Surface disinfection using a PR3+-doped inorganic phosphor

Abstract

Described herein is a method for disinfecting a surface using a photon-emitting inorganic phosphor-doped substrate material. In addition, a method for preparing a photon-emitting inorganic phosphor-doped substrate material is described.

Description

Technical Field

[0001] Cross - Reference to Related Applications This application claims the benefit of priority to U.S. Provisional Patent Application No. 63 / 366,576, filed on June 17, 2022, the entire content of which is incorporated herein by reference in its entirety.

[0002] Field The subject matter disclosed herein generally relates to methods for disinfecting surfaces by utilizing the luminescence properties of rare - earth phosphors.

Background Art

[0003] Phosphor materials have the property of emitting ultraviolet light, visible light, or infrared light under the action of external excitation means such as irradiation with electromagnetic waves (e.g., electron beam, X - ray, ultraviolet light, visible light, etc.) or application of an electric field, and thus are used in a number of photoelectric converters or photoelectric conversion devices. Examples of such devices are light - emitting devices including white - light - emitting diodes, fluorescent lamps, electron - beam tubes, plasma display panels, inorganic electroluminescence displays, and scintillators. In particular, inorganic phosphors have been widely studied to meet the demand for low - voltage - stimulated lighting sources due to the increase in global energy consumption. Due to the advantages of being environmentally friendly, having a long lifespan, low energy consumption, high reliability, and high luminous efficiency, the latest white - light - emitting diodes (WLEDs) have replaced the less effective incandescent lamps and conventional mercury - enclosed fluorescent lamps.

[0004] Lanthanoids are often used as phosphors for luminescent applications. For example, the shielded f - orbitals of praseodymium enable a long excited - state lifetime and a high luminescence yield. In fact, Pr 3+ is often a dopant ion used in red, blue, green, and ultraviolet phosphors.

Summary of the Invention

[0005] In one aspect, the subject matter disclosed herein relates to a method for disinfecting a surface, the method comprising exposing a surface of a substrate material comprising an inorganic phosphor dopant to an ultraviolet light source, the exposing causing the inorganic phosphor dopant in the substrate material to emit photons that irradiate the surface, thereby disinfecting the surface.

[0006] In another aspect, the subject matter disclosed herein relates to a photon-emitting inorganic phosphor-doped substrate material, the material comprising a substrate material comprising an inorganic phosphor dopant, the inorganic phosphor dopant in the substrate material being capable of emitting photons upon exposure of the surface of the photon-emitting inorganic phosphor-doped substrate material to an ultraviolet light source.

[0007] In another aspect, the subject matter disclosed herein relates to a method for preparing a photon-emitting material for surface disinfection, the method comprising contacting a substrate material with an inorganic phosphor dopant to prepare an inorganic phosphor-doped substrate material, the inorganic phosphor dopant in the inorganic phosphor-doped substrate material being capable of emitting photons upon exposure of the surface of the inorganic phosphor-doped substrate material to an ultraviolet light source.

[0008] These and other aspects are described fully herein.

Brief Description of the Drawings

[0009]

Figure 1

Figure 2

Figure 3

Modes for Carrying Out the Invention

[0010] Subject matter The subject matter described in this specification relates to a method for disinfecting a surface by utilizing the luminescence characteristics of an inorganic phosphor dopant material. The method described in this specification provides several advantages over current methods in the art. In fact, the latest technological methods for disinfecting surfaces involve the application of expensive and heavy ultraviolet light sources. Prolonged exposure to these light sources can affect the substrate surface. Generally, in areas with high contact, prolonged exposure to pulsed ultraviolet light is required. Other disinfection methods in the art generally involve wiping the surface with a disinfectant solution that loses its effectiveness in a short time. Furthermore, exposure to such chemicals can have unintended effects on the substrate surface.

[0011] As described in this specification, by incorporating an inorganic phosphor into a substrate material, an emission surface of UV-C light (from 200 nm to 280 nm) can be obtained for use in disinfecting the substrate surface over a long period. After exposing the phosphor-doped substrate surface to a UV excitation source, the surface emits photons over an adjustable period after the excitation light is removed. The phosphor in the substrate directly absorbs ultraviolet light. The phosphor then emits radiative energy, and this energy disinfects the substrate surface. In this regard, the disinfection is brought about by the substrate surface itself. Furthermore, the disinfection method described in this specification is durable during operation because the inorganic phosphor is uniformly incorporated into the surface material, and wear or degradation due to exposure of the surface to chemicals is minimized. The disinfection method described in this specification can significantly shorten the time required to disinfect a surface using conventional methods.

[0012] UV-C light is weak at the Earth's surface because it is blocked by the ozone layer in the atmosphere. Many disinfection methods use short-wavelength ultraviolet light (ultraviolet C or UV-C) to kill or inactivate microorganisms by breaking down nucleic acids and destroying their DNA, making them unable to perform important cell functions. The inorganic phosphor in the phosphor-doped substrate material described in this specification emits such bactericidal UV-C light, which acts to disinfect the substrate surface.

[0013] A and B in FIG. 3 are schematic diagrams for charging the inorganic phosphor dopant in the substrate material and disinfecting the surface of the substrate material, respectively, by the method described in this specification. Briefly, in FIG. 3A, the surface (101a) of the substrate material (101) containing the inorganic phosphor dopant (100) is exposed to an ultraviolet light source to charge the inorganic phosphor dopant (100). As shown in FIG. 3B, after charging the inorganic phosphor dopant (100) in the substrate material (101), the ultraviolet light in FIG. 3A is removed, and the inorganic phosphor dopant (100) emits photons (105) having a wavelength in the UV-C range of light, and the photons (105) irradiate the surface (101a) of the substrate material (101), thereby disinfecting the surface (101a).

[0014] Hereinafter, the subject matter disclosed in this specification will be described in more detail. However, those skilled in the art related to the technology of the subject matter disclosed in this specification, who benefit from the teachings presented in the foregoing description, will envision numerous modifications and other embodiments of the subject matter of the disclosure shown herein. Accordingly, the subject matter disclosed in this specification is not limited to the specific embodiments disclosed, and it is to be understood that modifications and other embodiments are intended to be included within the scope of the claims. In other words, the subject matter described in this specification covers all alternatives, modifications, and equivalents. Unless otherwise specified, all technical and scientific terms used in this specification have the same meaning as commonly understood by one of ordinary skill in the art. All publications, patent applications, patents, and other references mentioned in this specification are incorporated by reference in their entirety. If one or more of the incorporated references, patents, and the like differ from or conflict with this application, including but not limited to defined terms, term usage, or described techniques, this application shall prevail.

[0015] I. Definitions As used in this specification, "and / or" refers to and encompasses any and all possible combinations of one or more of the associated listed items, as well as the absence of a combination (i.e., "or") when interpreted alternatively.

[0016] As used herein, the terms "approximately", "about", and "substantially" represent an amount close to the recited amount that still performs or achieves the desired function. For example, in some embodiments, as the context indicates, the terms "approximately", "about", and "substantially" may refer to an amount that is less than or equal to 10% of the recited amount. As used herein, the term "generally" represents a value, amount, or property that mainly includes a specific value, amount, or property, or a value, amount, or property that tends towards a specific value, amount, or property.

[0017] As used herein, language that includes conditions, such as, among others, "can", "could", "might", "may", "e.g.", etc., is generally intended to convey that some embodiments include certain features, components, and / or steps, while other embodiments do not, unless otherwise specified or understood in the context in which it is used. Thus, such language that includes conditions generally does not intend that a feature, configuration, and / or step is required in any way in one or more embodiments, or that one or more embodiments necessarily include logic for determining whether these features, elements, and / or steps are included or implemented in any particular embodiment, regardless of the presence or absence of the author's input or prompt. Terms such as "comprising", "including", "having", etc. are synonymous and are used inclusively and non-limitingly, and do not exclude additional elements, features, acts, operations, etc. The term "consisting of" and its grammatical variations are each synonymous and are used restrictively, excluding additional elements, features, acts, operations, etc. The term "consisting essentially of" and its grammatical variations are each synonymous and are semi-restrictive terms, indicating that the claimed item is limited to the components specified in the claim and does not materially affect the basic and novel characteristics of the claim. Additionally, the term "or" is used in an inclusive sense (not an exclusive sense), such that, for example, when used to connect listed elements, the term "or" means one, some, or all of the listed components.

[0018] As used herein, "contacting" refers to contacting a substrate material (101) with an inorganic phosphor dopant (100) to prepare a photon-emitting inorganic phosphor-doped substrate material. The inorganic phosphor dopant (100) as used herein refers to a metal oxide (106) or metal fluoride containing rare earth ions (107) or transition metals (108). The substrate material (101) acts as a host material, and the inorganic phosphor dopant (100) is incorporated into this host material, for example, through the application of heat and / or pressure. In some embodiments, the photon-emitting inorganic phosphor-doped substrate material comprises from about 0.05 to about 10 wt% or from about 0.01 to about 5 wt% of the inorganic phosphor dopant. In some other embodiments, the photon-emitting inorganic phosphor-doped substrate material comprises from about 0.05 to about 0.15 wt%, from about 0.10 to about 0.25 wt%, from about 0.15 to about 3 wt%, from about 0.25 to about 4 wt%, from about 1 to about 5 wt%, from about 1.5 to about 3.5 wt%, from about 2.5 to about 4 wt%, from about 0.50 to about 4.5 wt%, from about 4 to about 5 wt%, from about 5 to about 10 wt%, from about 3 to about 7 wt%, from about 4 to about 8 wt%, from about 6 to about 9 wt%, or from about 7 to about 10 wt% of the inorganic phosphor dopant.

[0019] As used herein, "photo-oxidation" refers to the degradation of the polymer surface due to the combined action of light and oxygen. Photo-oxidation causes the scission of polymer chains, resulting in an increase in the vulnerability of the material.

[0020] II. Methods for disinfecting a surface In some embodiments, as shown, for example, in FIG. 2, the subject matter described herein relates to a method (101a) for disinfecting a surface, the method comprising at step 250 of FIG. 2, exposing a surface (101a) of a substrate material (101) comprising an inorganic phosphor dopant (100) to an ultraviolet light source (104) to charge the inorganic phosphor dopant in the substrate material (101), Exposing causes the inorganic phosphor dopant (100) in the substrate material (101) to emit photons (105) having a wavelength of light in the UV-C range at step 255 of FIG. 2, and the photons (105) irradiate the surface (101a) of the photon-emitting inorganic phosphor-doped substrate material, thereby disinfecting the surface (101a).

[0021] When a phosphor is exposed to radiation, the orbital electrons within its molecules are excited to a higher energy level and emit energy as light of a specific color when returning to the original level. In fact, the scintillation process in inorganic materials is due to the electronic band structure found in crystals. Incident particles can excite electrons from the valence band to the conduction band or the exciton band (located just below the conduction band and separated from the valence band by an energy gap). This leaves a related hole in the valence band. Impurities create electron energy levels in the forbidden gap. An exciton is a loosely bound pair of an electron and a hole and diffuses through the crystal lattice until it is entirely captured by the center of an impurity. The latter then rapidly de-excites by emitting scintillation light (i.e., photons). The wavelength emitted depends on the atom itself and the surrounding crystal structure.

[0022] In some embodiments, the ultraviolet light source (104) used to excite (charge) the orbital electrons of the inorganic phosphor dopant has a wavelength between about 160 nm and 320 nm. In other embodiments, the ultraviolet light source (104) has a wavelength between about 160 nm and 260 nm, about 160 nm and 200 nm, about 180 nm and 240 nm, about 200 nm and 250 nm, about 210 nm and 250 nm, about 225 nm and 260 nm, about 230 nm and 250 nm, or about 190 nm and 260 nm. In some other embodiments, the ultraviolet light source has a wavelength of about 222 nm, 254 nm, or 275 nm.

[0023] Non-limiting examples of the ultraviolet light source (104) include, for example, black light, short-wavelength ultraviolet lamps, incandescent lamps, discharge lamps, ultraviolet LEDs, deuterium lamps, pulsed xenon light, and ultraviolet lasers. In one embodiment, the ultraviolet light source (104) is a pulsed xenon-ultraviolet device, which can be in the form of a handheld wand. The ultraviolet light emitted from the pulsed xenon device enables efficient charging of the inorganic phosphor dopant (100) in the substrate material (101), and the surface (101a) can be disinfected by hovering the xenon-ultraviolet wand about 1 to 5 inches above the surface (101a). In another embodiment, the ultraviolet light source (104) is a deuterium lamp, which has light in the range of about 185 nm to about 400 nm.

[0024] In addition to ultraviolet light, other excitation energy sources may be used in the methods described herein. Personal protective equipment (PPE) may be required for the operation of such energy sources.

[0025] In some embodiments of the above method, the inorganic phosphor dopant (100) in the substrate material (101) emits photons (105) having a wavelength of light between about 200 nm and 280 nm. In other embodiments, the inorganic phosphor dopant (100) in the substrate material (101) emits photons (105) having a wavelength of light between about 200 nm and 270 nm, between about 200 nm and 250 nm, between about 225 nm and 250 nm, between about 200 nm and 225 nm, between about 200 nm and 275 nm, or between about 225 nm and 275 nm. The emission wavelength of the inorganic phosphor dopant (100) can be adjusted by changing the excitation wavelength of the phosphor. In a preferred embodiment, the inorganic phosphor dopant emits UV-C light having a wavelength of about 200 to 280 nm.

[0026] In some embodiments, the inorganic phosphor dopant (100) is a metal oxide (106) or a metal fluoride (108) containing rare earth ions (107) or transition metal ions. In some embodiments, the rare earth ions (107) or transition metal ions are referred to as "activator ions". As used herein, "activator ions" are ions added as dopants to the crystal structure. The activator ions are surrounded by host crystal ions and form the luminescence centers where the excitation-emission process of the phosphor occurs. The wavelength emitted by the activator ions is affected by the ions themselves, their electron coordination, and the surrounding crystal structure.

[0027] Activator ions have unique characteristics that contribute to the optical properties of the phosphor, but the electronic energy levels of the activator ions in the crystal are different from those of the free ions. The separation of the energy levels results in luminescence from ultraviolet to visible wavelengths depending on the properties of the host crystal. The local shape around the activator ions affects the spectroscopic behavior of the activator ions incorporated into the host matrix, especially lanthanoid ions. Specific effects within the crystal lattice, such as ligand field splitting and center-of-gravity shifts, can affect the energy gap between the f and d orbitals of the activator ions and thereby influence the luminescence properties of such materials (Lin, YC., et al. Top Curr Chem(Z) 374, 21 (2016)).

[0028] In some embodiments, the inorganic phosphor dopant (100) is a metal oxide (106) containing rare earth ions (107). In some embodiments, the rare earth ions (107) are lanthanide ions. In some embodiments, the rare earth ions (107) are m 3+ , Pr 3+ , Ho 3+ , Er 3+ , Sm 3+ , Nd 3+ , Yb 3+ , Eu 3+ , Eu 2+ , Gd 3+ , Ce 3+ , Ce 2+ , Tb 3+ , Tb4+ , Dy 3+ , Yb 3+ , and Lu 3+ , or selected from the group consisting of combinations thereof. In some embodiments, the inorganic phosphor dopant (100) is Pr 3+ , Ce 3+ , Eu 3+ , Eu 2+ , Gd 3+ , Tb 3+ , and Dy 3+ , or a metal oxide (106) containing a rare earth ion (107) selected from the group consisting of mixtures thereof. In some embodiments, the rare earth ion (107) is Pr 3+ .

[0029] Pr 3+ -activated UV-C phosphor has a broad UV-C emission, and the parity-allowed Pr 3+ 4f 1 5d 1 ->4f 2 configuration transition is dominant. In the solid state, for the Pr 3+ 4f 1 5d 1 ->4f 2 transition to occur reliably, two general conditions are required. It is a small Stokes shift of less than about 3000 cm -1 (0.37 eV), and the appropriate energy position of the first (lowest energy) Pr 3+ 4f 2 ->4f 1 5d 1 excitation transition related to the composition and crystal structure of the host lattice. Under these conditions, the non-radiative relaxation from the Pr 3+ 4f 1 5d 1 level to the 4f 2 ( 3 P J , 1 I6, 1 D2) level is minimized. Otherwise, the crossing between the 4f 1 5d 1 level and the 4f 2 level occurs, and as a result, distinct lines of visible and infrared light emission 4f2 ->4f 2 Internal emission transmission becomes dominant (Wang, X., et al. Nat Commun 11, 2040 (2020)).

[0030] In some embodiments of the inorganic phosphor dopant (100), the metal oxide (106) (host lattice) is selected from the group consisting of silicates, phosphates, borates, oxides, oxynitrides, oxysulfides, and aluminates, or combinations thereof. Since such metal oxides (106) are ceramic materials, they exhibit several advantages including chemical, thermal, and photochemical stability. In some embodiments, the silicate is selected from the group consisting of melilite, cyclic silicate, silicate garnet, oxyorthosilicate, and orthosilicate. Non-limiting examples of silicates include Sr2MgSi2O7, Ca2Al2SiO7, SrAl2O4, MgSiO3, SrSiO3, CdSiO3, Ba2SiO4, BaMg2Si2O7, Ca2MgSi2O7, Sr 0.5 Ca 1.5 MgSi2O7, (Ca, Sr)2MgSi2O7, Sr3MgSi2O8, Sr2MgSi2O7, Ca 0.5 Sr 1.5 Al2SiO7, Sr3Al 10 SiO 20 , and Y2SiO5. Non-limiting examples of borates include YBO3 and CaAl2B2O7. Non-limiting examples of oxynitrides include MSi2O2N2 (M = Ba, Sr, or Ca). Non-limiting examples of phosphates include YPO4 and Zn3(PO4)2. Non-limiting examples of oxides include CaO, SrO, BaO, Y3Ga5O 12 , NaGdGeO4, Cd3Al2Ge3O 12 , CaTiO3, Ca 0.8 Zn 0.2 TiO3, and Ca2Zn4Ti 15 O 36 . Non-limiting examples of oxysulfides include Y2O2S, Gd2O2S, and Sr5Al2O7S. Non-limiting examples of aluminates include MgAl2O 4、 CaAl2O4, SrAl2O4, and Sr4Al14 O 25 is included.

[0031] In some embodiments of the inorganic phosphor dopant (100), the metal oxide (106) is Pr 3+ (Ca2Al2SiO7 doped with Ca2Al2SiO7 (Ca2Al2SiO7:Pr 3+ ). Ca2Al2SiO7 is Ca 2+ ions are sandwiched between layers where tetrahedra of AlO4 and SiO4 are arranged alternately along the c-axis and is characterized by a melilite structure with octahedral coordination. Each Ca 2+ ion is bonded to four nearest neighbor O 2- ligand ions, and thus the four Ca 2+ complexes within the unit cell are structurally equivalent. In Ca2Al2SiO7, Pr 3 +, trivalent Pr 3+ ions (1.126 Å) replace the smaller divalent Ca 2+ ions (1.12 Å). Thus, the doped Pr 3+ ions are octahedrally coordinated. Such a highly coordinated, smaller, and charge-imbalanced cation site can generate a suitably strong crystal field for Pr 3+ ions, thereby resulting in a small Stokes shift and thus efficient Pr 3+ 4f 1 5d 1 ->4f 2 intraconfigurational transitions are likely to occur. Furthermore, without wishing to be bound by theory, the cation size mismatch and charge imbalance are expected to create more effective energy traps (such as oxygen vacancies) around Pr 3+ ions and assist in the formation of effective persistent phosphors (Wang, X., et al. Nat Commun 11, 2040 (2020)).

[0032] In some embodiments of the inorganic phosphor dopant (100), the metal fluoride (108) (host lattice) is selected from the group consisting of Cs2NaYF6, NaCeF4, NaYF4, and NaGd4. Such metal fluoride hosts often have the characteristics of a large bandgap, structural defects that are likely to act as electron traps, and anionic defects that make it useful for inorganic phosphors. In some embodiments, the inorganic phosphor dopant (100) is Pr 3+ -doped Cs2NaYF6 (Cs2NaYF6:Pr 3+ ). In one embodiment, Pr 3+ substitutes the yttrium ion sites of Cs2NaYF6 in an amount from about 0.3% to about 10%. In other embodiments, Pr 3+ substitutes the yttrium ion sites of Cs2NaYF6 in an amount from about 1% to 5%, from 1.5% to 4.5%, from 2.5% to 5%, from 2% to 7%, from 3% to 8%, or from 4% to 9%.

[0033] In some embodiments, the substrate material (101) includes one or more synthetic polymers. Synthetic polymers are efficient, durable, and inexpensive materials that can be easily modified by heating techniques and / or pressure techniques to incorporate the inorganic phosphors described herein. In some embodiments, the substrate material (101) includes a material selected from the group consisting of fluorinated thermoplastic and thermosetting resins, and electro-negative resins. In other some embodiments, the substrate material (101) includes a material selected from the group consisting of tetrafluoroethylene, polyvinyl fluoride, polyurethane, polyester, epoxy, phenol, vinyl ester, polyamide, polyamide-imide, polyetherimide, polyvinyl chloride, polyether ketone, polycarbonate, polyphenyl sulfone, polymethyl methacrylate, polyacrylate, and benzoxazine, or combinations thereof. In particular, fluorine is known to be highly resistant to photo-oxidation because of its high electronegativity and its tendency to accept electrons. Thus, in some embodiments, fluorinated synthetic polymers such as tetrafluoroethylene or polyvinyl fluoride are useful as synthetic polymers in the methods described herein. Additionally, thermosetting polymers are generally known to have a high degree of cross-linking compared to other types of polymers, which further enhances their resistance to photo-oxidation.

[0034] A substrate material (101) containing one or more synthetic polymers can be applied to virtually any surface disinfection environment. In some embodiments, a substrate material (101) containing one or more synthetic polymers is located in an airplane, a hospital, a stadium, a school, or other areas with a high risk of vector movement.

[0035] In some embodiments of the above method, the surface (101a) is the interior of an airplane. In other some embodiments of the above method, the surface (101a) is located in a hospital, a stadium, or a school. In another example of the above method, the surface is present in a place with a high risk of vector movement.

[0036] In some embodiments, the material can be used to reduce the effect of the shadow of the surface area, thereby assisting in disinfecting surfaces that are not exposed to incident ultraviolet light. For example, the inorganic phosphor dopant (100) can be incorporated into polyvinyl fluoride (PVF) used in decorative laminates to increase the surface area of the substrate material (101) that can emit photons.

[0037] In an embodiment of the above method for disinfecting a surface, exposing the substrate material (101) comprising the inorganic phosphor dopant (100) to an ultraviolet light source (104) is carried out for a time sufficient to charge the inorganic phosphor dopant (100) in the substrate material (101). In some embodiments, a time sufficient to charge the inorganic phosphor dopant (100) in the substrate material (101) is from about 1 second to 2 seconds, 1 second to 30 seconds, 1 second to 25 seconds, 1 second to 20 seconds, 1 second to 15 seconds, 1 second to 10 seconds, 1 second to 5 seconds, 2 seconds to 5 seconds, 3 seconds to 15 seconds, 5 seconds to 10 seconds, 1 minute, 2 minutes, 3 minutes, 4 minutes, 5 minutes, 10 minutes, 15 minutes, 20 minutes, 30 minutes, 45 minutes, 1 hour, 2 hours, 3 hours, 5 hours, 7 hours, 10 hours, 15 hours, 20 hours, or 24 hours. The amount of time sufficient to charge the inorganic phosphor dopant (100) in the substrate material will vary depending on the wavelength of the ultraviolet light from the ultraviolet light source (104) and the inorganic phosphor dopant (100) itself.

[0038] In an embodiment of the above method for disinfecting a surface, the inorganic phosphor dopant (100) in the substrate material (101) emits photons (105) for about 2 minutes, 3 minutes, 4 minutes, 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes, 10 minutes, 11 minutes, 12 minutes, 13 minutes, 14 minutes, 15 minutes, 16 minutes, 17 minutes, 18 minutes, 19 minutes, 20 minutes, 25 minutes, 30 minutes, 45 minutes, or 60 minutes. The amount of time that the inorganic phosphor dopant (100) emits photons (105) can be adjusted, for example, by changing the length of time for charging the inorganic phosphor dopant (100). The duration of the emission can also be adjusted according to the desired application. For example, if the surface to be disinfected is located inside an airplane, the appropriate maximum emission time is about 10 minutes, 15 minutes, 20 minutes, 25 minutes, or 30 minutes so that the disinfection operation can be carried out between flights. In some other embodiments, a longer emission time may correlate with a higher disinfection level. For example, if the surface to be disinfected is located inside a hospital or a medical facility, in this type of environment, a higher disinfection level may be desired, so the emission time can range between about 30 minutes and 60 minutes.

[0039] One or more dopant ions can be used to not only change the emission intensity but also adjust the emissivity to a longer wavelength or a shorter wavelength. For example, doping SrAl2O4 with Eu 2 + results in a phosphor that emits light at 520 nm. However, SrAl2O4 can also be co-doped with Eu 2+ and Dy 3+ and acts to greatly enhance the persistent emission intensity. At room temperature, the afterglow of SrAl2O4:Eu 2+ , Dy 3+It lasts for several hours, which is the result of the gradual release of the charges trapped in the phosphor by heat. Such long afterglow is in contrast to the mutant without codopant which lasts only for a few minutes (Xingdong, L., et al. J. Wuhan Univ. Technol.-Mat. Sci. Edit. 23, 652-657 (2008)). Furthermore, it can be stabilized with an inorganic phosphor dopant (100) having an energy trap that can be filled during excitation. The energy trap can be adjusted by adjusting the required penetration depth of the UV energy to adjust the decay time required to decontaminate the surface over time.

[0040] The light emitted by the inorganic phosphor dopant (100) in the photon-emitting inorganic phosphor-doped substrate material irradiates the substrate surface (101a) isotropically as it moves away from the surface (101a), thereby disinfecting the surface (101a). Isotropic irradiation refers to the radiation from a point source that irradiates uniformly in all directions with the same intensity regardless of the measurement direction. The light emitted by the inorganic phosphor dopant (100) is short-wavelength ultraviolet (ultraviolet C or UV-C) light having a wavelength range of 200 nm to 280 nm or 225 nm to 250 nm, which is known to have a bactericidal effect.

[0041] In some embodiments of the method for disinfecting the surface, the substrate material (101) comprises tetrafluoroethylene or polyvinyl fluoride, the ultraviolet light source (104) has a wavelength of about 160 to 260 nm, and the inorganic phosphor dopant (100) is Pr 3 + -containing silicate, and the inorganic phosphor dopant (100) emits photons (105) having a wavelength of light of about 265 nm.

[0042] III. Photon-emitting inorganic phosphor-doped substrate material In some embodiments, the subject matter described herein relates to a photon-emitting inorganic phosphor-doped substrate material, which material A substrate material (101) comprising an inorganic phosphor dopant (100), wherein the inorganic phosphor dopant (100) in the substrate material (101) is capable of emitting photons (105) upon exposure of the surface of the photon-emitting inorganic phosphor-doped substrate material to an ultraviolet light source (104), and comprising the substrate material (101).

[0043] In some embodiments of the photon-emitting inorganic phosphor-doped substrate material, the substrate material comprises one or more synthetic polymers. In some embodiments, the substrate material comprises a material selected from the group consisting of fluorinated thermoplastic and thermosetting resins, and electronegative resins. In some embodiments, the substrate material comprises a material selected from the group consisting of tetrafluoroethylene, polyvinyl fluoride, polyurethane, polyester, epoxy, phenol, vinyl ester, polyamide, polyamide-imide, polyetherimide, polyvinyl chloride, polyetherketoneketone, polycarbonate, polyphenylsulfone, polymethyl methacrylate, polyacrylate, and benzoxazine. In some embodiments of the photon-emitting inorganic phosphor-doped substrate material, the substrate material is an aircraft interior.

[0044] In some embodiments of the photon-emitting inorganic phosphor-doped substrate material, the inorganic phosphor dopant (100) is a metal oxide (106) or a metal fluoride (108) comprising rare earth ions (107) or transition metal ions. In some embodiments of the photon-emitting inorganic phosphor-doped substrate material, the inorganic phosphor dopant (100) is a metal oxide (106). In some embodiments, the rare earth ions (107) are lanthanide ions. In some embodiments, the rare earth ions (107) are m 3+ , Pr 3+ , Ho 3+ , Er 3+ , Sm 3+ , Nd 3+ , Yb 3+ , Eu 3+ , Eu 2+ , Gd 3+ , Ce 3+ , Ce 2+ , Tb 3+ , Tb 4+ , Dy 3+ , Yb3+ and Lu 3+ is selected from the group consisting of, or combinations thereof. In some embodiments, the inorganic phosphor dopant (100) is Pr 3+ Ce 3+ Eu 3+ Eu 2+ Gd 3+ Tb 3+ and Dy 3+ is a metal oxide (106) containing a rare earth ion (107) selected from the group consisting of, or a mixture thereof. In some embodiments, the rare earth ion (107) is Pr 3+ is.

[0045] In some embodiments of the inorganic phosphor dopant (100) where the inorganic phosphor dopant (100) is a metal oxide (106), the metal oxide (106) is selected from the group consisting of silicates, phosphates, borates, oxides, oxynitrides, oxysulfides, and aluminates, or combinations thereof. In some embodiments, the silicate is selected from the group consisting of melilite, cyclic silicate, silicate garnet, oxyorthosilicate, and orthosilicate. Non-limiting examples of silicates include Sr2MgSi2O7, Ca2Al2SiO7, SrAl2O4, MgSiO3, SrSiO3, CdSiO3, Ba2SiO4, BaMg2Si2O7, Ca2MgSi2O7, Sr 0.5 Ca 1.5 MgSi2O7, (Ca,Sr)2MgSi2O7, Sr3MgSi2O8, Sr2MgSi2O7, Ca 0.5 Sr 1.5 Al2SiO7, Sr3Al 10 SiO 20 and Y2SiO5 are included. Non-limiting examples of borates include YBO3 and CaAl2B2O7. Non-limiting examples of oxynitrides include MSi2O2N2 (M = Ba, Sr, or Ca). Non-limiting examples of phosphates include YPO4 and Zn3(PO4)2. Non-limiting examples of oxides include CaO, SrO, BaO, Y3Ga5O 12 NaGdGeO4, Cd3Al2Ge3O 12 CaTiO3, Ca 0.8 Zn0.2 TiO3, and Ca2Zn4Ti 15 O 36 is included. Non-limiting examples of oxysulfides include Y2O2S, Gd2O2S, and Sr5Al2O7S. Non-limiting examples of aluminates include MgAl2O 4、 CaAl2O4, SrAl2O4, and Sr4Al 14 O 25 is included.

[0046] In some embodiments of the inorganic phosphor dopant (100), the metal oxide (106) is Ca2Al2SiO7 doped with Pr 3+ .

[0047] In some embodiments of the inorganic phosphor dopant (100), the metal fluoride (108) (host lattice) is selected from the group consisting of Cs2NaYF6, NaCeF4, NaYF4, and NaGd4. Such metal fluoride hosts often have the characteristics of a large bandgap, structural defects that are likely to act as electron traps, and anionic defects that make them useful for inorganic phosphors. In some embodiments, the inorganic phosphor dopant (100) is Cs2NaYF6 doped with Pr 3+ (Cs2NaYF6:Pr 3+ ). In one embodiment, Pr 3+ substitutes the yttrium ion sites of Cs2NaYF6 in an amount from about 0.3% to about 10%. In other embodiments, Pr 3+ substitutes the yttrium ion sites of Cs2NaYF6 in an amount from about 1% to 5%, from 1.5% to 4.5%, from 2.5% to 5%, from 2% to 7%, from 3% to 8%, or from 4% to 9%.

[0048] In some embodiments of the photon-emitting inorganic phosphor-doped substrate material, the inorganic phosphor dopant (100) in the substrate material (101) can emit photons (105) having a wavelength of light between 200 nm and 280 nm upon exposure of the surface (101a) of the photon-emitting inorganic phosphor-doped substrate material to an ultraviolet light source (104). In some embodiments of the photon-emitting inorganic phosphor-doped substrate material, the inorganic phosphor dopant (100) in the substrate material (101) can emit photons having a wavelength of light between about 200 nm and 270 nm, between about 200 nm and 250 nm, between about 225 nm and 250 nm, between about 200 nm and 225 nm, between about 200 nm and 275 nm, or between about 225 nm and 275 nm (105).

[0049] IV. Method for Preparing a Photon-Emitting Material In some embodiments, as shown, for example, in FIG. 1, the subject matter described herein relates to a method for preparing a photon-emitting material for surface disinfection, the method comprising at step 150 of FIG. 1, preparing an inorganic phosphor dopant (100); and at step 155 of FIG. 1, contacting a substrate material (101) with the inorganic phosphor dopant (100) to prepare a photon-emitting inorganic phosphor-doped substrate material, wherein the inorganic phosphor dopant (100) in the photon-emitting inorganic phosphor-doped substrate material can emit photons (105) upon exposure of the surface (101a) of the photon-emitting inorganic phosphor-doped substrate material to an ultraviolet light source (104), preparing a photon-emitting inorganic phosphor-doped substrate material and including.

[0050] In some embodiments of a method for preparing a photon-emitting material for surface disinfection, the inorganic phosphor dopant (100) in the photon-emitting inorganic phosphor-doped substrate material can emit photons having a wavelength of light between about 200 nm and 280 nm (105). In some embodiments of a method for preparing a photon-emitting material for surface disinfection, the inorganic phosphor dopant (100) in the photon-emitting inorganic phosphor-doped substrate material can emit photons having a wavelength of light between about 200 nm and 270 nm, between about 200 nm and 250 nm, between about 225 nm and 250 nm, between about 200 nm and 225 nm, between about 200 nm and 275 nm, or between about 225 nm and 275 nm (105).

[0051] In some embodiments of a method for preparing a photon-emitting material for surface disinfection, the inorganic phosphor dopant (100) is a metal oxide (106) or a metal fluoride (108) containing rare earth ions (107) or transition metal ions. In some embodiments of a method for preparing a photon-emitting material for surface disinfection, the inorganic phosphor dopant (100) is a metal oxide (106). In some embodiments, the rare earth ions (107) are lanthanide ions. In some embodiments, the rare earth ions (107) are m 3+ , Pr 3+ , Ho 3+ , Er 3+ , Sm 3+ , Nd 3+ , Yb 3+ , Eu 3+ , Eu 2+ , Gd 3+ , Ce 3+ , Ce 2+ , Tb 3+ , Tb 4+ , Dy 3+ , Yb 3+ , and Lu 3+ , or are selected from the group consisting of combinations thereof. In some embodiments, the inorganic phosphor dopant (100) is Pr 3+ , Ce 3+ , Eu 3+ , Eu 2+ , Gd 3+ , Tb 3+ , and Dy 3+, or a metal oxide (106) containing a rare earth ion (107) selected from the group consisting of their mixtures. In some embodiments, the rare earth ion (107) is Pr 3+ is.

[0052] In some embodiments of a method for preparing a photon-emitting material for surface disinfection, the metal oxide (106) is selected from the group consisting of silicates, phosphates, borates, oxides, oxynitrides, oxysulfides, and aluminates, or combinations thereof. In some embodiments, the silicate is selected from the group consisting of melilite, cyclic silicate, silicate garnet, oxyorthosilicate, and orthosilicate. Non-limiting examples of silicates include Sr2MgSi2O7, Ca2Al2SiO7, SrAl2O4, MgSiO3, SrSiO3, CdSiO3, Ba2SiO4, BaMg2Si2O7, Ca2MgSi2O7, Sr 0.5 Ca 1.5 MgSi2O7, (Ca, Sr)2MgSi2O7, Sr3MgSi2O8, Sr2MgSi2O7, Ca 0.5 Sr 1.5 Al2SiO7, Sr3Al 10 SiO 20 , and Y2SiO5. Non-limiting examples of borates include YBO3 and CaAl2B2O7. Non-limiting examples of oxynitrides include MSi2O2N2 (M = Ba, Sr, or Ca). Non-limiting examples of phosphates include YPO4 and Zn3(PO4)2. Non-limiting examples of oxides include CaO, SrO, BaO, Y3Ga5O 12 , NaGdGeO4, Cd3Al2Ge3O 12 , CaTiO3, Ca 0.8 Zn 0.2 TiO3, and Ca2Zn4Ti 15 O 36 are included. Non-limiting examples of oxysulfides include Y2O2S, Gd2O2S, and Sr5Al2O7S. Non-limiting examples of aluminates include MgAl2O 4、 CaAl2O4, SrAl2O4, and Sr4Al 14 O 25 are included.

[0053] In some embodiments of the inorganic phosphor dopant (100), the metal oxide (106) is Pr 3+ doped Ca2Al2SiO7.

[0054] In some embodiments of the inorganic phosphor dopant (100), the metal fluoride (108) (host lattice) is selected from the group consisting of Cs2NaYF6, NaCeF4, NaYF4, and NaGd4. Such metal fluoride hosts often have the characteristics of a large bandgap, structural defects that are likely to act as electron traps, and anionic defects that make it useful for inorganic phosphors. In some embodiments, the inorganic phosphor dopant (100) is Pr 3+ doped Cs2NaYF6 (Cs2NaYF6:Pr 3+ ). In one embodiment, Pr 3+ substitutes the yttrium ion sites of Cs2NaYF6 in an amount from about 0.3% to about 10%. In other embodiments, Pr 3+ substitutes the yttrium ion sites of Cs2NaYF6 in an amount from about 1% to 5%, from 1.5% to 4.5%, from 2.5% to 5%, from 2% to 7%, from 3% to 8%, or from 4% to 9%.

[0055] In some embodiments of a method for preparing a photon-emitting material for surface disinfection, the substrate material (101) comprises one or more synthetic polymers. In some embodiments, the substrate material (101) comprises a material selected from the group consisting of fluorinated thermoplastic and thermosetting resins, and electronegative resins. In some embodiments, the substrate material (101) comprises a material selected from the group consisting of tetrafluoroethylene, polyvinyl fluoride, polyurethane, polyester, epoxy, phenol, vinyl ester, polyamide, polyamide-imide, polyetherimide, polyvinyl chloride, polyether ketone ketone, polycarbonate, polyphenyl sulfone, polymethyl methacrylate, polyacrylate, and benzoxazine. As described in other embodiments herein, fluorinated polymers are particularly resistant to photooxidation.

[0056] In some embodiments of a method for preparing a photon-emitting material for surface disinfection, the substrate material (101) comprises tetrafluoroethylene or polyvinyl fluoride, and the inorganic phosphor dopant (100) is Pr 3+ -containing silicate. In some embodiments, the silicate is Ca2Al2SiO7.

[0057] Methods for preparing the inorganic phosphor dopant (100) are known in the art. See, for example, Broxtermann et al., ECS Journal of Solid State Science and Technology, 6(4) R47-R52 (2017); and Poelman et al., Journal of Applied Physics 128, 240903 (2020). In an embodiment, the metal oxide (106) host material and the rare earth oxide are weighed such that a certain amount of rare earth ions (107) are substituted or doped into the metal oxide lattice. The amount of ions added can be determined by calculating the stoichiometry of the material presented and then weighing out the appropriate amount of starting materials using dimensional analysis. The metal oxide (106) powder is thoroughly ground using a mortar and pestle to maximize contact between the particles in the mixture. After placing it in a suitable crucible (often alumina), the mixture is heated in a tube furnace or muffle furnace to a temperature sufficient to induce a solid reaction but below the melting point of the final compound. From a temperature about 200 - 300 °C lower than this melting temperature, the particle size of the final compound significantly increases. This heating process is called sintering and generally results in a very dense and strongly agglomerated material. This material cannot be directly applied as a phosphor. Therefore, in many cases, it is necessary to grind it manually or using a ball mill after synthesis.

[0058] Ball milling is a mechanical method of reducing particle size by mechanical impact and friction. Typically, the powder is placed in a grinding jar together with a number of hard grinding balls (often Al2O3 or ZrO2) and a solvent so that a slurry is obtained. Then, the grinding jar is moved so that the friction is maximized. Similar to the case of manual grinding using a mortar and pestle, the effect of this process depends greatly on the size and hardness of the starting material.

[0059] In the case of the solid synthesis described above, the atmosphere used for heating can vary depending on the host material. In the case of oxides, air can usually be applied. However, some dopants, especially europium, are oxidized within the oxygen lattice while being heated in oxygen, leading to the formation of a fully oxidized Eu 3+ dopant. If Eu 2+ is the preferred valence state of this dopant, additional heat treatment may be required in a reducing atmosphere such as helium or argon.

[0060] Other methods for preparing inorganic phosphor dopants (100) include sol-gel synthesis, colloidal synthesis, and co-precipitation. In the sol-gel method, for example, the powder is weighed out, dissolved in a concentrated acid such as HNO3 (e.g., 70% w / w), and then diluted with deionized water. This solution is then cooled to room temperature and added dropwise to a low-temperature saturated aqueous solution of another acid such as oxalic acid. The solid material is then precipitated and then washed with deionized water and other polar solvents (such as acetone, acetonitrile, dimethylformamide (DMF), dimethyl sulfoxide (DMSO), isopropanol, or methanol). The solid material is then calcined at a temperature of about 1000 °C to 1200 °C for several hours, followed by intermittent grinding and sintering. In some embodiments, after weighing and mixing, the metal oxide host powder and the rare earth oxide powder are directly placed in a furnace at 1000 - 1100 °C for 2 - 48 hours.

[0061] Next, the prepared inorganic phosphor dopant (100) is inserted into the substrate (host) material (101). The substrate (host) material (101) is, in some embodiments, the host material of a synthetic polymer substrate. The host material of the synthetic polymer substrate can be purchased from commercial suppliers such as Dupont or Sigma. The inorganic phosphor dopant (100) is in powder form and can be incorporated into the substrate material (101) by melting the polymer substrate and then mixing it into the inorganic phosphor dopant (100). Mixing can be facilitated, for example, by further heating the materials and / or by using a mixing paddle. An amount of the inorganic phosphor dopant (100) sufficient for disinfecting the substrate surface (101a) can be incorporated into the synthetic polymer substrate (host) material (101).

[0062] After incorporating the inorganic phosphor dopant (100) into the substrate material (101), the photon-emitting inorganic phosphor-doped (synthetic polymer) substrate material is cured. Curing can be carried out, for example, at room temperature in air. Curing can be effected by the inorganic phosphor dopant (100) dispersed throughout the substrate (polymer host) material (101) in the photon-emitting inorganic phosphor-doped (synthetic polymer) substrate material. The smaller the difference in polarity between the substrate (polymer host) material (101) and the inorganic phosphor dopant (100), the more uniformly the inorganic phosphor dopant (100) will be dispersed throughout the polymer.

[0063] Furthermore, the present disclosure includes examples according to the following clauses.

[0064] Clause 1. A method for disinfecting a surface, comprising: exposing the surface of a substrate material containing an inorganic phosphor dopant to an ultraviolet light source, wherein the exposure causes the inorganic phosphor dopant in the substrate material to emit photons, and the photons irradiate the surface, thereby disinfecting the surface. Method.

[0065] Clause 2. The method according to Clause 1, wherein the inorganic phosphor dopant in the substrate material emits photons having a wavelength of light between about 200 nm and 280 nm.

[0066] Clause 3. The method according to Clause 2, wherein the inorganic phosphor dopant in the substrate material emits photons having a wavelength of light between about 225 nm and 250 nm.

[0067] Clause 4. The method according to any one of Clauses 1 to 3, wherein the ultraviolet light source has a wavelength between about 160 nm and 320 nm.

[0068] Clause 5. The method according to any one of Clauses 1 to 4, wherein the ultraviolet light source has a wavelength of about 222 nm, 254 nm, or 275 nm.

[0069] Clause 6. The inorganic phosphor dopant is a metal oxide or metal fluoride containing rare earth ions selected from the group consisting of Pr 3+ , Ce 3+ , Eu 3+ , Eu 2+ , Gd 3+ , Tb 3+ , and Dy 3+ , or a mixture thereof. The method according to any one of Clauses 1 to 5.

[0070] Clause 7. The method according to Clause 6, wherein the rare earth ion is Pr 3+ .

[0071] Clause 8. The method according to Clause 6 or 7, wherein the metal oxide is selected from the group consisting of silicate, phosphate, borate, oxide, oxynitride, oxysulfide, and aluminate, or a combination thereof.

[0072] Clause 9. The method according to any one of Clauses 1 to 8, wherein the substrate material comprises one or more synthetic polymers.

[0073] Clause 10. The method according to Clause 9, wherein the substrate material comprises a material selected from the group consisting of optionally fluorinated thermoplastic and thermosetting resins, and electro-negative resins.

[0074] Clause 11. The method according to clause 9 or 10, wherein the substrate material comprises a material selected from the group consisting of tetrafluoroethylene, polyvinyl fluoride, polyurethane, polyester, epoxy, phenol, vinyl ester, polyamide, polyamide-imide, polyetherimide, polyvinyl chloride, polyether ketone ketone, polycarbonate, polyphenyl sulfone, polymethyl methacrylate, polyacrylate, and benzoxazine.

[0075] Clause 12. The method according to any one of clauses 1 to 11, wherein exposing the substrate material containing the inorganic phosphor dopant to an ultraviolet light source is performed for a time sufficient to charge the inorganic phosphor dopant in the substrate material.

[0076] Clause 13. The method according to any one of clauses 1 to 12, wherein the ultraviolet light source is a pulsed xenon-ultraviolet device.

[0077] Clause 14. A photon-emitting inorganic phosphor-doped substrate material, comprising a substrate material containing an inorganic phosphor dopant, wherein the inorganic phosphor dopant in the substrate material can emit photons upon exposure to an ultraviolet light source on the surface of the photon-emitting inorganic phosphor-doped substrate material. Photon-emitting inorganic phosphor-doped substrate material.

[0078] Clause 15. The photon-emitting inorganic phosphor-doped substrate material according to clause 14, comprising one or more synthetic polymers.

[0079] Clause 16. The photon-emitting inorganic phosphor-doped substrate material according to clause 14 or 15, wherein the substrate material comprises a material selected from the group consisting of thermoplastic and thermosetting resins which may be fluorinated, and electro-negative resins.

[0080] Item 17. The inorganic phosphor-doped substrate material according to any one of Items 14 to 16, comprising a material selected from the group consisting of tetrafluoroethylene, polyvinyl fluoride, polyurethane, polyester, epoxy, phenol, vinyl ester, polyamide, polyamide-imide, polyetherimide, polyvinyl chloride, polyether ketone ketone, polycarbonate, polyphenyl sulfone, polymethyl methacrylate, polyacrylate, and benzoxazine.

[0081] Item 18. The inorganic phosphor dopant is Pr 3+ , Ce 3+ , Eu 3+ , Eu 2+ , Gd 3+ , Tb 3+ , and Dy 3+ , or a metal oxide or metal fluoride containing a rare earth ion selected from the group consisting of a mixture thereof, the inorganic phosphor-doped substrate material according to any one of Items 14 to 17.

[0082] Item 19. The inorganic phosphor-doped substrate material according to Item 18, wherein the rare earth ion is Pr 3+ .

[0083] Item 20. The inorganic phosphor-doped substrate material according to Item 18 or 19, wherein the metal oxide is selected from the group consisting of silicate, phosphate, borate, oxide, oxynitride, oxysulfide, and aluminate, or a combination thereof.

[0084] Item 21. The inorganic phosphor dopant in the substrate material can emit photons having a wavelength of light between about 180 nm and 320 nm by exposure of the surface of the inorganic phosphor-doped substrate material to an ultraviolet light source, the inorganic phosphor-doped substrate material according to any one of Items 14 to 20.

[0085] Item 22. A method for preparing a photon-emitting material for surface disinfection, A method comprising contacting a substrate material with an inorganic phosphor dopant to prepare a photon-emitting inorganic phosphor-doped substrate material, wherein the inorganic phosphor dopant in the photon-emitting inorganic phosphor-doped substrate material can emit photons upon exposure of the surface of the inorganic phosphor-doped substrate material to an ultraviolet light source.

[0086] Clause 23. The method according to clause 22, wherein the inorganic phosphor dopant in the photon-emitting inorganic phosphor-doped substrate material can emit photons having a wavelength of light between about 180 nm and 320 nm.

[0087] Clause 24. The inorganic phosphor dopant is a metal oxide or metal fluoride containing a rare earth ion selected from the group consisting of Pr 3+ , Ce 3+ , Eu 3+ , Eu 2+ , Gd 3+ , Tb 3+ , and Dy 3+ , or a mixture thereof, according to the method of clause 22 or 23.

[0088] Clause 25. The method according to clause 24, wherein the rare earth ion is Pr 3+ .

[0089] Clause 26. The method according to clause 24 or 25, wherein the metal oxide is selected from the group consisting of silicates, phosphates, borates, oxides, oxynitrides, oxysulfides, and aluminates, or combinations thereof.

[0090] Clause 27. The method according to any one of clauses 22 to 26, wherein the substrate material comprises one or more synthetic polymers.

[0091] Clause 28. The method according to clause 27, wherein the substrate material comprises a material selected from the group consisting of a thermoplastic and thermosetting resin, which may be fluorinated, and an electro-negative resin.

[0092] Clause 29. The method according to clause 27 or 28, wherein the substrate material comprises a material selected from the group consisting of tetrafluoroethylene, polyvinyl fluoride, polyurethane, polyester, epoxy, phenol, vinyl ester, polyamide, polyamide-imide, polyetherimide, polyvinyl chloride, polyether ketone ketone, polycarbonate, polyphenyl sulfone, polymethyl methacrylate, polyacrylate, and benzoxazine.

[0093] The following examples are provided for illustrative purposes and are not intended to be limiting. Those skilled in the art will understand that other synthetic routes may be used to synthesize the inorganic phosphor dopants and inorganic phosphor-doped substrate materials described herein. Specific starting materials and reagents are shown and described in the examples, but other starting materials and reagents may be readily substituted to provide various derivative materials and / or reaction conditions. In addition, many of the exemplary materials prepared by the methods described can be further modified in light of the present disclosure using conventional chemicals well known to those skilled in the art.

Examples

[0094] Example 1: Preparation of a Photon-Emitting Inorganic Phosphor-Doped Substrate Material (Ca 2-x Al2SiO7: x Pr 3+ Doped Polyvinyl Fluoride) Step 1. Preparation of Ca 2-x Al 2 SiO 7 : x Pr 3+ (100) CaO, Al2O3, SiO2, and Pr6O 11 were purchased from Sigma Aldrich. CaO, Al2O3, SiO2, and Pr6O 11 were used with Pr6O in the mixture 11Weigh out an amount that results in 0.5 - 5% substitution of praseodymium on the calcium sites. Then, using an agate mortar and pestle, grind the powder for approximately 5 minutes until a fine gray mixture is formed. Subsequently, place the mixed powder in a ceramic alumina crucible and pre - burn it in air at 900 °C for 2 hours. Next, completely grind the mixed powder with an agate mortar and pestle for approximately 3 minutes. Then, return the mixed powder to the alumina crucible, place it in a furnace, and heat it in air at 1300 °C for 7 hours. Remove the powder from the furnace and cool it to room temperature.

[0095] The prepared Ca 2-x Al2SiO7: x Pr 3+ The inorganic phosphor dopant (100) is analyzed by powder X - ray diffraction. The crystal structure is analyzed using FullProf to verify the Ca / Pr site mixing in the Ca2Al2SiO7 crystal structure.

[0096] Step 2. Preparation of Ca 2-x Al 2 SiO 7 : x Pr 3+ Doped polyvinyl fluoride Polyvinyl fluoride (Dupont) (101) is heated to approximately 180 °C in an argon atmosphere to melt the material. The Ca 2-x Al2SiO7: x Pr 3+ (100) powder prepared in Step 1 is completely mixed with the melted polyvinyl fluoride and a phosphor / volume polymer in an amount of about 10 volume % so that the Ca 2-x Al2SiO7: x Pr 3+ is uniformly incorporated into the polyvinyl fluoride host material (101). Then, the doped polyvinyl fluoride is cured to form a substrate material of solidified Ca 2-x Al2SiO7: x Pr 3+ In some embodiments, Ca 2-x Al2SiO7: x Pr3+ The substrate material of doped polyvinyl fluoride can be molded, for example, using a mold, during curing. The mold is Ca 2-x Al2SiO7: x Pr 3+ The substrate material of doped polyvinyl fluoride can help to constitute usable products, such as cabinets, counters, wallpapers, or covers for various household products, medical products, automotive products, or aerospace products. In addition, the solidified Ca 2-x Al2SiO7: x Pr 3+ After preparing the doped polyvinyl fluoride substrate material, the material can be easily molded and modified, for example, using a saw, sandpaper, or an appropriate mold.

[0097] Example 2: Disinfection using an inorganic phosphor-doped substrate material (Ca 2-x Al2SiO7: x Pr 3+ doped polyvinyl fluoride) The Ca 2-x Al2SiO7: x Pr 3+ doped polyvinyl fluoride substrate material prepared in Step 2 is exposed to an ultraviolet lamp having a wavelength between about 160 nm and 280 nm. This is the radiative excitation energy of the Ca 2-x Al2SiO7: x Pr 3+ phosphor (100) in the polyvinyl fluoride host substrate material (101). The Ca 2-x Al2SiO7: x Pr 3+ doped polyvinyl fluoride substrate material is exposed to an ultraviolet light source (104), such as an ultraviolet lamp, for approximately 2 to 10 minutes to charge the Ca 2-x Al2SiO7: x Pr 3+ phosphor (100). Then the ultraviolet lamp is turned off. Then the Ca 2-x Al2SiO7: x Pr 3+The phosphor (100) emits light in the range of 200 nm to 280 nm for about 2 to 10 minutes. This emission range corresponds to UV-C light, which is known to have germicidal effects. 2-x Al2SiO7: x Pr 3+ The germicidal light emitted by the phosphor is 2-x Al2SiO7: x Pr 3+ The surface (101a) of the doped polyvinyl fluoride substrate material is irradiated, thereby sterilizing the surface (101a).A spectrofluorometer is used to measure the afterglow intensity of the phosphor-doped substrate material.

[0098] In another embodiment, the ultraviolet light source (104) can be a pulsed xenon-ultraviolet device having a wavelength of about 222 nm, 254 nm, or 275 nm, and can be used to irradiate the Ca prepared in step 2. 2-x Al2SiO7: x Pr 3+ In one embodiment, the substrate is exposed to Ca doped polyvinyl fluoride. 2-x Al2SiO7: x Pr 3+ The surface (101a) of the doped polyvinyl fluoride substrate material is exposed to a pulsed xenon-ultraviolet light source having a wavelength of 254 nm for approximately 2 minutes. When the excitation light is removed, a UV-C continuous emission at 268 nm is obtained. Ca 2-x Al2SiO7: x Pr 3+ Doped polyvinyl fluoride material 3+ The observation of UV-C afterglow of Ca 2-x Al2SiO7: x Pr 3+ It was found that the energy traps in the phosphor (100) can be effectively filled by 254 nm light excitation, and that the energy traps were converted to Pr 3+ 4f 1 5d 1 The electrons are efficiently captured from the 4f state and released by the surrounding thermal stimulation after the excitation is stopped. 1 5d 1Suggests that it is located at an appropriate energy position so that it can be returned to the state. Isotropic emission is Ca 2-x Al2SiO7: x Pr 3+ Effectively disinfects the surface (101a) of the phosphor-doped polyvinyl fluoride substrate material. A spectrofluorometer is used to measure the afterglow intensity of the phosphor-doped substrate material.

[0099] Example 3: Preparation of a photon-emitting inorganic phosphor-doped substrate material (NaY( 1-x )F6: x Pr 3+ Doped tetrafluoroethylene) Step 1. Preparation of NaY( 1-x )F 6 : x Pr 3+ (100) Cs2NaY( 1-x )F6: x Pr 3+ (x = 0.01 - 0.10) having a nominal composition of Pr-doped polycrystalline fluoride elpasolite phosphor is prepared by solid-state synthesis. Powders of Cs2CO3 (1.6290 g, 99.99%, Aladdin, Shanghai, China), NaHCO3 (0.4200 g, 99.99%, Aladdin, Shanghai, China), Y2O3 (0.5588 g, 99.99%, Aladdin, Shanghai, China), NH4F (2.2222 g, 99.99%, Aladdin, Shanghai, China), and Pr6O 11 (0.0085 g, 99.996%, Alfa, USA) are mixed together with 3 mL of acetone and then ground thoroughly for about 5 minutes. The resulting powder is heat-treated in air at 150 °C for 7 hours, followed by grinding again to obtain a fine powder. This mixture is then sintered in air at 450 °C for 30 minutes. The resulting powder is then ground again and subsequently sintered in a nitrogen atmosphere at 700 °C for 10 hours. For the above synthesis, a corundum boat and a platinum crucible with a purity of 99% are used as containers.

[0100] The prepared Cs2NaY( 1-x )F6: x Pr3+ The inorganic phosphor dopant (100) is analyzed by powder X-ray diffraction. The crystal structure is analyzed using FullProf, and Cs2NaY( 1-x )F6: x Pr 3+ Verify the Y / Pr site mixing in the crystal structure. The structure crystallizes in the Fm-3m space group corresponding to cubic elpasolite. In this double perovskite structure, both Y and Na are coordinated with six fluorine atoms, and the doped Pr 3+ ions replace the Y 3+ ions.

[0101] Step 2. Preparation of Cs 2 NaY( 1-x )F 6 : x Pr 3+ Doped tetrafluoroethylene The substrate (host) material (101), tetrafluoroethylene (Dupont), is heated to about 327 °C in an argon atmosphere to melt the material. The Cs2NaY( 1-x )F6: x Pr 3+ (100) powder is thoroughly mixed with the molten tetrafluoroethylene and a phosphor / volume polymer in an amount of about 10 volume % so that Cs2NaY( 1-x )F6: x Pr 3+ is uniformly incorporated into the tetrafluoroethylene substrate (host) material (101). The doped tetrafluoroethylene is then cured to form a solidified Cs2NaY( 1-x )F6: x Pr 3+ doped tetrafluoroethylene substrate material. In some embodiments, the Cs2NaY( 1-x )F6: x Pr 3+ doped tetrafluoroethylene substrate material can be molded, for example, using a mold, during curing. The mold is Cs2NaY( 1-x )F6: x Pr 3+It can aid in the construction of doped tetrafluoroethylene substrate materials into usable products, such as cabinets, counters, wallpaper, or covers for a variety of household, medical, automotive, or aeronautical products. In addition, the solidified Cs2NaY( 1-x )F6: x Pr 3+ After the doped tetrafluoroethylene substrate material is prepared, the material can be easily shaped and modified, for example, using a saw, sandpaper, or a suitable mold.

[0102] Example 4: Inorganic phosphor-doped substrate material (Cs2NaY( 1-x )F6: x Pr 3+ Disinfection using doped tetrafluoroethylene Cs2NaY( 1-x )F6: x Pr 3+ The doped tetrafluoroethylene substrate material is exposed to a pulsed xenon lamp having a wavelength between 100 nm and 225 nm for approximately 30 seconds. The pulsed light dissolves Cs2NaY( 1-x )F6: x Pr 3+ This is sufficient to charge the phosphor (100). Then, Cs2NaY( 1-x )F6: x Pr 3+ The phosphor (100) emits light in the range of 200 nm to 280 nm (germicidal light) for about 10 to 20 minutes. 1-x )F6: x Pr 3+ The germicidal light emitted by the phosphor is Cs2NaY( 1-x )F6: x Pr 3+ The surface (101a) of the doped tetrafluoroethylene substrate material (101) is isotropically irradiated, thereby disinfecting the surface (101a). A spectrofluorometer is used to measure the afterglow intensity of the phosphor-doped substrate material.

[0103] Efforts have been made to ensure accuracy with respect to the numerical values (amounts, temperatures, etc.) used, but some experimental errors and deviations should be taken into account.

[0104] Those skilled in the art will recognize many methods and materials similar or equivalent to those described herein that can be used when practicing the subject matter described herein. This disclosure is not limited in any sense to only the methods and materials described.

[0105] Where a range of values is specified, unless the context clearly indicates otherwise, each intervening value between the upper and lower limits of that range to one-tenth of the unit of the lower limit, and other stated values or intervening values within the stated range are to be understood as being included. Upper and lower limits of these smaller ranges that may be independently included within a smaller range are also included, subject to the upper and lower limits specifically excluded in the stated range. Where one or both of the upper and lower limits of the stated range are included, ranges excluding one or both of them are also included.

[0106] Those skilled in the art related to the subject matter, benefiting from the teachings presented in the foregoing description and the accompanying drawings, will envision numerous modifications and other embodiments of the subject matter shown herein. Accordingly, it is to be understood that the subject matter is not limited to the specific embodiments disclosed, and that modifications and other embodiments are intended to be included within the scope of the claims. Specific terms are used herein, but they are used only in a general and illustrative sense and not for purposes of limitation.

Claims

1. A method for disinfecting a surface, This includes exposing the surface of a substrate material containing an inorganic phosphor dopant to an ultraviolet light source. The aforementioned exposure causes the inorganic phosphor dopant in the substrate material to emit photons, The photons irradiate the surface, thereby disinfecting the surface. method.

2. The method according to claim 1, wherein the inorganic phosphor dopant in the substrate material emits photons having wavelengths of light between approximately 200 nm and approximately 280 nm, and / or the inorganic phosphor dopant in the substrate material emits photons having wavelengths of light between approximately 225 nm and approximately 250 nm.

3. The method according to claim 1 or 2, wherein the ultraviolet light source has wavelengths between approximately 160 nm and approximately 320 nm.

4. The inorganic phosphor dopant is Pr ３＋ Ce ３＋ , Eu ３＋ , Eu ２＋ , Gd ３＋ , Tb ３＋ , and Dy ３＋ The method according to claim 1, wherein the metal oxide or metal fluoride is a rare earth ion selected from the group consisting of, or a mixture thereof.

5. The method according to claim 4, wherein the metal oxide is selected from the group consisting of silicates, phosphates, borates, oxides, oxynitrides, oxysulfides, and aluminates, or combinations thereof.

6. The method according to claim 1, wherein the substrate material comprises one or more types of synthetic polymers.

7. The method according to claim 6, wherein the substrate material includes a material selected from the group consisting of a thermoplastic resin which may be fluorinated, a thermosetting resin, and an electronegative resin.

8. The method according to claim 1, wherein the substrate material containing the inorganic phosphor dopant is exposed to an ultraviolet light source for a sufficient amount of time to charge the inorganic phosphor dopant in the substrate material.

9. A photon-emitting inorganic phosphor-doped substrate material, The substrate material comprises an inorganic phosphor dopant, wherein the inorganic phosphor dopant in the substrate material is capable of emitting photons upon exposure of the surface of the photon-emitting inorganic phosphor doped substrate material to an ultraviolet light source. Photon-emitting inorganic phosphor-doped substrate material.

10. The photon-emitting inorganic phosphor-doped substrate material according to claim 9, wherein the substrate material comprises one or more types of synthetic polymers.

11. wherein the inorganic phosphor dopant is Pr ３＋ , Ce ３＋ , Eu ３＋ , Eu ２＋ , Gd ３＋ , Tb ３＋ , and Dy ３＋ , or a metal oxide or metal fluoride containing rare earth ions selected from the group consisting of mixtures thereof, the photon-emitting inorganic phosphor-doped substrate material according to claim 9 or 10.

12. The photon-emitting inorganic phosphor-doped substrate material according to claim 11, wherein the metal oxide is selected from the group consisting of silicates, phosphates, borates, oxides, oxynitrides, oxysulfides, and aluminates, or combinations thereof.

13. The photon-emitting inorganic phosphor-doped substrate material according to claim 11, wherein the inorganic phosphor dopant in the substrate material can emit photons having wavelengths of light between approximately 200 nm and approximately 280 nm when the surface of the photon-emitting inorganic phosphor-doped substrate material is exposed to an ultraviolet light source.

14. A method for preparing a photon-emitting material for surface disinfection, A method comprising preparing a photon-emitting inorganic phosphor-doped substrate material by contacting a substrate material with an inorganic phosphor dopant, wherein the inorganic phosphor dopant in the photon-emitting inorganic phosphor-doped substrate material is capable of emitting photons upon exposure of the surface of the photon-emitting inorganic phosphor-doped substrate material to an ultraviolet light source.

15. The method according to claim 14, wherein the inorganic phosphor dopant in the photon-emitting inorganic phosphor doped substrate material is capable of emitting photons having wavelengths of light between approximately 200 nm and approximately 280 nm.

16. The inorganic phosphor dopant is Pr ３＋ Ce ３＋ , Eu ３＋ , Eu ２＋ , Gd ３＋ , Tb ３＋ , and Dy ３＋ The method according to claim 14 or 15, wherein the metal oxide or metal fluoride is a rare earth ion selected from the group consisting of, or mixtures thereof.

17. The method according to claim 16, wherein the metal oxide is selected from the group consisting of silicates, phosphates, borates, oxides, oxynitrides, oxysulfides, and aluminates, or combinations thereof.

18. The method according to claim 14, wherein the substrate material comprises one or more types of synthetic polymers.

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