 2 / 3 (Na 2 O) 1 / 3 )·Al 2 O 3 2SiO 2 9 / 2H 2 The 4 Å molecular sieve can be considered to have the approximate chemical formula of NaO. 2 O.Al 2 O 3 2SiO 2 9 / 2H 2 O.

[0053] The present disclosure further relates to a device comprising the radiation sensing material defined herein. The device may be a sensor, a detector, or an indicator.

[0054] A sensor may be an active sensor or a passive sensor. An active sensor is a sensing device that requires an external power source to operate. An active sensor is in contrast to a passive sensor, which detects and responds to some type of input from the physical environment. A passive sensor does not require an external power source to operate.

[0055] The detector may be an image detector. The image detector may be used, for example, as a detector in radiation-based imaging technology. The detector may be used in imaging, non-destructive testing, and / or welding imaging performed in industry. The detector may further be used, for example, in point-of-care analysis or point-of-care testing. Point-of-care testing (POCT), also called bedside testing, may be defined as medical diagnostic testing at or near the point-of-care, i.e., at the time and place of patient care. This is in contrast to situations where testing is entirely or mostly confined to medical laboratories, which involve sending samples away from the point-of-care and then waiting, for example, for hours or days, to know the results.

[0056] The indicator can be applied, for example, to the label of a bottle of skin cream or sunscreen, and the color change alerts the user to apply sunscreen. The material can be used, for example, on the outside of a window to alert the occupant before going outside about the UV intensity. The radiation detection material can also be mixed as a powder into the raw materials used to manufacture plastic bottles, stickers, glass, and similar products that are provided, for example, with a UV indicator. The radiation detection material can also be used in clothing, for example swimsuits, and the color change can indicate that there is too much UV radiation and alert the user to seek shade. Products that include the radiation detection material can be considered jewelry. The radiation detection material can be used as the display of a meter calibrated according to shade.

[0057] The sensor, detector, or indicator may be reusable. The radiation sensing material has the added utility of being able to change its color back to colorless (white), i.e., decolorized, by visible light or heat, thus allowing for reuse. That is, as a result of the radiation sensing material being reusable, the same sensor, detector, or indicator can be reused once or several times.

[0058] The present disclosure further relates to the use of the radiation sensing material defined herein as a light source in consumer products; security devices; detection; imaging; image acquisition; display, screen, window, or touch screen solutions; medicine; drug development; and / or diagnostics.

[0059] Further disclosed is the use of the radiation detection materials disclosed herein to detect disease in combination with antibodies or staining entities, in biomarker test kits, in screening platforms, and / or with additional materials.

[0060] The light source may be selected from the group consisting of displays, screens, backlight units, frontlight units, lighting elements, decorative elements, spatial applications, and fluorescent lamps, for example for presenting alphabetical, numerical, and graphic information. Cosmic ultraviolet, X-ray, or gamma rays may be used as light sources to generate blue and red light emissions or combinations thereof, which may implement color and light in, for example, displays, head-up displays (HUDs), screens, or windows.

[0061] The security device may be selected from the group consisting of ink, thread, paper, foil, hologram, and powder. The powder may be mixed with, for example, paint, polymer, liquid, etc. In one embodiment, the security device is used on a banknote, passport document, or identity card.

[0062] The security device may be used in commercial products. The security device may be used in works of art or historical artefacts.

[0063] The radiation detecting material may be used to diagnose a sample received from the human or animal body or to diagnose the human or animal body directly. The sample may be selected from the group consisting of body fluids, teeth, bone, and tissue. The sample may include blood, skin, tissue and / or cells. The radiation detecting material may be used for in vivo imaging or in vivo diagnosis. The imaging may be medical imaging.

[0064] The radiation sensing material can further be used for imaging, such as stimulated emission depletion (STED) imaging, fluorescence resonance energy transfer (FRET) imaging, or dynamic imaging.

[0065] The present disclosure further relates to the use of radiation sensing materials as defined herein to indicate the presence and / or intensity of ultraviolet, x-ray, gamma ray, infrared, near infrared, and / or particle radiation.

[0066] The radiation sensing materials described herein have the ability to retain radiation energy, i.e., they can capture radiation to which they are exposed within them. The retained radiation can later be released from the radiation sensing material at a predetermined time. The radiation sensing material may emit visible light as a result of a change, such as an increase or decrease in its temperature, and / or as a result of optical stimulation.

[0067] The radiation detecting material may be configured to retain radiation exposed thereto for a predetermined period of time. The radiation detecting material may be configured to emit the retained radiation as visible light when subjected to thermal treatment and / or light stimulation. The irradiated radiation may be retained within the radiation detecting material for a predetermined period of time. The predetermined period of time may be at least 1 minute, or at least 2 minutes, or at least 5 minutes, or at least 10 minutes, or at least 15 minutes, or at least 0.5 hours, or at least 1 hour, or at least 2 hours, or at least 5 hours, or at least 6 hours, or at least 8 hours, or at least 12 hours, or at least 18 hours, or at least 24 hours, or at least 1 week, or at least 1 month. The predetermined period of time may be 3 months or less, or 1 month or less, or 1 week or less, or 24 hours or less. The predetermined period of time may be 1 minute to 3 months, or 10 minutes to 1 month, or 0.5 hours to 1 week. In one embodiment, the predetermined period of time is 0.5 hours to 3 months.

[0068] The radiation sensing material may then be subjected to, for example, heating and / or optical stimulation to release the retained radiation from the radiation sensing material. Optical stimulation of the radiation sensing material may include subjecting the radiation sensing material to electromagnetic radiation having a wavelength between 310 nm and 1400 nm. In one embodiment, optical stimulation of the radiation sensing material includes subjecting the radiation sensing material to visible light, ultraviolet light, and / or near infrared light. Optical stimulation of the radiation sensing material may be performed by using a laser, a light emitting diode (LED), a micro LED, an organic light emitting diode (OLED), an active matrix organic light emitting diode (AMOLED), an incandescent lamp, a halogen lamp, any other optically stimulated luminescent light source, or any combination thereof.

[0069] The radiation detecting material can be used in a thermoluminescent dosimeter or an optically stimulated luminescent dosimeter. Thus, the device comprising the radiation detecting material may be a thermoluminescent dosimeter or an optically stimulated luminescent dosimeter.

[0070] The amount of visible light emitted by the sensor material can be determined by optical imaging, by photography, by thermally stimulated luminescence, and / or by optically stimulated luminescence. The amount of visible light emitted by the sensor material can be determined visually.

[0071] Radiation sensitive materials have the additional utility of exhibiting, as a result of being subjected to radiation, a color intensity that is proportional to the dose of radiation to which they are exposed.

[0072] Radiation sensing materials can be used to determine the intensity of radiation present. For example, radiation sensing materials may be used to indicate the intensity of ultraviolet radiation emitted by the sun. The intensity of radiation can be determined by methods including, for example: a) providing a radiation sensing material as disclosed herein; b) subjecting the radiation detecting material provided in step a) to radiation; c) determining the change in color of the material as a result of being subjected to radiation; and d) Comparing the color of the material to a standard that correlates the intensity of radiation with the color of the radiation detection material.

[0073] Step c) may be carried out by visually determining the color change of the material. The reference may for example be a card showing the correlation between the intensity of the radiation and the color intensity of the radiation-sensing material. The color intensity of the radiation-sensing material may for example be used to indicate the value of the UV index.

[0074] Thus, the present disclosure further relates to the use of radiation sensing materials represented by formula (I) disclosed herein to indicate the amount or intensity of radiation present in an environment. The radiation sensing material has the additional utility of being able to change color under exposure to radiation. The intensity of the color depends on the amount of radiation, such as ultraviolet light, that reaches the radiation sensing material. The color change of the radiation sensing material may be based on photochromism. The radiation may induce color centers in the radiation sensing material. The more radiation that hits the material, the more color centers are formed, thus resulting in a deeper color. In one embodiment, the radiation sensing material is a photochromic material.

[0075] In use, the radiation detecting material may be exposed to radiation for a predetermined period of time, such as from 0.01 seconds to 24 hours, or from 0.05 seconds to 1 hour, or from 0.1 seconds to 20 minutes, or from 1 second to 10 minutes, or from 5 seconds to 5 minutes, or from 30 seconds to 1 minute, etc. The time that the radiation detecting material may be exposed to radiation may depend on the application in which the radiation detecting material is used, and therefore on the amount of radiation to which the radiation detecting material is exposed.

[0076] The present disclosure further relates to materials derived from the radiation sensing materials disclosed herein, i.e., the radiation sensing materials disclosed herein can be used to derive or produce additional materials.

[0077] Radiation sensing materials have the additional utility of allowing them to detect the presence of radiation, such as ultraviolet, x-ray, gamma ray, infrared, near infrared, and / or particle radiation, etc. Furthermore, radiation sensing materials have the additional utility of indicating the intensity of radiation that is applied to them.

[0078] Radiation sensing materials have the added utility of being low cost materials used in a variety of devices in a variety of applications. EXAMPLES

[0079] Reference will now be made in detail to various embodiments, examples of which are illustrated in the accompanying drawings. The following description discloses several embodiments in detail to enable one skilled in the art to utilize the embodiments based on the present disclosure. Not every step or feature of the embodiments is described in detail, as many of the steps or features will be apparent to one skilled in the art based on this specification.

[0080] Example 1 - Preparation of materials In this example, the formula Na 8-x-y K x Ca y (AlSi) 6 O 24 (Cl,S) 2 A radiation sensing material represented by the formula: (wherein x=0-6, and y may vary and be between 0.28 and 1, and was 0.36 in this example) was prepared in the following manner: 0.7 g of dry 3 Å molecular sieve (Purmol® 3ST from Zeochem), 0.06 g of dry Na 2 SO 4 , 0.197 g dry NaCl, and 0.162 g CaCl 2 6H 2 The mixture was then reground and returned to the aluminum oxide boat for reduction. The reduction was carried out using H 2 / N 2 The mixture was heated at 850° C. for 2 hours under flowing atmosphere, and the product was then ground again.

[0081] Similarly, the formula Na 8-2y Ca y (AlSi) 6 O 24 (Cl,S) 2 A radiation sensing material represented by the formula: (wherein y=0.28-1) was prepared using 4 Å molecular sieve (Purmol® 4ST from Zeochem) instead of the 3 Å molecular sieve.

[0082] Similarly, the formula Na 8-2y Ca y (AlSi) 6 O 24 (Cl,S)2 A radiation-sensing material represented by the formula (where y = 0.28-1) was prepared using zeolite A (Sigma-Aldrich, CAS # 1318-02-1) instead of 3 Å molecular sieves.

[0083] Example 2 - Preparation of different materials Following the general instructions provided in Example 1, the following materials were prepared by using the following starting materials.

[0084] [Table 1]

[0085] Example 3 - Preparation of different materials In this example, the formula Na 7.32 Ca 0.34 (AlSi) 6 O 24 (Cl,S) 2 A radiation-sensing material represented by the formula: 2 , 0.3 g SiO 2 , 0.06g dry Na 2 SO 4 , 0.199 g dry NaCl and 0.153 g CaCl 2 . 6H 2 The powders were ground together and placed in an autoclave with approximately 20 ml of distilled water. The autoclave was placed in an oven at 180°C for 48 hours. The autoclave was cooled to room temperature, after which the samples were removed from the autoclave and dried at 100°C for 15 minutes. The dried powders were ground and placed in an alumina boat for reduction. The reduction was carried out in a 12% flowing H 2 and 88% N 2 The reaction was carried out at 850° C. for 2 hours under atmospheric pressure. After cooling, the product was collected.

[0086] Example 4 - Preparation of different materials Following the general instructions provided in Example 3, the following materials were prepared by using the following starting materials.

[0087] [Table 2]

[0088] Example 5 - Testing of samples of prepared materials Samples of the prepared materials were tested by: Huber G670 detector and copper K α1 Powder X-ray diffraction (XRD) measured using radiation (λ=1.54060 Å), see Figures 1a and 1b. The XRD patterns show that increasing the amount of calcium tends to make the structure less sodalite-type.

[0089] The elemental composition of the prepared materials was determined by X-ray fluorescence (XRF) measurements using a PANalytical Epsilon 1 instrument equipped with an internal omni-an calibration and a Na 1 time measurement program.

[0090] The photochromism of the material was investigated by reflectance measurements using an Avantes SensLine AvaSpec-HS-TEC spectrometer connected to an optical fiber. The reference spectrum of the material was measured before irradiation. The material was irradiated with a 254 nm UV lamp for 5 minutes and the final reflectance spectrum after irradiation was measured. See Figures 2a, 2b and 2c. The F center at 426 nm causes a yellow color change.

[0091] Tenebrescens color development curves were measured using an Avantes SensLine AvaSpec-HS-TEC spectrometer connected to an optical fiber and a LOT-QuantumDesign monochromator. The samples were illuminated with a 254 nm UV lamp and reflectance values ​​were measured every 4 seconds for 10 minutes. The same setup was used to measure tenebrescens excitation spectra. Reflectance was measured from 200 nm to 300 nm in 20 nm increments and from 300 nm to 450 nm in 25 nm increments. See Figures 3a, 3b, and 3c. The graphs show that the color change depends on the UV dose.

[0092] The luminescence (see Figures 4a and 4b) and persistent luminescence (see Figures 5a and 5b) characteristics of the samples were measured on a Varian Cary Eclipse fluorescence spectrophotometer equipped with a Hamamatsu R928 photomultiplier tube and a 150 W xenon lamp. For persistent emission spectra, the materials were excited with a 254 nm UV lamp for 5 minutes and the spectra were measured with a 30 second delay after irradiation.

[0093] The optical energy storage properties of the materials were investigated by thermoluminescence measurements using a MikroLab Thermoluminescent Materials Laboratory Reader RA'04, see Figure 6.

[0094] Figure 7 shows the yellow photochromism of the material. On the left, Na 7.28 Ca 0.36 (AlSiO 4 ) 6 (Cl,S) 2 On the right are two additional samples after staining. Number 32 is Na 6.72-x K x Ca 0.64 (AlSiO 4 ) 6 (Cl,S) 2 The number 35 represents the sample of Na 6.6-x K x Ca 0.7 (AlSiO 4 ) 6 (Cl,S) 2 Represents a sample of.

[0095] Figure 8 shows photographs of the near-infrared photochromism of the materials. The areas above the dashed line in each photograph were colored by approximately 15 minutes of exposure to 254 nm UV. The areas below the line were uncolored. The photographs were taken under 900 nm light using an 8 second exposure time on the camera. The contrast of the images was enhanced to show the difference between the colored and uncolored areas. Sample a was Na 6.72-x Kx Ca 0.64 (AlSiO 4 ) 6 (Cl,S) 2 and sample b is Na 6.6-x K x Ca 0.7 (AlSiO 4 ) 6 (Cl,S) 2 It was.

[0096] 9a and 9b and FIG. 10 show the results of the dual excitation emission simulation: Na 7.4-x K x Ca 0.3 (AlSiO 4 ) 6 (Cl,S) 2 A sample of (prepared using 3 Å molecular sieves) was excited with a 302 nm UV lamp and its emission spectrum was recorded. The same material was excited with a 365 nm UV lamp and its emission spectrum was recorded. To simulate a dual excitation setup of 302 nm and 365 nm UV lamps, an average spectrum was calculated weighted by the percentage of each UV lamp used. The calculated spectra were plotted and the CIE x,y color coordinates were calculated for the series using Osram Color Calculator software. The results show that with dual excitation the color of the emission can be controlled to blue and red and all shades and combinations in between.

[0097] It is obvious to those skilled in the art that with the advancement of technology, the basic idea can be realized in various ways. Therefore, the embodiments are not limited to the above examples. Instead, they can vary within the scope of the claims.

[0098] The above-mentioned embodiments may be used in any combination with each other. Some embodiments may be combined to form further embodiments. The radiation detection material, device, or use disclosed herein may include at least one of the above-mentioned embodiments. It will be understood that the above benefits and advantages may relate to one embodiment or to several embodiments. The embodiments are not limited to those that solve any or all of the stated problems or have any or all of the stated benefits and advantages. It will be further understood that a reference to "an" item refers to one or more of those items. The term "comprising" is used herein to mean including the features or operations that follow it without excluding the presence of one or more additional features or operations.

Claims

1. The following formula (I) (M1' ８－２ａ M2' ａ )(M'' １４－（４ｂ／３） M''' ｂ )O ２４ (X ２－ｄｃ dX' ｎ ｃ－ ) : M'''' Formula (I) (wherein M1′ represents a monovalent monoatomic cation of an alkali metal selected from Group 1 of the IUPAC periodic table of elements, or any combination of such cations, M2′ represents a divalent monoatomic cation of an alkaline earth metal selected from Group 2 of the IUPAC periodic table of elements, or any combination of such cations, M″ represents a trivalent monoatomic cation of an element selected from Group 13 of the IUPAC periodic table of elements, or any combination of such cations, M″′ represents a monoatomic cation of an element selected from Group 14 of the IUPAC periodic table of elements, or any combination of such cations, X represents an anion of an element selected from the halogens of Group 17 of the IUPAC periodic table of elements, or any combination of such anions, X′ represents an anion of one or more elements selected from the chalcogens of Group 16 of the IUPAC periodic table of elements, or any combination of such anions, M″″ represents a dopant cation of an element selected from the rare earth metals of the IUPAC periodic table of elements or from the transition metals of the IUPAC periodic table of elements, or a dopant cation of Ba, Sr, Tl, Pb or Bi, or any combination of such cations, or M″″ is absent, a is a value from 0.05 to 4, b is a value from 1 to 10, c is a value of 1, 2, 3 or 4, d is a value greater than 0 and less than or equal to 2, n is a value of 1, 2, 3 or 4) A radiation detection material represented by the formula.

2. The charge of M1′ is 1+, The charge of M2′ is 2+, The charge of M″ is 3+, The charge of M″′ is 4+, The charge of X is 1−, The charge of X′ is from 0.5− to 3.5−, The radiation detection material according to claim 1.

3. M1′ represents a monovalent monoatomic cation of Li, Na, K, Rb, Cs or Fr, The radiation detection material according to claim 1.

4. M2′ represents a divalent monoatomic cation of Be, Mg, Ca, Sr, Ba or Ra, The radiation detection material according to claim 1.

5. M1′ represents a monovalent monoatomic cation of Na, and M2′ represents a divalent monoatomic cation of Ca, The radiation detection material according to claim 1.

6. The radiation detection material according to claim 1, wherein M’’ represents a trivalent monoatomic cation of a metal selected from the group consisting of Al and Ga, or a trivalent monoatomic cation of B, or any combination of such cations.

7. The radiation detection material according to claim 1, wherein M’’’ represents a monoatomic cation of an element selected from the group consisting of Si and Ge, or a combination of such cations.

8. The radiation detection material according to claim 1, wherein X represents an anion of an element selected from the group consisting of F, Cl, Br, I, and At, or any combination of such anions.

9. The radiation detection material according to claim 1, wherein X’ represents a monoatomic or polyatomic anion of one or more elements selected from the group consisting of O, S, Se, and Te, or any combination of such anions.

10. The radiation detection material according to claim 1, wherein M’’’’ represents an element selected from the group consisting of Yb, Er, Tb, and Eu, or a cation of an element selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Ag, W, and Zn, or any combination of such cations.

11. The radiation detection material according to claim 1, wherein the radiation detection material is an ultraviolet ray, X-ray, gamma ray, infrared ray, near-infrared ray, and / or particle radiation detection material.

12. The radiation detection material according to claim 1, wherein the radiation detection material is a photochromic material that changes its color from white to yellow upon exposure to radiation.

13. The radiation detection material according to claim 1, wherein the radiation detection material is a material that absorbs radiation in the near-infrared region of the electromagnetic spectrum.

14. The radiation detection material according to claim 1, wherein the radiation detection material is a luminescent material, a material exhibiting persistent luminescence, and / or a material exhibiting afterglow.

15. An apparatus comprising the radiation detection material defined in any one of claims 1 to 14.

16. A material derived from the radiation detection material defined in any one of claims 1 to 14.

17. Use of the radiation detection material defined in any one of claims 1 to 14 for indicating the presence and / or intensity of ultraviolet rays, X-rays, gamma rays, infrared rays, near-infrared rays, and / or particle radiation.

18. Use of a radiation detection material as defined in any one of claims 1 to 14 as a light source in consumer products; security devices; detection; imaging; image acquisition; display, screen, window, or touch screen solutions; medicine; drug development; and / or diagnosis.

19. Use of a radiation detection material as defined in any one of claims 1 to 14 for detecting a disease in an antibody or staining entity, in a biomarker assay kit, in a screening platform, and / or in combination with a further material.

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