Surface disinfection with Pr3 + doped inorganic phosphors

Abstract

Described herein are methods of disinfecting a surface using a photon-emitting inorganic phosphor doped substrate. Further described is a method for preparing a photon-emitting inorganic phosphor doped substrate.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to U.S. Provisional Patent Application No. 63 / 366,576, filed on June 17, 2022, the contents of which are incorporated herein by reference in their entirety. Technical Field

[0003] The presently disclosed subject matter generally relates to methods of disinfecting surfaces by utilizing the luminescent properties of rare earth phosphors. Background Art

[0004] Phosphor materials have the property of emitting ultraviolet, visible and infrared light by the action of external excitation means such as irradiation of electromagnetic waves (e.g., electron beams, X-rays, ultraviolet rays, visible light, etc.) or application of electric fields, and are therefore used in a large number of photoelectric transducers 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 electroluminescent displays and scintillators. In particular, inorganic phosphors are widely studied to meet the demand for low-voltage stimulated lighting sources due to the increased global energy consumption. Modern white light-emitting diodes (WLEDs) have replaced less efficient incandescent lamps and conventional fluorescent lighting sources containing mercury due to their environmental protection, long life, low energy consumption, reliability, and high luminous efficiency.

[0005] Lanthanides are often used as phosphors for luminescence applications. For example, the shielded f orbitals of praseodymium allow for long excited state lifetimes and high luminescence yields. In fact, Pr 3+ Typically a dopant ion for red, blue, green and ultraviolet phosphors. Summary of the invention

[0006] In one aspect, the presently disclosed subject matter is directed to a method for disinfecting a surface, comprising: exposing a surface of a substrate comprising an inorganic phosphor dopant to a UV light source; wherein the exposure causes the inorganic phosphor dopant in the substrate to emit photons; and wherein the photons irradiate the surface, thereby disinfecting the surface.

[0007] In another aspect, the subject matter of the present disclosure relates to a photon-emitting inorganic phosphor doped substrate, comprising: a substrate containing an inorganic phosphor dopant, wherein the inorganic phosphor dopant in the substrate is capable of emitting photons when a surface of the photon-emitting inorganic phosphor doped substrate is exposed to a UV light source.

[0008] In another aspect, the subject matter of the present disclosure relates to a method for preparing a photon emitting material for surface disinfection, comprising: contacting a substrate with an inorganic phosphor dopant to prepare an inorganic phosphor-doped substrate, wherein the inorganic phosphor dopant in the inorganic phosphor-doped substrate is capable of emitting photons when a surface of the inorganic phosphor-doped substrate is exposed to a UV light source.

[0009] These and other aspects are fully described in this article. BRIEF DESCRIPTION OF THE DRAWINGS

[0010] Figure 1 A process for preparing the photon-emitting inorganic phosphor-doped substrates described herein is shown.

[0011] Figure 2 A process for disinfecting a surface according to the methods described herein is shown.

[0012] Figure 3A A schematic diagram showing the process of charging an inorganic phosphor dopant in a substrate according to the sterilization method described herein.

[0013] Figure 3B A schematic diagram is shown of a process for disinfecting the surface of a substrate according to the methods described herein. DETAILED DESCRIPTION

[0014] The subject matter described herein relates to methods for disinfecting surfaces by utilizing the luminescent properties of inorganic phosphor dopant materials. The methods described herein provide multiple advantages over those methods of the prior art. In fact, prior art methods for disinfecting surfaces include the application of expensive and heavy ultraviolet light sources. Extended exposure to these light sources can affect the substrate surface. High touch areas typically require prolonged exposure to pulsed UV light. Other prior art disinfection methods include wiping the surface with a disinfectant solution that typically loses effectiveness in a short period of time. In addition, exposure to such chemicals may have unintended effects on the substrate surface.

[0015] As described herein, incorporating an inorganic phosphor into a substrate provides an emitting surface of UV-C light (200nm to 280nm) that can be used to disinfect the substrate surface over an extended period of time. After the phosphor-doped substrate surface is exposed to a UV excitation source, the surface emits photons within an adjustable time after the excitation light has been removed. The phosphor in the substrate directly absorbs the UV light. The phosphor then emits radiant energy, which disinfects the substrate surface. In this regard, the disinfection comes from the substrate surface itself. In addition, the disinfection method described herein is durable in operation because the inorganic phosphor is uniformly incorporated into the surface material, which minimizes degradation due to wear or exposure to surface chemicals. The disinfection method described herein can significantly reduce the time required to disinfect a surface using conventional methods.

[0016] UV-C light is weak at the Earth's surface because the atmosphere's ozone layer blocks it. Many disinfection methods use short-wavelength ultraviolet (ultraviolet C or UV-C) light to kill or inactivate microorganisms by damaging nucleic acids and interfering with their DNA, rendering them unable to perform important cellular functions. The inorganic phosphors in the phosphor-doped substrates described herein emit this germicidal UV-C light, which serves to disinfect the surface of the substrate.

[0017] Figure 3A and 3B Schematic diagrams of charging the inorganic phosphor dopant in the substrate and sterilizing the surface of the substrate according to the method described herein are shown respectively. Figure 3A In the method, a surface (101a) of a substrate (101) containing an inorganic phosphor dopant (100) is exposed to a UV light source to charge the inorganic phosphor dopant (100). Figure 3B As shown, after charging the inorganic phosphor dopant (100) in the substrate (101), removing Figure 3A The inorganic phosphor dopant (100) emits photons (105) having a light wavelength in the UV-C range under the UV light, wherein the photons (105) irradiate the surface (101a) of the substrate (101), thereby sterilizing the surface (101a).

[0018] The subject matter of the present disclosure will now be described more fully below. However, the technical personnel of the field of the subject matter of the present disclosure that benefits from the teaching presented in the foregoing description will think of many modifications and other examples of the subject matter of the present disclosure set forth herein. Therefore, it should be understood that the subject matter of the present disclosure is not limited to the disclosed specific examples, and modifications and other examples should be included in the scope of the appended claims. In other words, the subject matter described herein covers all substitutions, modifications and equivalents. Unless otherwise defined, all technical and scientific terms used herein have the same meanings as those of ordinary skill in the art are generally understood. All publications, patent applications, patents and other references mentioned herein are incorporated herein by reference as a whole. In the case where one or more of the documents, patents and similar materials incorporated are different or contradictory from the present application (including but not limited to the terms, term usage, described technology, etc. defined), the present application shall prevail.

[0019] I. Definitions

[0020] As used herein, "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 when interpreted in the alternative ("or").

[0021] As used herein, the terms "approximately," "about," "substantially," and "substantially" refer to an amount that is close to a stated amount and still performs a desired function or achieves a desired result. For example, in some instances, as the context may dictate, the terms "approximately," "about," and "substantially" may refer to an amount that is within less than or equal to 10% of a stated amount. As used herein, the term "generally" refers to a value, amount, or characteristic that primarily includes or tends toward a particular value, amount, or characteristic.

[0022] As used herein, conditional language, such as "can", "may", "possibly", "could", "for example", etc., unless otherwise specifically stated or otherwise understood in the context of use, is generally intended to convey that certain instances include (while other instances do not include) certain features, elements, and / or steps. Therefore, such conditional language is generally not intended to imply that one or more instances require features, elements, and / or steps in any way, or that one or more instances must include logic for determining whether these features, elements, and / or steps are included or will be performed in any particular instance with or without author input or prompting. The terms "comprising", "including", "having", etc. are synonymous and are used inclusively in an open-ended manner and do not exclude additional elements, features, actions, operations, etc. The terms "consisting of" and "composed of", etc. are synonymous and used in a closed manner and do not exclude additional elements, features, actions, operations, etc. The terms "consisting essentially of" and "consisting essentially of", etc. are synonymous semi-closed terms that indicate that the items in the claim are limited to the components specified in the claim and those components that do not materially affect the basic and novel characteristics of the claim. Additionally, the term "or" is used in its inclusive sense (rather than in its exclusive sense) such that when used, for example, to connect a list of elements, the term "or" means one, some, or all of the elements in the list.

[0023] As used herein, "contacting" refers to contacting a substrate (101) with an inorganic phosphor dopant (100) to prepare an inorganic phosphor-doped substrate that emits photons. As used herein, an inorganic phosphor dopant (100) refers to a metal oxide (106) or a metal fluoride (108) containing a rare earth ion (107) or a transition metal. The substrate (101) serves as a host material, wherein the inorganic phosphor dopant (100) is incorporated into the host material by, for example, applying heat and / or pressure. In some instances, the inorganic phosphor-doped substrate that emits photons contains about 0.05 wt % to about 10 wt % or about 0.01 wt % to about 5 wt % of the inorganic phosphor dopant. In certain other instances, the photon-emitting inorganic phosphor-doped substrate comprises about 0.05 wt % to about 0.15 wt %, about 0.10 wt % to about 0.25 wt %, about 0.15 wt % to about 3 wt %, about 0.25 wt % to about 4 wt %, about 1 wt % to about 5 wt %, about 1.5 wt % to about 3.5 wt %, about 2.5 wt % to about 4 wt %, about 0.50 wt % to about 4.5 wt %, about 4 wt % to about 5 wt %, about 5 wt % to about 10 wt %, about 3 wt % to about 7 wt %, about 4 wt % to about 8 wt %, about 6 wt % to about 9 wt %, or about 7 wt % to about 10 wt % of the inorganic phosphor dopant.

[0024] As used herein, "photooxidation" refers to the degradation of polymer surfaces due to the combined action of light and oxygen. Photooxidation breaks polymer chains, causing the material to become increasingly brittle.

[0025] II. Methods for Disinfecting Surfaces

[0026] In some instances, such as Figure 2 As shown, the subject matter described herein relates to a method for disinfecting a surface (101a), the method comprising:

[0027] exist Figure 2 In step 250, a surface (101a) of a substrate (101) containing an inorganic phosphor dopant (100) is exposed to a UV light source (104) to charge the inorganic phosphor dopant in the substrate (101);

[0028] Among them, Figure 2 In step 255, the exposure causes the inorganic phosphor dopant (100) in the substrate (101) to emit photons (105) having a light wavelength in the UV-C range, wherein the photons (105) irradiate the surface (101a) of the substrate doped with the inorganic phosphor that emits the photons, thereby disinfecting the surface (101a).

[0029] When a phosphor is exposed to radiation, orbital electrons in its molecules are excited to a higher energy level; when they return to their previous energy level, they emit energy as light of a specific color. In fact, the scintillation process in inorganic materials is due to the electronic band structure present in the crystal. Incoming particles can excite electrons from the valence band to the conduction band or exciton band (located just below the conduction band and separated from the valence band by an energy gap). This leaves associated holes in the valence band. Impurities create electronic energy levels in the forbidden band. Excitons are loosely bound electron-hole pairs that diffuse through the crystal lattice until they are captured as a whole by an impurity center. The latter then quickly de-excite by emitting scintillation light (i.e., photons). The wavelength of the emission depends on the atoms themselves and the surrounding crystal structure.

[0030] In some examples, the UV light source (104) used to excite (charge) the orbital electrons of the inorganic phosphor dopant has a wavelength of about 160nm to 320nm. In other examples, the UV light source (104) has a wavelength of about 160nm to 260nm, about 160nm to 200nm, about 180nm to 240nm, about 200nm to 250nm, about 210nm to 250nm, about 225nm to 260nm, about 230nm to 250nm, or about 190nm to 260nm. In some other examples, the UV light source has a wavelength of about 222nm, 254nm, or 275nm.

[0031] Non-limiting examples of UV light sources (104) include, for example, black lights, short-wave UV lamps, incandescent lamps, gas discharge lamps, UV LEDs, deuterium lamps, pulsed xenon lamps, and UV lasers. In an example, the UV light source (104) is a pulsed xenon UV device, which can be in the form of a handheld wand. The UV light emitted from the pulsed xenon device enables effective charging of the inorganic phosphor dopant (100) in the substrate (101), and can sterilize the surface (101a) by suspending the xenon UV wand about 1 to 5 inches above the surface (101a). In another example, the UV light source (104) is a deuterium lamp, which has a light range of about 185nm to about 400nm.

[0032] In addition to UV light, other excitation energy sources can also be used in the methods described herein. Personal protective equipment (PPE) may be required to operate such energy sources.

[0033] In certain examples of the above method, the inorganic phosphor dopant (100) in the substrate (101) emits photons (105) having a wavelength of light of about 200 nm to 280 nm. In other examples, the inorganic phosphor dopant (100) in the substrate (101) emits photons (105) having a wavelength of light of about 200 nm to 270 nm, about 200 nm to 250 nm, about 225 nm to 250 nm, about 200 nm to 225 nm, about 200 nm to 275 nm, or about 225 nm to 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 example, the inorganic phosphor dopant emits UV-C light having a wavelength of about 200 to 280 nm.

[0034] In some instances, the inorganic phosphor dopant (100) is a metal oxide (106) or metal fluoride (108) containing a rare earth ion (107) or a transition metal ion. In some instances, the rare earth ion (107) or the transition metal ion is referred to as an "activator ion". As used herein, an "activator ion" is an ion added to a crystal structure as a dopant. The activator ion is surrounded by the host crystal ion and forms a luminescent center where the excitation-emission process of the phosphor occurs. The wavelength emitted by the activator ion is affected by the ion itself, its electronic configuration, and its surrounding crystal structure.

[0035] Although the activator ions have intrinsic properties that contribute to the optical properties of the phosphor, the electronic energy levels of the activator ions in the crystal are different from those of the free ions. Depending on the properties of the host crystal, the separation of the energy levels can cause light emission from UV across visible wavelengths. The local geometric structure around the activator ions affects the spectral behavior of the activator ions, especially lanthanide ions, incorporated into the host matrix. Certain effects in the lattice, such as ligand field splitting and mass center shift, may affect the energy gap between the f and d orbitals of the activator ions, thereby affecting the luminescent properties of this material (Lin, YC et al., Top Curr Chem (Z) 374, 21 (2016)).

[0036] In some examples, the inorganic phosphor dopant (100) is a metal oxide (106) containing a rare earth ion (107). In some examples, the rare earth ion (107) is a lanthanide ion. In some examples, the rare earth ion (107) is selected from Tm 3+ , Pr 3+ 、Ho 3+ , Er 3+ 、Sm 3+ 、Nd 3+ , Yb 3+ 、Eu 3+ 、Eu 2+ , Gd3+ 、Ce 3+ 、Ce 2+ , Tb 3+ , Tb 4+ 、Dy 3+ , Yb 3+ He Lu 3+ In some examples, the inorganic phosphor dopant (100) is a metal oxide (106) containing a rare earth ion (107), wherein the rare earth ion is 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. In certain embodiments, the rare earth ion (107) is Pr 3+ .

[0037] Pr 3+ The UV-C emission of the activated UV-C phosphor consists of a broad, parity-allowed Pr 3+ 4f 1 5d 1 →4f 2 In order to ensure that Pr 3+ 4f 1 5d 1 →4f 2 Transition requires two general conditions: less than about 3000cm -1 The small Stokes shift of (0.37 eV) and the first (lowest energy) Pr 3+ 4f 2 →4f 1 5d 1 The appropriate energy position for the excitation transition is related to the composition and crystal structure of the host lattice. Under these conditions, Pr 3+ 4f 1 5d 1 Energy level to lower 4f 2 ( 3 P J , 1 I 6 , 1 D 2 ) levels is minimized; otherwise, 4f 1 5d 1 Energy levels and lower 4f 2 Energy level jumps, resulting in sharp lines of visible and infrared emission 4f 2 →4f 2Inter-configuration emission transmission will dominate (Wang, X. et al., Nat Commun 11, 2040 (2020)).

[0038] In certain examples 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. Such metal oxides (106) are ceramic materials and therefore exhibit several advantages, including chemical, thermal and photochemical stability. In certain examples, the silicate is selected from the group consisting of pyroxene, cyclosilicates, silicate garnets, oxyorthosilicates and orthosilicates. Non-limiting examples of silicates include Sr. 2 MgSi 2 O 7 , Ca 2 Al 2 SiO 7 、SrAl 2 O 4 MgSiO 3 、SrSiO 3 、CdSiO 3 , Ba 2 SiO 4 、BaMg 2 Si 2 O 7 , Ca 2 MgSi 2 O 7 , Sr 0.5 Ca 1.5 MgSi 2 O 7 、(Ca,Sr) 2 MgSi 2 O 7 , Sr 3 MgSi 2 O 8 , Sr 2 MgSi 2 O 7 , Ca 0.5 Sr 1.5 Al 2 SiO 7 , Sr 3 Al 10 SiO 20 and Y 2 SiO 5 Non-limiting examples of borates include YBO 3 and CaAl 2 B 2 O 7 Non-limiting examples of oxynitrides include MSi2 O 2 N 2 , where M = Ba, Sr or Ca. Non-limiting examples of phosphates include YPO 4 and Zn 3 (PO 4 ) 2 Non-limiting examples of oxides include CaO, SrO, BaO, Y 3 Ga 5 O 12 、NaGdGeO 4 、Cd 3 Al 2 Ge 3 O 12 、CaTiO 3 , Ca 0.8 Zn 0.2 TiO 3 and Ca 2 Zn 4 Ti 15 O 36 Non-limiting examples of oxysulfides include Y 2 O 2 S, Gd 2 O 2 S and Sr 5 Al 2 O 7 S. Non-limiting examples of aluminates include MgAl 2 O 4 , CaAl 2 O 4 、SrAl 2 O 4 and Sr 4 Al 14 O 25 .

[0039] In some examples of the inorganic phosphor dopant (100), the metal oxide (106) is doped with Pr 3+ Ca 2 Al 2 SiO 7 (Ca 2 Al 2 SiO 7 :Pr 3+ ). Ca 2 Al 2 SiO 7 is characterized by a pyroxene structure in which Ca 2+ The ions are sandwiched between the AlO 4 and SiO 4between tetrahedral layers and are eight-coordinated. Each Ca 2+ Ions and AlO 4 Layer and SiO 4 The four nearest neighbors of the two layers O 2- The ligands are ionically bonded, so the four Ca 2+ The complexes are structurally identical. 2 Al 2 SiO 7 :Pr 3+ In the trivalent Pr 3+ ion Replace smaller divalent Ca 2+ ion Therefore, the doped Pr 3+ The ion is eight-coordinated. This highly coordinated, small, and charge-unbalanced cationic site can be used for Pr 3+ The ions generate a suitably strong crystal field through which a small Stokes shift and thus efficient Pr for UV-C emission can occur. 3+ 4f 1 5d 1 →4f 2 Again, without wishing to be bound by theory, it is expected that cation size mismatch and charge imbalance will occur in the Pr 3+ More efficient energy traps (such as oxygen vacancies) are created around the ions, which helps to produce efficient persistent phosphors (Wang, X et al., Nat Commun 11, 2040 (2020)).

[0040] In some examples of the inorganic phosphor dopant (100), the metal fluoride (108) (host lattice) is selected from Cs 2 NeA 6 、NaCeF 4 ,NaYF 4 and NaGd 4 Such metal fluoride hosts are generally characterized by having large band gaps, structural defects that may act as electron traps, and anion defects, which make them useful in inorganic phosphors. In some examples, the inorganic phosphor dopant (100) is doped with Pr 3+ Cs 2 Yf 6 (Cs 2 Yf 6 :Pr 3+ ). In one example, Pr 3+ Substitute Cs in an amount of about 0.3% to about 10% 2 NeA 6In other examples, Pr 3+ Substituting Cs in an amount of about 1% to 5%, 1.5% to 4.5%, 2.5% to 5%, 2% to 7%, 3% to 8%, or 4% to 9%. 2 NeA 6 Yttrium ion sites in.

[0041] In some instances, the substrate (101) comprises one or more synthetic polymers. Synthetic polymers are effective, durable and inexpensive materials and can be easily modified by heating and / or pressure techniques to incorporate the inorganic phosphors described herein. In some instances, the substrate (101) comprises a material selected from the group consisting of optionally fluorinated thermoplastics, thermosetting resins and electronegative resins. In some other instances, the substrate (101) comprises a material selected from the group consisting of tetrafluoroethylene, polyvinyl fluoride, polyurethane, polyester, epoxy resin, phenolic resin, vinyl ester, polyamide, polyamide-imide, polyetherimide, polyvinyl chloride, polyether ketone, polycarbonate, polyphenyl sulfone, polymethyl methacrylate, polyacrylate and benzoxazine or a combination thereof. In particular, fluorine is known to strongly resist photooxidation due to its high electronegativity and the need to accept electrons. Therefore, in some instances, fluorinated synthetic polymers such as tetrafluoroethylene or polyvinyl fluoride can be used for the synthetic polymer in the methods described herein. Additionally, thermosetting polymers are generally known to have a higher degree of crosslinking than other types of polymers, which makes them further resistant to photo-oxidation.

[0042] The substrate (101) comprising one or more synthetic polymers can be used in almost any environment where surface disinfection is performed. In some examples, the substrate (101) comprising one or more synthetic polymers is located in an airplane, hospital, gym, school, or other area where there is a significant risk of contaminant transfer.

[0043] In some instances of the above method, the surface (101a) is the interior of an aircraft. In some other instances of the above method, the surface (101a) is located in a hospital, a gymnasium, or a school. In another instance of the above method, the surface is located where there is a significant risk of contaminant transfer.

[0044] In some examples, the material can be used to reduce the shadowing effect of surface areas, thereby facilitating disinfection of surfaces not exposed to incident UV light. For example, an inorganic phosphor dopant (100) can be incorporated into polyvinyl fluoride (PVF) used in decorative laminates to increase the surface area of ​​the substrate (101) that is capable of emitting photons.

[0045] In an example of the above method for disinfecting a surface, a substrate (101) containing an inorganic phosphor dopant (100) is exposed to a UV light source (104) for a time sufficient to charge the inorganic phosphor dopant (100) in the substrate (101). In certain examples, the time sufficient to charge the inorganic phosphor dopant (100) in the substrate (101) is 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 will vary depending on the wavelength of the UV light from the UV light source (104) and the inorganic phosphor dopant (100) itself.

[0046] In an example of the above method for disinfecting a surface, the inorganic phosphor dopant (100) in the substrate (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 modifying the length of time used to charge the inorganic phosphor dopant (100). The duration of emission can also be adjusted depending on the desired application. For example, if the surface being disinfected is located in an airplane, a suitable maximum emission time is about 10 minutes, 15 minutes, 20 minutes, 25 minutes, or 30 minutes, so that the disinfection process can be performed between flights. In certain other examples, longer emission times can be associated with higher levels of disinfection. For example, if the surface being disinfected is located in a hospital or healthcare facility, the emission time may be approximately 30 minutes to 60 minutes, as higher levels of disinfection may be required in this type of facility.

[0047] One or more dopant ions can be used to tune the emission to longer or shorter wavelengths, as well as to vary the emission intensity. For example, SrAl 2 O 4 Can be doped with Eu 2+ , a phosphor emitting at 520 nm is obtained. However, SrAl 2 O 4 You can also use Eu 2+ and Dy 3+Co-doping can significantly enhance the sustained luminescence intensity. 2 O 4 :Eu 2+ ,Dy 3+ The afterglow lasts for hours, which is the result of the gradual thermally assisted release of trapped charges in the phosphor. This long afterglow contrasts with the duration of only a few minutes of the variant without the co-dopant (Xingdong, L. et al., J. Wuhan Univ. Technol.-Mat. Sci. Edit. 23, 652–657 (2008)). In addition, the material can be stabilized with an inorganic phosphor dopant (100) having an energy well that can be filled during excitation. The energy well can be adjusted by adjusting the desired penetration depth of the UV energy to adjust the decay time required to clean the surface over time.

[0048] When light emitted by the inorganic phosphor dopant (100) in the photon-emitting inorganic phosphor-doped substrate leaves the surface (101a), it isotropically irradiates the substrate surface (101a), thereby sterilizing the surface (101a). Isotropic irradiation means that the radiation from a point source radiates uniformly in all directions with the same intensity regardless of the direction of measurement. The light emitted by the inorganic phosphor dopant (100) is short-wavelength ultraviolet (ultraviolet C or UV-C) light having a wavelength of 200nm to 280nm or 225nm to 250nm, which is known to be sterilizing.

[0049] In certain embodiments of the method for disinfecting a surface, the substrate (101) comprises tetrafluoroethylene or polyvinyl fluoride; the UV light source (104) has a wavelength of about 160 to 260 nm; the inorganic phosphor dopant (100) is a Pr 3+ silicate; and the inorganic phosphor dopant (100) emits photons (105) having a light wavelength of about 265 nm.

[0050] III. Photon-emitting inorganic phosphor doped substrates

[0051] In certain examples, the subject matter described herein relates to a photon-emitting inorganic phosphor-doped substrate comprising:

[0052] A substrate (101) comprising an inorganic phosphor dopant (100), wherein the inorganic phosphor dopant (100) in the substrate (101) is capable of emitting photons (105) when a surface of the inorganic phosphor-doped substrate emitting photons is exposed to a UV light source (104).

[0053] In some examples of inorganic phosphor doped substrates that emit photons, the substrate comprises one or more synthetic polymers. In some examples, the substrate comprises a material selected from the group consisting of optionally fluorinated thermoplastics, thermosetting resins, and electronegative resins. In some examples, the substrate comprises a material selected from the group consisting of tetrafluoroethylene, polyvinyl fluoride, polyurethane, polyester, epoxy resin, phenolic resin, vinyl ester, polyamide, polyamide-imide, polyetherimide, polyvinyl chloride, polyetherketoneketone, polycarbonate, polyphenylsulfone, polymethyl methacrylate, polyacrylate, and benzoxazine. In some examples of inorganic phosphor doped substrates that emit photons, the substrate is an aircraft interior.

[0054] In certain examples of inorganic phosphor doped substrates that emit photons, the inorganic phosphor dopant (100) is a metal oxide (106) or a metal fluoride (108) containing a rare earth ion (107) or a transition metal ion. In certain examples of inorganic phosphor doped substrates that emit photons, the inorganic phosphor dopant (100) is a metal oxide (106). In certain examples, the rare earth ion (107) is a lanthanide ion. In certain examples, the rare earth ion (107) is selected from Tm 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+ He Lu 3+ In some examples, the inorganic phosphor dopant (100) is a metal oxide (106) containing a rare earth ion (107), wherein the rare earth ion (107) is 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. In certain embodiments, the rare earth ion (107) is Pr 3+ .

[0055] In certain examples of inorganic phosphor dopants (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 certain examples, the silicate is selected from the group consisting of pyroxene, cyclosilicates, silicate garnets, oxyorthosilicates, and orthosilicates. Non-limiting examples of silicates include Sr, 2 MgSi 2 O 7 , Ca 2 Al 2 SiO 7 、SrAl 2 O 4 MgSiO 3 、SrSiO 3 、CdSiO 3 , Ba 2 SiO 4 、BaMg 2 Si 2 O 7 , Ca 2 MgSi 2 O 7 , Sr 0.5 Ca 1.5 MgSi 2 O 7 、(Ca,Sr) 2 MgSi 2 O 7 , Sr 3 MgSi 2 O 8 , Sr 2 MgSi 2 O 7 , Ca 0.5 Sr 1.5 Al 2 SiO 7 , Sr 3 Al 10 SiO 20 and Y 2 SiO 5 Non-limiting examples of borates include YBO 3 and CaAl 2 B 2 O 7 Non-limiting examples of oxynitrides include MSi 2 O 2 N 2 , where M = Ba, Sr or Ca. Non-limiting examples of phosphates include YPO 4 and Zn 3(PO 4 ) 2 Non-limiting examples of oxides include CaO, SrO, BaO, Y 3 Ga 5 O 12 、NaGdGeO 4 、Cd 3 Al 2 Ge 3 O 12 、CaTiO 3 , Ca 0.8 Zn 0.2 TiO 3 and Ca 2 Zn 4 Ti 15 O 36 Non-limiting examples of oxysulfides include Y 2 O 2 S, Gd 2 O 2 S and Sr 5 Al 2 O 7 S. Non-limiting examples of aluminates include MgAl 2 O 4 , CaAl 2 O 4 、SrAl 2 O 4 and Sr 4 Al 14 O 25 .

[0056] In some embodiments of the inorganic phosphor dopant (100), the metal oxide (106) is doped with Pr 3+ Ca 2 Al 2 SiO 7 .

[0057] In some examples of the inorganic phosphor dopant (100), the metal fluoride (108) (host lattice) is selected from Cs 2 NeA 6 、NaCeF 4 ,NaYF 4 and NaGd 4 Such metal fluoride hosts are generally characterized by having large band gaps, structural defects that may act as electron traps, and anion defects, which make them useful in inorganic phosphors. In some examples, the inorganic phosphor dopant (100) is doped with Pr 3+ Cs 2 Yf 6 (Cs2 Yf 6 :Pr 3+ ). In one example, Pr 3+ Substitute Cs in an amount of about 0.3% to about 10% 2 Yf 6 In other examples, Pr 3+ Substituting Cs in an amount of about 1% to 5%, 1.5% to 4.5%, 2.5% to 5%, 2% to 7%, 3% to 8%, or 4% to 9%. 2 Yf 6 Yttrium ion sites in.

[0058] In certain examples of the inorganic phosphor doped substrate emitting photons, the inorganic phosphor dopant (100) in the substrate (101) is capable of emitting photons (105) having a wavelength of light of about 200 nm to 280 nm when the surface (101a) of the inorganic phosphor doped substrate emitting photons is exposed to a UV light source (104). In certain examples of the inorganic phosphor doped substrate emitting photons, the inorganic phosphor dopant (100) in the substrate (101) is capable of emitting photons (105) having a wavelength of light of about 200 nm to 270 nm, about 200 nm to 250 nm, about 225 nm to 250 nm, about 200 nm to 225 nm, about 200 nm to 275 nm, or about 225 nm to 275 nm.

[0059] IV. Methods for Preparing Photon Emitting Materials

[0060] In some instances, such as Figure 1 As shown in , the subject matter described herein relates to a method for preparing a photon emitting material for surface disinfection, comprising:

[0061] exist Figure 1 In step 150, an inorganic phosphor dopant (100) is prepared; and

[0062] exist Figure 1 In step 155, the substrate (101) is contacted with an inorganic phosphor dopant (100) to prepare a photon-emitting inorganic phosphor-doped substrate, wherein the inorganic phosphor dopant (100) in the photon-emitting inorganic phosphor-doped substrate is capable of emitting photons (105) when a surface (101a) of the photon-emitting inorganic phosphor-doped substrate is exposed to a UV light source (104).

[0063] In some examples of the method for preparing a photon emitting material for surface disinfection, the inorganic phosphor dopant (100) in the inorganic phosphor doped substrate that emits photons can emit photons (105) having a light wavelength of about 200nm to 280nm. In some examples of the method for preparing a photon emitting material for surface disinfection, the inorganic phosphor dopant (100) in the inorganic phosphor doped substrate that emits photons can emit photons (105) having a light wavelength of about 200nm to 270nm, about 200nm to 250nm, about 225nm to 250nm, about 200nm to 225nm, about 200nm to 275nm, or about 225nm to 275nm.

[0064] In some examples of the 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 a rare earth ion (107) or a transition metal ion. In some examples of the method for preparing a photon emitting material for surface disinfection, the inorganic phosphor dopant (100) is a metal oxide (106). In some examples, the rare earth ion (107) is a lanthanide ion. In some examples, the rare earth ion (107) is selected from Tm 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+ He Lu 3+ or a combination thereof. In some embodiments, the inorganic phosphor dopant (100) is 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. In certain embodiments, the rare earth ion (107) is Pr 3+ .

[0065] In some examples of the 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 examples, the silicate is selected from the group consisting of pyroxene, cyclosilicates, silicate garnets, oxyorthosilicates and orthosilicates. Non-limiting examples of silicates include Sr 2 MgSi 2 O 7 , Ca 2 Al 2 SiO 7 、SrAl 2 O 4 MgSiO 3 、SrSiO 3 、CdSiO 3 , Ba 2 SiO 4 、BaMg 2 Si 2 O 7 , Ca 2 MgSi 2 O 7 , Sr 0.5 Ca 1.5 MgSi 2 O 7 、(Ca,Sr) 2 MgSi 2 O 7 , Sr 3 MgSi 2 O 8 , Sr 2 MgSi 2 O 7 , Ca 0.5 Sr 1.5 Al 2 SiO 7 , Sr 3 Al 10 SiO 20 and Y 2 SiO 5 Non-limiting examples of borates include YBO 3 and CaAl 2 B 2 O 7 Non-limiting examples of oxynitrides include MSi 2 O 2 N 2 , where M = Ba, Sr or Ca. Non-limiting examples of phosphates include YPO 4 and Zn 3 (PO 4 )2 Non-limiting examples of oxides include CaO, SrO, BaO, Y 3 Ga 5 O 12 、NaGdGeO 4 、Cd 3 Al 2 Ge 3 O 12 、CaTiO 3 , Ca 0.8 Zn 0.2 TiO 3 and Ca 2 Zn 4 Ti 15 O 36 Non-limiting examples of oxysulfides include Y 2 O 2 S, Gd 2 O 2 S and Sr 5 Al 2 O 7 S. Non-limiting examples of aluminates include MgAl 2 O 4 , CaAl 2 O 4 、SrAl 2 O 4 and Sr 4 Al 14 O 25 .

[0066] In some embodiments of the inorganic phosphor dopant (100), the metal oxide (106) is doped with Pr 3+ Ca 2 Al 2 SiO 7 .

[0067] In some examples of the inorganic phosphor dopant (100), the metal fluoride (108) (host lattice) is selected from Cs 2 Yf 6 、NaCeF 4 ,NaYF 4 and NaGd 4 Such metal fluoride hosts are generally characterized by having large band gaps, structural defects that may act as electron traps, and anion defects, which make them useful in inorganic phosphors. In some examples, the inorganic phosphor dopant (100) is doped with Pr 3+ Cs 2 Yf 6 (Cs 2 Yf 6:Pr 3+ ). In one example, Pr 3+ Substitute Cs in an amount of about 0.3% to about 10% 2 Yf 6 In other examples, Pr 3+ Substituting Cs in an amount of about 1% to 5%, 1.5% to 4.5%, 2.5% to 5%, 2% to 7%, 3% to 8%, or 4% to 9%. 2 Yf 6 Yttrium ion sites in.

[0068] In some examples of the method for preparing a photon emitting material for surface disinfection, the substrate (101) comprises one or more synthetic polymers. In some examples, the substrate (101) comprises a material selected from the group consisting of optionally fluorinated thermoplastics, thermosetting resins and electronegative resins. In some examples, the substrate (101) comprises a material selected from the group consisting of tetrafluoroethylene, polyvinyl fluoride, polyurethane, polyester, epoxy resin, phenolic resin, vinyl ester, polyamide, polyamide-imide, polyetherimide, polyvinyl chloride, polyetherketoneketone, polycarbonate, polyphenylsulfone, polymethyl methacrylate, polyacrylate and benzoxazine. As described in other examples herein, fluorinated polymers are particularly strongly resistant to photooxidation.

[0069] In certain embodiments of the method for preparing a photon emitting material for surface disinfection, the substrate (101) comprises tetrafluoroethylene or polyvinyl fluoride, and the inorganic phosphor dopant (100) comprises Pr 3+ In certain embodiments, the silicate is Ca 2 Al 2 SiO 7 .

[0070] Methods for preparing inorganic phosphor dopants (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 example, a metal oxide (106) host material and a rare earth oxide are weighed so that a certain amount of rare earth ions (107) are substituted or doped into the metal oxide (106) lattice. The amount of ion addition can be determined by calculating the suggested stoichiometry of the material and then weighing an appropriate amount of the raw material using dimensional analysis. The metal oxide (106) powder is thoroughly ground using a mortar and pestle to maximize contact between particles in the mixture. After being placed in a suitable crucible (usually alumina), the mixture is heated in a tubular or muffle furnace to a temperature sufficient to cause a solid-state reaction but below the melting temperature of the final compound. From a temperature of about 200°C below the melting temperature, the grain size of the final compound increases strongly. This heating process is called sintering, which usually results in a very dense and firmly agglomerated material. Such a material cannot be used directly as a phosphor. Therefore, post-synthesis grinding is usually required, either manually or using a ball mill.

[0071] Ball milling is a mechanical process that reduces particle size by mechanical impact and friction. Typically, a powder is milled against a number of hard grinding balls (usually Al 2 O 3 or ZrO 2 ) and a solvent are placed in a grinding jar to obtain a slurry. The grinding jar is then moved so as to achieve maximum friction. Similar to manual grinding using a mortar and pestle, the effectiveness of this process is highly dependent on the size and hardness of the raw materials.

[0072] For the above solid-state synthesis, the atmosphere used for heating may vary depending on the host material. In the case of oxides, air may generally be applied. However, some dopants, particularly europium, may oxidize in the oxygen lattice while being heated in oxygen, resulting in the formation of fully oxidized Eu 3+ Dopant. If Eu 2+ is the preferred valence state of the dopant, additional heat treatment in a reducing atmosphere such as helium or argon may be required.

[0073] Other methods for preparing the inorganic phosphor dopant (100) include sol-gel synthesis, colloidal synthesis, and coprecipitation. For example, in the sol-gel process, the powder is weighed and dissolved in a concentrated acid, such as HNO 3(e.g. 70 wt %), and then diluted with deionized water. The solution can then be cooled to room temperature and added dropwise to a cold saturated aqueous solution of another acid (e.g. oxalic acid). The solid material is then precipitated and then washed with deionized water and other polar solvents (e.g. acetone, acetonitrile, dimethylformamide (DMF), dimethyl sulfoxide (DMSO), isopropanol or methanol). The solid material will then undergo calcination at a temperature of about 1000° C. to 1200° C. for several hours, followed by intermittent grinding and sintering. In some instances, after weighing and mixing, the metal oxide (106) host powder and the rare earth oxide powder are directly placed in a furnace at 1000-1100° C. for 2-48 hours.

[0074] The prepared inorganic phosphor dopant (100) is then inserted into the substrate (host) material (101). The substrate (host) material (101) is a synthetic polymer substrate host material in some instances. The synthetic polymer substrate host material can be purchased from a commercial supplier, such as Dupont or Sigma. The inorganic phosphor dopant (100) is a powder and can be incorporated into the substrate (101) by melting the polymer substrate and then mixing in the inorganic phosphor dopant (100). Mixing can be promoted, for example, by further heating the material and / or using a mixing blade. The inorganic phosphor dopant (100) in an amount sufficient to disinfect the substrate surface (101a) can be incorporated into the synthetic polymer substrate (host) material (101).

[0075] After the inorganic phosphor dopant (100) is incorporated into the substrate (101), the photon-emitting inorganic phosphor doped (synthetic polymer) substrate is cured. Curing can be performed, for example, in air at room temperature. Curing causes the photon-emitting inorganic phosphor doped (synthetic polymer) substrate to harden together with the inorganic phosphor dopant (100) dispersed throughout the substrate (polymer host) material (101). The smaller the polarity difference 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.

[0076] In addition, the present disclosure includes examples according to the following clauses:

[0077] Clause 1. A method for disinfecting a surface, comprising:

[0078] exposing a surface of a substrate comprising an inorganic phosphor dopant to a UV light source;

[0079] wherein the exposing causes the inorganic phosphor dopant in the substrate to emit photons; and

[0080] The photons irradiate the surface, thereby sterilizing the surface.

[0081] Clause 2. The method of Clause 1, wherein the inorganic phosphor dopant in the substrate emits photons having a light wavelength of about 200 nm to 280 nm.

[0082] Clause 3. The method of Clause 2, wherein the inorganic phosphor dopant in the substrate emits photons having a light wavelength of about 225 nm to 250 nm.

[0083] Clause 4. The method of any of Clauses 1-3, wherein the UV light source has a wavelength of about 160 nm to 320 nm.

[0084] Clause 5. The method of any of Clauses 1-4, wherein the UV light source has a wavelength of approximately 222 nm, 254 nm, or 275 nm.

[0085] Clause 6. The method according to any one of clauses 1 to 5, wherein the inorganic phosphor dopant is a metal oxide or metal fluoride containing a rare earth ion, wherein the rare earth ion is selected from Pr 3+ 、Ce 3+ 、Eu 3+ 、Eu 2+ , Gd 3+ , Tb 3+ and Dy 3+ or a mixture thereof.

[0086] Clause 7. The method of clause 6, wherein the rare earth ion is Pr 3+ .

[0087] Clause 8. The method of clause 6 or 7, wherein the metal oxide is selected from the group consisting of silicates, phosphates, borates, oxides, oxynitrides, oxysulfides and aluminates, or combinations thereof.

[0088] Clause 9. The method of any of Clauses 1-8, wherein the substrate comprises one or more synthetic polymers.

[0089] Clause 10. The method of Clause 9, wherein the substrate comprises a material selected from the group consisting of optionally fluorinated thermoplastics, thermosetting resins, and electronegative resins.

[0090] Item 11. The method of Item 9 or 10, wherein the substrate comprises a material selected from the group consisting of tetrafluoroethylene, polyvinyl fluoride, polyurethane, polyester, epoxy resin, phenolic resin, vinyl ester, polyamide, polyamide-imide, polyetherimide, polyvinyl chloride, polyetherketoneketone, polycarbonate, polyphenylsulfone, polymethyl methacrylate, polyacrylate and benzoxazine.

[0091] Clause 12. The method of any one of Clauses 1-11, wherein the substrate comprising the inorganic phosphor dopant is exposed to a UV light source for a time sufficient to charge the inorganic phosphor dopant in the substrate.

[0092] Clause 13. The method of any of Clauses 1-12, wherein the UV light source is a pulsed xenon ultraviolet device.

[0093] Item 14. A photon-emitting inorganic phosphor-doped substrate comprising:

[0094] A substrate comprising an inorganic phosphor dopant, wherein the inorganic phosphor dopant in the substrate is capable of emitting photons when a surface of the photon-emitting inorganic phosphor-doped substrate is exposed to a UV light source.

[0095] Item 15. The photon-emitting inorganic phosphor-doped substrate of Item 14, wherein the substrate comprises one or more synthetic polymers.

[0096] Item 16. The photon-emitting inorganic phosphor-doped substrate of Item 14 or 15, wherein the substrate comprises a material selected from the group consisting of optionally fluorinated thermoplastics, thermosetting resins, and electronegative resins.

[0097] Item 17. A photon-emitting inorganic phosphor doped substrate as described in any of Items 14-16, wherein the substrate comprises a material selected from the group consisting of tetrafluoroethylene, polyvinyl fluoride, polyurethane, polyester, epoxy resin, phenolic resin, vinyl ester, polyamide, polyamide-imide, polyetherimide, polyvinyl chloride, polyetherketoneketone, polycarbonate, polyphenylsulfone, polymethyl methacrylate, polyacrylate and benzoxazine.

[0098] Item 18. A photon-emitting inorganic phosphor-doped substrate as described in any one of Items 14-17, wherein 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.

[0099] Item 19. The photon-emitting inorganic phosphor-doped substrate of Item 18, wherein the rare earth ion is Pr 3+ .

[0100] Item 20. The photon-emitting inorganic phosphor-doped substrate of Item 18 or 19, wherein the metal oxide is selected from the group consisting of silicates, phosphates, borates, oxides, oxynitrides, oxysulfides, and aluminates, or combinations thereof.

[0101] Item 21. A photon-emitting inorganic phosphor-doped substrate as described in any of Items 14-20, wherein the inorganic phosphor dopant in the substrate is capable of emitting photons having a light wavelength of approximately 180 nm to 320 nm when the surface of the photon-emitting inorganic phosphor-doped substrate is exposed to a UV light source.

[0102] Clause 22. A method of preparing a photon emitting material for surface disinfection, comprising:

[0103] A substrate is contacted with an inorganic phosphor dopant to prepare a photon-emitting inorganic phosphor-doped substrate, wherein the inorganic phosphor dopant in the photon-emitting inorganic phosphor-doped substrate is capable of emitting photons when a surface of the photon-emitting inorganic phosphor-doped substrate is exposed to a UV light source.

[0104] Clause 23. The method of Clause 22, wherein the inorganic phosphor dopant in the photon-emitting inorganic phosphor-doped substrate is capable of emitting photons having a light wavelength of about 180 nm to 320 nm.

[0105] Item 24. The method of Item 22 or 23, wherein the inorganic phosphor dopant is a metal oxide or metal fluoride containing a rare earth ion, wherein the rare earth ion is selected from Pr 3+ 、Ce 3+ 、Eu 3+ 、Eu 2+ , Gd 3+ , Tb 3+ and Dy 3+ or a mixture thereof.

[0106] Clause 25. The method of Clause 24, wherein the rare earth ion is Pr 3+ .

[0107] Clause 26. The method of 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.

[0108] Clause 27. The method of any of Clauses 22-26, wherein the substrate comprises one or more synthetic polymers.

[0109] Clause 28. The method of Clause 27, wherein the substrate comprises a material selected from the group consisting of optionally fluorinated thermoplastics, thermosetting resins, and electronegative resins.

[0110] Item 29. The method of Item 27 or 28, wherein the substrate comprises a material selected from the group consisting of tetrafluoroethylene, polyvinyl fluoride, polyurethane, polyester, epoxy resin, phenolic resin, vinyl ester, polyamide, polyamide-imide, polyetherimide, polyvinyl chloride, polyetherketoneketone, polycarbonate, polyphenylsulfone, polymethyl methacrylate, polyacrylate and benzoxazine.

[0111] The following examples are provided by way of illustration and not limitation. It will be appreciated by those skilled in the art that other synthetic routes may be used to synthesize the inorganic phosphor dopants and inorganic phosphor-doped substrates described herein. Although specific raw materials and reagents are described and discussed in the embodiments, other raw materials and reagents may be easily substituted to provide various derivative materials and / or reaction conditions. In addition, many exemplary materials prepared by the method may be further modified according to the present disclosure using conventional chemistry known to those skilled in the art.

[0112] Example

[0113] Example 1: Photon-emitting inorganic phosphor doped substrate (Ca 2-x Al 2 SiO 7 : x Pr 3+ Preparation of doped polyvinyl fluoride

[0114] Step 1. Ca 2-x Al 2 SiO 7 : x Pr 3+ Preparation of (100)

[0115] CaO、Al 2 O 3 、SiO 2 and Pr 6 O 11 Purchased from Sigma Aldrich. Weigh CaO, Al 2 O 3 、SiO 2 and Pr 6 O 11 , so that the mixture Pr 6 O 11The amount will produce 0.5-5% praseodymium substitution on the calcium site. The powder is then ground using an agate mortar and pestle for about 5 minutes until the powder forms a gray fine mixture. Thereafter, the mixed powder is placed in a ceramic alumina crucible and pre-fired at 900°C in air for 2 hours. Thereafter, the mixed powder is ground in an agate mortar and pestle for about 3 minutes. The mixed powder is then placed back into the alumina crucible and in a furnace for heating at 1300°C in air for 7 hours. The powder is removed from the furnace and allowed to cool to room temperature.

[0116] Powder X-ray diffraction analysis of the prepared Ca 2-x Al 2 SiO 7 : x Pr 3+ Inorganic phosphor dopant (100). FullProf was used to analyze the crystal structure to verify the Ca 2 Al 2 SiO 7 Ca / Pr site mixing in the crystal structure.

[0117] Step 2. Ca 2-x Al 2 SiO 7 : x Pr 3+ Preparation of doped polyvinyl fluoride

[0118] Polyvinyl fluoride (Dupont) was heated to about 180°C under an argon atmosphere to melt the material. 2-x Al 2 SiO 7 : x Pr 3+ (100) powder was thoroughly mixed with molten polyvinyl fluoride at an amount of about 10% by volume of phosphor / volume of polymer, so that Ca 2-x Al 2 SiO 7 : x Pr 3+ The doped polyvinyl fluoride is then solidified to form a solidified Ca 2-x Al 2 SiO 7 : x Pr 3+ In some embodiments, Ca 2- x Al 2 SiO 7 : x Pr 3+ The doped polyvinyl fluoride substrate can be formed using, for example, a mold while it is curing. The mold can assist in forming the Ca 2-x Al 2 SiO 7 : x Pr 3+The doped polyvinyl fluoride substrate is constructed into useful products such as cabinets, countertops, wall coverings or covers for various household, healthcare, automotive or aviation products. 2-x Al 2 SiO 7 : x Pr 3+ After forming the doped polyvinyl fluoride substrate, the material can be easily shaped and modified, for example using a saw, sandpaper or suitable molds.

[0119] Example 2: Using an inorganic phosphor-doped substrate (Ca 2-x Al 2 SiO 7 : x Pr 3+ Sterilization with polyvinyl fluoride

[0120] The Ca prepared in step 2 2-x Al 2 SiO 7 : x Pr 3+ The doped polyvinyl fluoride substrate is exposed to UV light with a wavelength of about 160nm to 280nm. This is the Ca in the polyvinyl fluoride main matrix (101). 2-x Al 2 SiO 7 : x Pr 3+ The radiation excitation energy of the phosphor (100). 2-x Al 2 SiO 7 : x Pr 3+ The doped polyvinyl fluoride substrate is exposed to a UV light source (104) (e.g., a UV lamp) for about 2 minutes to 10 minutes to allow Ca 2-x Al 2 SiO 7 : x Pr 3+ The phosphor (100) is charged. Then the UV lamp is turned off. Ca in the polyvinyl fluoride base material (main body) (101) 2-x Al 2 SiO 7 : x Pr 3+ The phosphor (100) then emits light in the range of 200 nm to 280 nm for about 2 to 10 minutes. This range of light emission corresponds to UV-C light, which is known to kill bacteria. 2-x Al 2 SiO 7 : x Pr3+ The bactericidal light emitted by the fluorescent body irradiates Ca 2-x Al 2 SiO 7 : x Pr 3+ The surface (101a) of the doped polyvinyl fluoride substrate is sterilized. The afterglow intensity of the phosphor-doped substrate is measured using a spectrofluorometer.

[0121] In another example, the UV light source (104) can be a pulsed xenon UV device having a wavelength of about 222 nm, 254 nm, or 275 nm, which is exposed to the Ca prepared in step 2. 2-x Al 2 SiO 7 : x Pr 3+ In one embodiment, Ca 2-x Al 2 SiO 7 : x Pr 3+ The surface (101a) of the doped polyvinyl fluoride substrate was exposed to a pulsed xenon UV device with a wavelength of 254 nm for about 2 minutes. When the excitation light was removed, a UV-C continuous luminescence emission of 268 nm was obtained. Ca 2-x Al 2 SiO 7 : x Pr 3+ Pr in doped polyvinyl fluoride materials 3+ UV-C afterglow shows that Ca 2-x Al 2 SiO 7 : x Pr 3+ The energy wells in the phosphor (100) can be efficiently filled by 254 nm light excitation, and the energy wells are located at appropriate energy positions so that they can be transferred from Pr 3+ 4f 1 5d 1 The electron is effectively trapped in the 4f state and released back to the 4f state due to the ambient thermal stimulation after the excitation stops. 1 5d 1 state. Isotropic light emission effectively 2-x Al 2 SiO 7 : x Pr 3+ The surface (101a) of the doped polyvinyl fluoride substrate is sterilized. The afterglow intensity of the phosphor-doped substrate is measured using a spectrofluorometer.

[0122] Example 3: Photon-emitting inorganic phosphor doped substrate (NaY( 1-x )F 6 : x Pr 3+ Preparation of doped tetrafluoroethylene

[0123] Step 1. NaY( 1-x )F 6 : x Pr 3+ Preparation of (100)

[0124] Preparation of Cs 2 NaY( 1-x )F 6 : x Pr 3+ (where x = 0.01-0.10) of the nominal composition of Pr doped polycrystalline potassium chloride cryolite phosphor. 2 CO 3 (1.6290 g, 99.99%, Aladdin, Shanghai, China), NaHCO 3 (0.4200 g, 99.99%, Aladdin, Shanghai, China), Y 2 O 3 (0.5588 g, 99.99%, Aladdin, Shanghai, China), NH 4 F (2.2222 g, 99.99%, Aladdin, Shanghai, China) and Pr 6 O 11 (0.0085 g, 99.996%, Alfa, USA) powder was mixed with 3 mL of acetone and then fully ground for about 5 minutes. The resulting powder was heat treated in air at 150°C for 7 hours and then ground again to obtain a fine powder. The mixture was then sintered in air at 450°C for 30 minutes. The resulting powder was then ground again and subsequently sintered at 700°C for 10 hours under a nitrogen atmosphere. A corundum boat with a purity of 99% and a platinum crucible were used as containers for the above synthesis.

[0125] Powder X-ray diffraction analysis of the prepared Cs 2 NaY( 1-x )F 6 : x Pr 3+ Inorganic phosphor dopant (100). FullProf was used to analyze the crystal structure to verify the Cs 2 NaY( 1-x )F 6 : x Pr 3+ The Y / Pr sites in the crystal structure are mixed. The structure crystallizes in the Fm-3m space group corresponding to cubic lysozyme. In this double perovskite structure, both Y and Na are coordinated with 6 boron atoms, and the doped Pr 3+ Ion substitution Y3+ ion.

[0126] Step 2.Cs 2 NaY( 1-x )F 6 : x Pr 3+ Preparation of doped tetrafluoroethylene

[0127] Tetrafluoroethylene (Dupont) was heated to about 327°C under an argon atmosphere to melt the material. 2 NaY( 1-x )F 6 : x Pr 3+ (100) powder was thoroughly mixed with molten tetrafluoroethylene at a volume of about 10% phosphor / volume polymer to make Cs 2 NaY( 1-x )F 6 : x Pr 3+ The doped tetrafluoroethylene is then cured to form a cured Cs 2 NaY( 1-x )F 6 : x Pr 3+ In some embodiments, Cs 2 NaY( 1-x )F 6 : x Pr 3+ The doped PTFE substrate can be formed using, for example, a mold while it is curing. The mold can assist in forming the Cs 2 NaY( 1-x )F 6 : x Pr 3+ The doped PTFE substrate is constructed into useful products such as cabinets, countertops, wall coverings or covers for various household, healthcare, automotive or aviation products. 2 NaY( 1-x )F 6 : x Pr 3+ After the doped tetrafluoroethylene substrate is formed, the material can be easily shaped and modified, for example using a saw, sandpaper or a suitable mold.

[0128] Example 4: Using an inorganic phosphor-doped substrate (Cs 2 NaY( 1-x )F 6 : x Pr 3+ Sterilization with doped tetrafluoroethylene

[0129] The Cs prepared in step 22 NaY( 1-x )F 6 : x Pr 3+ The doped tetrafluoroethylene substrate is exposed to a pulsed xenon lamp with a wavelength of 100 nm to 225 nm for about 30 seconds. The pulsed light is sufficient to degrade the Cs 2 NaY( 1-x )F 6 : x Pr 3+ The phosphor (100) is charged. Cs in the tetrafluoroethylene base material (host) material (101) 2 NaY( 1-x )F 6 : x Pr 3+ The phosphor (100) then emits light (bactericidal light) in the range of 200nm to 280nm for about 10 to 20 minutes. 2 NaY( 1-x )F 6 : x Pr 3+ The germicidal light emitted by the phosphor irradiates the Cs 2 NaY( 1-x )F 6 : x Pr 3+ The surface (101a) of the doped tetrafluoroethylene substrate (101) is sterilized, thereby sterilizing the surface (101a). The afterglow intensity of the phosphor-doped substrate is measured using a spectrofluorometer.

[0130] Efforts have been made to ensure accuracy with respect to numbers used (eg amounts, temperature, etc.) but some experimental errors and deviations should be accounted for.

[0131] One skilled in the art will recognize many methods and materials similar or equivalent to those described herein that can be used to practice the subject matter described herein.The present disclosure is in no way limited to the methods and materials described.

[0132] Where a numerical range is provided, unless the context clearly dictates otherwise, it is understood that the upper and lower limits of the range and any other stated value or intervening value in the stated range are included to the tenth of the unit of the lower limit. The upper and lower limits of these smaller ranges, which may be independently included in the smaller ranges, are also included, subject to any specifically excluded limits in the stated range. Where the stated range includes one or both of these limits, then ranges excluding one or both of those included limits are also included.

[0133] Many modifications and other examples set forth herein will occur to one skilled in the art having the benefit of the teachings presented in the foregoing description and the associated drawings. Therefore, it should be understood that the subject matter is not limited to the specific examples disclosed, and modifications and other examples are intended to be included within the scope of the appended claims. Although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.

Claims

1. A method for disinfecting a surface, comprising: exposing a surface of a substrate including an inorganic phosphor dopant to a UV light source; wherein the exposing causes the inorganic phosphor dopant in the substrate to emit photons; and The photons irradiate the surface, thereby sterilizing the surface.

2. The method of claim 1, wherein: The inorganic phosphor dopant in the substrate emits photons having a light wavelength of about 200 nm to 280 nm, and / or the inorganic phosphor dopant in the substrate emits photons having a light wavelength of about 225 nm to 250 nm.

3. The method according to any one of claims 1 to 3, wherein: The UV light source has a wavelength of about 160 nm to 320 nm, optionally, the UV light source has a wavelength of about 222 nm, 254 nm or 275 nm.

4. The method according to any one of claims 1 to 3, wherein: The inorganic phosphor dopant is a metal oxide or metal fluoride containing rare earth ions, wherein the rare earth ions are selected from Pr 3+ 、Ce 3+ 、Eu 3+ 、Eu 2+ , Gd 3+ , Tb 3+ and Dy 3+ or a mixture thereof, or optionally, the rare earth ion is Pr 3+ .

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

6. The method according to any one of claims 1 to 5, wherein: The substrate comprises one or more synthetic polymers.

7. The method of claim 6, wherein: The substrate comprises a material selected from the group consisting of optionally fluorinated thermoplastics, thermosetting resins and electronegative resins, or the substrate comprises a material selected from the group consisting of tetrafluoroethylene, polyvinyl fluoride, polyurethane, polyester, epoxy resin, phenolic resin, vinyl ester, polyamide, polyamide-imide, polyetherimide, polyvinyl chloride, polyetherketoneketone, polycarbonate, polyphenylsulfone, polymethyl methacrylate, polyacrylate and benzoxazine.

8. The method according to any one of claims 1 to 7, wherein: The substrate including the inorganic phosphor dopant is exposed to a UV light source for a time sufficient to charge the inorganic phosphor dopant in the substrate, optionally the UV light source is a pulsed xenon ultraviolet device.

9. A substrate doped with an inorganic phosphor that emits photons, comprising: A substrate comprising an inorganic phosphor dopant, wherein the inorganic phosphor dopant in the substrate is capable of emitting photons when a surface of the photon-emitting inorganic phosphor-doped substrate is exposed to a UV light source.

10. The photon-emitting inorganic phosphor-doped substrate of claim 9, wherein: The substrate comprises one or more synthetic polymers and / or the substrate comprises a material selected from the group consisting of optionally fluorinated thermoplastics, thermosetting resins and electronegative resins, and / or the substrate comprises a material selected from the group consisting of tetrafluoroethylene, polyvinyl fluoride, polyurethane, polyester, epoxy resin, phenolic resin, vinyl ester, polyamide, polyamide-imide, polyetherimide, polyvinyl chloride, polyetherketoneketone, polycarbonate, polyphenylsulfone, polymethyl methacrylate, polyacrylate and benzoxazine.

11. The photon-emitting inorganic phosphor-doped substrate according to claim 9 or 10, wherein: The inorganic phosphor dopant is a metal oxide or metal fluoride containing rare earth ions, wherein the rare earth ions are selected from Pr 3+ 、Ce 3+ 、Eu 3 + 、Eu 2+ , Gd 3+ , Tb 3+ and Dy 3+ or a mixture thereof, or optionally, the rare earth ion is Pr 3+ .

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

13. The photon-emitting inorganic phosphor-doped substrate according to claim 11 or 12, wherein: The inorganic phosphor dopant in the substrate is capable of emitting photons having a light wavelength of about 200 nm to 280 nm when a surface of the photon-emitting inorganic phosphor-doped substrate is exposed to a UV light source.

14. A method for preparing a photon emitting material for surface disinfection, comprising: A substrate is contacted with an inorganic phosphor dopant to prepare a photon-emitting inorganic phosphor-doped substrate, wherein the inorganic phosphor dopant in the photon-emitting inorganic phosphor-doped substrate is capable of emitting photons when a surface of the photon-emitting inorganic phosphor-doped substrate is exposed to a UV light source.

15. The method of claim 14, wherein: The inorganic phosphor dopant in the photon-emitting inorganic phosphor-doped substrate is capable of emitting photons having a light wavelength of about 200 nm to 280 nm.

16. The method according to claim 14 or 15, wherein: The inorganic phosphor dopant is a metal oxide or metal fluoride containing rare earth ions, wherein the rare earth ions are selected from Pr 3+ 、Ce 3+ 、Eu 3+ 、Eu 2+ , Gd 3+ , Tb 3+ and Dy 3+ or a mixture thereof, or optionally, the rare earth ion is Pr 3+ .

17. The method according to any one of claims 14 to 16, wherein: The metal oxide is selected from the group consisting of silicates, phosphates, borates, oxides, oxynitrides, oxysulfides and aluminates or a combination thereof.

18. The method according to any one of claims 14 to 17, wherein: The substrate comprises one or more synthetic polymers and / or the substrate comprises a material selected from the group consisting of optionally fluorinated thermoplastics, thermosetting resins and electronegative resins, and / or the substrate comprises a material selected from the group consisting of tetrafluoroethylene, polyvinyl fluoride, polyurethane, polyester, epoxy resin, phenolic resin, vinyl ester, polyamide, polyamide-imide, polyetherimide, polyvinyl chloride, polyetherketoneketone, polycarbonate, polyphenylsulfone, polymethyl methacrylate, polyacrylate and benzoxazine.

Images