Injection and compression molding of MN 4+ doped fluoride phosphors

Abstract

Methods for compression molding materials including Mn4+ doped fluoride phosphors and molded articles including Mn4+ doped fluoride phosphors are disclosed. More particularly, a molded article formed from a molding material is disclosed. The molding material comprises at least one phosphor material and at least one resin. The at least one phosphor material includes K2SiF6:Mn4+ (also known as PFS or KSF) and the least one resin comprises polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), and / or polycarbonate (PC).

Description

INJECTION AND COMPRESSION MOLDING OF MN4+DOPED FLUORIDEPHOSPHORSRELATED APPLICATIONS

[0001] This application claims priority to U.S. Provisional Application No. 63 / 682,012, filed 12 August 2024.FIELD OF THE INVENTION

[0002] The subject matter described herein relates generally to forming molded articles for lighting applications.BACKGROUND

[0003] Compression molding is a forming process in which heat and pressure are used to create a part. More particularly, a molding material, such as a resin, is placed into a mold and then heated to a specific temperature. The mold is closed and high pressure is applied. The combined heat and pressure cause the molding material to conform to the shape of the mold cavity. Compression molding is a simple and cost-effective process for manufacturing high volumes of strong and durable parts.

[0004] Injection molding is another forming process which involves injecting the molding material into a mold. More particularly, in injection molding, the molding material is heated until it can flow and then injected into a mold. The molding material is then cooled. In this way, the molding material confirms to the configuration of the cavity. Injection molding a simple and cost-effective process for manufacturing high volumes of uniform, complex parts.

[0005] Narrow band emission phosphor materials achieve high color quality in lighting based on LEDs. Cost-effective and efficient methods of forming color conversion components for lighting applications are highly desirable.SUMMARY OF THE INVENTION

[0006] In one aspect, a molded article is disclosed. The molded article is formed from a molding material. The molding material comprises at least one phosphor material and at least one resin. The at least one phosphor material includes a Mn4+doped phosphor of formula I,Ax[MFy]:Mn4+Iwhere A is Li, Na, K, Rb, Cs, NH4, or a combination thereof; M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd, or a combination thereof; x is the absolute value of the charge of the [MFy] ion; and y is 5, 6 or 7.

[0007] In another aspect, a molded article is disclosed. The molded article is formed from a molding material. The molding material comprises at least one phosphor material and at least one resin. The at least one phosphor material includes a Mn4+doped phosphor of formula I,Ax[MFy]:Mn4+I where A is Li, Na, K, Rb, Cs, NFL, or a combination thereof; M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd, or a combination thereof; x is the absolute value of the charge of the [MFy] ion; and y is 5, 6 or 7. The Mn4+ doped phosphor has a D50 particle size of less than 15 microns.

[0008] In another aspect, a molded article is disclosed. The resin formulation comprises at least one phosphor material, at least one resin, and at least one solvent. The at least one phosphor material comprises a Mn4+doped phosphor of formula I,Ax[MFy]:Mn4+I where A is Li, Na, K, Rb, Cs, NFL, or a combination thereof; M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd, or a combination thereof; x is the absolute value of the charge of the [MFy] ion; and y is 5, 6 or 7. The resin formulation is cured to form the molded article.

[0009] In another aspect, a device is disclosed. The device comprises an LED light source optically coupled and / or radiationally connected to a molded article. The molded article is formed from a molding material. The molding material comprises at least one resin and at least one phosphor material. The at least one phosphor material comprises a Mn4+doped phosphor of formula I,Ax[MFy]:Mn4+I where A is Li, Na, K, Rb, Cs, NFL, or a combination thereof; M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd, or a combination thereof; x is the absolute value of the charge of the [MFy] ion; and y is 5, 6 or 7. The device may be part of an illumination device, alighting apparatus, an automotive light, an automotive tail-light, an aviation light, and combinations thereof.

[0010] In another aspect, a device is disclosed. The device comprises a molded article and an LED light source. The molded article has a first side and a second side. The molded article is formed from a molding material. The molding material comprises at least one resin and at least one phosphor material. The LED light source is located remotely from the molded article. The LED light source is optically coupled and / or radiationally connected to at least the first side of the molded article. At least one of the first side of the molded article or the second side of the molded article has a reflectivity of at least 20% or the device further comprises a back reflective layer located on the second side of the molded article. The device may be part of an illumination device, a lighting apparatus, an automotive light, an automotive tail-light, an aviation light, and combinations thereof.

[0011] In another aspect, an automotive or aviation light is disclosed. The automotive or aviation light comprises an LED light source optically coupled and / or radiationally connected to a molded article. The molded article is formed from a molding material. The molding material comprises at least one resin and at least one phosphor material. The at least one phosphor material comprises a Mn4+doped phosphor of formula I,Ax[MFy]:Mn4+I where A is Li, Na, K, Rb, Cs, NEL, or a combination thereof; M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd, or a combination thereof; x is the absolute value of the charge of the [MFy] ion; and y is 5, 6 or 7.BRIEF DESCRIPTION OF THE DRAWINGS

[0012] These and other features, aspects, and advantages of the present disclosure will become better understood when the following detailed description is read with reference to the accompanying drawings in which like characters represent like parts throughout the drawings, wherein:

[0013] FIG. 1 A is a schematic cross-sectional view of a device, in accordance with one embodiment of the disclosure.

[0014] FIG. IB is a schematic cross-sectional view of a device, in accordance with one embodiment of the disclosure.

[0015] FIG. 1C is a schematic cross-sectional view of a device, in accordance with one embodiment of the disclosure.

[0016] FIG. ID is a schematic cross-sectional view of a device, in accordance with one embodiment of the disclosure.

[0017] FIG. IE is a schematic cross-sectional view of a device, in accordance with one embodiment of the disclosure.

[0018] FIG. 2 is a schematic cross-sectional view of a device, in accordance with one embodiment of the disclosure.

[0019] FIG. 3 is a schematic cross-sectional view of a device, in accordance with one embodiment of the disclosure.

[0020] FIG. 4 is a schematic cross-sectional view of a device, in accordance with one embodiment of the disclosure.

[0021] FIG. 5 is a schematic cross-sectional view of a device, in accordance with an exemplary embodiment.

[0022] FIG. 6 is a schematic cross-sectional view of a device, in accordance with one embodiment of the disclosure.

[0023] FIG. 7A is a schematic cross-sectional view of a first stage of a compression molding process, in accordance with one embodiment of the disclosure.

[0024] FIG. 7B is a schematic cross-sectional view of a second stage of a compression molding process, in accordance with one embodiment of the disclosure.

[0025] FIG. 8A is a schematic cross-sectional view of a first stage of a compression molding process, in accordance with one embodiment of the disclosure.

[0026] FIG. 8B is a schematic cross-sectional view of a second stage of a compression molding process, in accordance with one embodiment of the disclosure.

[0027] FIG. 9 is a schematic cross-sectional view of a device, in accordance with one embodiment of the disclosure.

[0028] FIG. 10 is a schematic cross-sectional view of a device, in accordance with one embodiment of the disclosure.

[0029] FIG. 11 is a schematic cross-sectional view of a device, in accordance with one embodiment of the disclosure.

[0030] FIG. 12A is a schematic cross-sectional view of a first stage of a compression molding process, in accordance with one embodiment of the disclosure.

[0031] FIG. 12B is a schematic cross-sectional view of a second stage of a compression molding process, in accordance with one embodiment of the disclosure.

[0032] FIG. 12C is a schematic cross-sectional view of a molded article, in accordance with one embodiment of the disclosure.

[0033] FIG. 13 A is a schematic cross-sectional view of a first stage of an injection molding process, in accordance with one embodiment of the disclosure.

[0034] FIG. 13B is a schematic cross-sectional view of a second stage of an injection molding process, in accordance with one embodiment of the disclosure.

[0035] FIG. 13C is a schematic cross-sectional view of a third stage of an injection molding process, in accordance with one embodiment of the disclosure.

[0036] Unless otherwise indicated, the drawings provided herein are meant to illustrate features of embodiments of the disclosure. These features are believed to be applicable in a wide variety of systems comprising one or more embodiments of the disclosure. As such, the drawings are not meant to include all conventional features known by those of ordinary skill in the art to be required for the practice of the embodiments disclosed herein.DETAILED DESCRIPTION

[0037] In the following specification and the claims, reference will be made to a number of terms, which shall be defined to have the following meanings.

[0038] The singular forms “a”, “an”, and “the” include plural references unless the context clearly dictates otherwise. As used herein, the term “or” is not meant to be exclusive and refers to at least one of the referenced components being present and includes instances in which a combination of the referenced components may be present, unless the context clearly dictates otherwise.

[0039] Approximating language, as used herein throughout the specification and claims, may be applied to modify any quantitative representation that could permissibly vary without resulting in a change in the basic function to which it is related. Accordingly, a value modified by a term or terms, such as “about,” “substantially,” and “approximately,” are not to be limited to the precise value specified. In at least some instances, the approximating language may correspond to the precision of an instrument for measuring the value. Here and throughout the specification and claims, range limitations may be combined and / or interchanged, such ranges are identified and include all the sub-ranges contained therein unless context or language indicates otherwise.

[0040] “Optional” or “optionally” means that the subsequently described event or circumstance may or may not occur, or that the subsequently identified material may or may not be present, and that the description includes instances wherein the event or circumstanceoccurs or wherein the material is present, and instances wherein the event or circumstance does not occur, or the material is not present.

[0041] As used herein, the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having,” “contains”, “containing,” “characterized by” or any other variation thereof, are intended to cover a non-exclusive inclusion, subject to any limitation explicitly indicated. For example, a composition, mixture, process or method that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, mixture, process or method.

[0042] The transitional phrase “consisting of’ excludes any element, step, or ingredient not specified. If in the claim, such would close the claim to the inclusion of materials other than those recited except for impurities ordinarily associated therewith. When the phrase “consisting of’ appears in a clause of the body of a claim, rather than immediately following the preamble, it limits only the element set forth in that clause; other elements are not excluded from the claim as a whole.

[0043] The transitional phrase “consisting essentially of’ is used to define a composition or method that includes materials, steps, features, components, or elements, in addition to those literally disclosed, provided that these additional materials, steps, features, components, or elements do not materially affect the basic and novel characteristic(s) of the claimed invention. The term “consisting essentially of’ occupies a middle ground between “comprising” and “consisting of’.

[0044] Where an invention or a portion thereof is defined with an open- ended term such as “comprising,” it should be readily understood that (unless otherwise stated) the description should be interpreted to also describe such an invention using the terms “consisting essentially of’ or “consisting of.”

[0045] As used herein, references to “example embodiment” or “one embodiment” or “some embodiments” of the present disclosure are not intended to be interpreted as excluding the existence of additional embodiments that also incorporate the recited features.

[0046] Although specific features of various embodiments of the invention may be shown in some drawings and not in others, this is for convenience only. In accordance with the principles of the invention, any feature of a drawing may be referenced and / or claimed in combination with any feature of any other drawing.

[0047] While the invention has been described in terms of various specific embodiments, those skilled in the art will recognize that the invention can be practiced with modification within the spirit and scope of the claims.

[0048] Unless otherwise indicated, the terms “first,” “second,” etc. are used herein merely as labels, and are not intended to impose ordinal, positional, or hierarchical requirements on the items to which these terms refer. Moreover, reference to, for example, a “second” item does not require or preclude the existence of, for example, a “first” or lower- numbered item or a “third” or higher-numbered item.

[0049] Square brackets in the formulas indicate that at least one of the elements is present in the phosphor material, and any combination of two or more thereof may be present. For example, the formula [Ca,Sr,Ba]3MgSi20s:Eu2+,Mn2+encompasses at least one of Ca, Sr or Ba or any combination of two or more of Ca, Sr or Ba. Examples include Ca3MgSi20s:Eu2+.Mn2+; Sr3MgSi20s:Eu2+.Mn2+; or Ba3MgSi20s:Eu2+.Mn2+. Formula with an activator after a colon indicates that the phosphor material is doped with the activator. Formula showing more than one activator separated by a after a colon indicates that the phosphor material is doped with either activator or both activators. For example, the formula [Ca,Sr,Ba]3MgSi20s:Eu2+,Mn2+encompasses [Ca,Sr,Ba]3MgSi20s:Eu2+, [Ca,Sr,Ba]3MgSi20s:Mn2+or [Ca,Sr,Ba]3MgSi20s:Eu2+and Mn2+.

[0050] The term “reflectivity”, as used herein, refers generally to a measure of the proportion of incident electromagnetic power that reflects away after striking a surface, for example blue or UV LEDs serving as the excitation source.

[0051] “Reflective geometry”, as used herein, refers generally to a configuration in which light emitted from a remote light source (e.g., an LED light source) and strikes a surface (e.g., a reflective surface) and is emitted in a desirable direction. The light travels through a layer (e.g., a color conversion layer) before or after striking the surface.

[0052] Transmissive geometry”, as used herein, refers generally to a configuration in which light emitted from a light source (e.g., an LED light source) is transmitted through (e.g., from one side to another, opposite side) one or more layers (e.g., a color conversion layer).

[0053] The term “layer”, as used herein, refers to a material disposed on at least a portion of an underlying surface in a continuous or discontinuous manner. The term “layer” does not necessarily mean a uniform thickness of the disposed material, and the disposed material may have a uniform or a variable thickness. As used herein, the term “disposed on” refers to layers or materials disposed directly in contact with each other or indirectly by having intervening layers or features there between, unless otherwise specifically indicated.

[0054] D50 (also expressed as Dso) is defined as the median particle size for a volume distribution. D90 (also expressed as D90) is the particle size for a volume distribution that isgreater than the particle size of 90% of the particles of the distribution. DIO (also expressed as Dio) is the particle size for a volume distribution that is greater than the particle size of 10% of the particles of the distribution. Particle size of the phosphors may be conveniently measured by laser diffraction or optical microscopy methods, and commercially available software can generate the particle size distribution and span. Span is a measure of the width of the particle size distribution curve for a particulate material or powder, and is defined according to the equation:wherein D90, Dio and D50 are defined above. For phosphor particles, span of the particle size distribution is not necessarily limited and may be <1.0 in some embodiments.

[0055] A “remote LED light source” indicates that the LED light source is remote in the sense that the LED light source and the color conversion component are separate elements and that the color conversion component is not integrated or in physical contact with the light source as a single element.

[0056] A “molding material”, as used herein, refers generally to a material used in the process of compression molding or injection molding.

[0057] “Compression molding”, as used herein, involves placing a molding material in an open, heated mold cavity. The molding material may be preheated before being placed in the mold cavity. Compression molding further involves closing the mold with a top force or plug member, applying pressure to force the material in contact with all mold areas, and maintaining heat and pressure until the molding material has cured.

[0058] “Injection molding”, as used herein, involves heating a molding material until it can flow and then injecting the molding material into a mold. The molding material then cools and hardens to the configuration of the cavity.

[0059] A “molded article” or “molded component”, as used herein, refers generally to a component formed at least in part by compression molding or injection molding. Molded articles as disclosed herein include at least one optically active material, such as a phosphor.

[0060] A molded article and methods of making the same are disclosed. In some embodiments, the molding material used to create the molded article comprises at least one resin material and at least one phosphor material. For example, in one embodiment, the at least one resin material includes one or more of polymethyl methacrylate (PMMA), polycarbonate (PC), and / or polyethylene terephthalate (PET). However various other resinmaterials may be used. In some embodiments, the molding material may include at least one solvent.

[0061] More particularly, in some embodiments, the molding material includes a phosphor material including a Mn4+doped phosphor of formula I and at least one resin material,Ax[MFy]:Mn4+I where A is Li, Na, K, Rb, Cs, NH4, or a combination thereof; M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd, or a combination thereof; x is the absolute value of the charge of the [MFy] ion; and y is 5, 6 or 7. In some embodiments, the Mn4+doped phosphor has a D50 particle size of less than 15 microns. In other embodiments, the Mn4+doped phosphor has a D50 particle size of greater than or equal to 15 microns.

[0062] The Mn4+doped phosphors of formula I are complex fluoride materials, or coordination compounds, containing at least one coordination center surrounded by fluoride ions acting as ligands, and charge-compensated by counter ions as necessary. For example, in K2SiFe:Mn4+, the coordination center is Si and the counterion is K. The activator ion (Mn4+) also acts as a coordination center, substituting part of the centers of the host lattice, for example, Si. The host lattice (including the counter ions) may further modify the excitation and emission properties of the activator ion.

[0063] In particular embodiments, the coordination center of the phosphor, that is, M in formula I, is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd, or a combination thereof. More particularly, the coordination center may be Si, Ge, Ti, or a combination thereof. The counterion, or A in formula I, may be Li, Na, K, Rb, Cs, NH4, or a combination thereof, more particularly K or Na. Examples of phosphors of formula I include K2[SiF6]:Mn4+, K2[TiF6]:Mn4+, K2[SnF6]:Mn4+, Cs2[TiF6]:Mn4+, K2[GeF6]Mn4+, Rb2[TiF6] Mn4+, Cs2[SiF6]:Mn4+, Rb2[SiF6]:Mn4+, Na2[SiF6]:Mn4+, Na2[TiF6]:Mn4+, Na2[ZrF6]:Mn4+, K3[ZrF7]:Mn4+, K3[BiF6] K3[YF6]:Mn4+, K3[LaF6]:Mn4+, K3[GdF6]:Mn4+, K3[NbF7]:Mn4+, K3[TaF7]:Mn4+. In particular embodiments, the phosphor of formula I is K2SiFe:Mn4+(also known as PFS or KSF) or Na2[SiFe]:Mn4+(NSF).

[0064] The amount of activator Mn incorporation in the Mn4+doped phosphors (referred to as Mn%) improves color conversion. Increasing the amount of Mn% incorporation improves color conversion by increasing the intensity of the red emission,maximizing absorption of excitation blue light and reducing the amount of unconverted blue light or bleed-through of blue light from a blue LED.

[0065] In one embodiment, the red-emitting Mn4+doped phosphor has a Mn loading or Mn% of at least 0.7 wt%. In another embodiment, the red-emitting phosphor has a Mn loading of at least 1.0 wt%. In another embodiment, the red-emitting phosphor has a Mn loading of at least 1.5 wt%. In another embodiment, the red-emitting phosphor has a Mn loading of at least 2 wt%. In another embodiment, the red-emitting phosphor has a Mn% of at least 3 wt%. In another embodiment the Mn% is greater than 3.0 wt%. In another embodiment, the content of Mn in the red-emitting phosphor is from about 1 wt% to about 4 wt%.

[0066] In one embodiment, the phosphor material comprises a KSF phosphor (K2SiFe:Mn) with small particle size and high manganese content. As opposed to quantum dot color filter solutions, KSF phosphor (K2SiFe:Mn) has a narrower emission intensity, less self-absorption issues in thicker color conversion components, less decrease in quantum efficiency when cured into a color conversion component, high thermal stability, and stability under high humidity. In one embodiment, the KSF phosphor has a D50 particle size from about 0.1 microns to about 15 microns and comprises a Mn content of at least 0.7 wt%. In one embodiment, the KSF phosphor has a D50 particle size of less than 15 microns and comprises a Mn content of about 1 wt% to about 4 wt%. In another embodiment, the KSF phosphor has a D50 particle size of more than 15 microns and comprises a Mn content of about 1 wt% to about 4 wt%. In other embodiments, the molding material includes an NSF phosphor (Na2SiFe) with small particle size and high manganese content.

[0067] In some embodiments, a molded article may be arranged on or adjacent to an LED light source. The molded article may be formed via compression molding or injection molding using a molding material comprising at least one resin (e.g., PMMA, polycarbonate, PET, and the like) and at least one optically active material (e.g., KSF). Such a molded article may enable a functioning lighting apparatus when excited by blue or UV light.

[0068] In one embodiment, the molded article is formed using a compression molding process. More particularly, a molding material is placed in one or more open, heated mold cavities. The molding material may be preheated before it is placed in the one or more cavities. The mold is then closed with a top force of plug member and pressure is applied to force the material into contact with all mold areas, while heat and pressure are maintained until the molding material is cured. In embodiments in accordance with the present disclosure, the molding material includes at least one resin and at least one optically activematerial. In one embodiment, the molding material further comprises at least one solvent. The resulting molded articles maintain the properties of the at least one optically active material (e.g., phosphor) while avoiding some of the drawbacks with conventional techniques for forming optically active components, such as air bubbles.

[0069] The molded article may be a variety of different shapes and geometries. For example, in one embodiment, the molded article comprises a disc. However, the molded article may comprise a variety of other shapes and geometries, including but not limited to, rectangular, square, and the like.

[0070] In one embodiment, a plurality of LED light sources are each optically coupled and / or radiationally connected to at least one molded article. In one embodiment, the Mn4+doped phosphor may be a manganese-doped potassium fluorosilicate, such as K2SiFe:Mn4+(PFS). PFS has a narrow band emission having multiple peaks with an average full width at half maximum (FWHM) of less than 4 nm. In another embodiment, the red-emitting phosphor may be Na2SiFe:Mn4+(NFS).

[0071] In one embodiment, Mn4+doped phosphors may be further treated, such as by annealing, wash treatment, roasting or any combination of these treatments. Post-treatment processes for Mn4+doped phosphors are described in US Patent No. 8,906,724, US Patent No. 8,252,613, US Patent No. 9,698,314, US Patent No. 9,982,190, US Patent No.11,193,059, and US Patent No. 11,261,375, the entire contents of each of which are incorporated herein by reference. In one embodiment, the Mn4+doped phosphors may be annealed, treated with multiple wash treatments and roasted.

[0072] To improve reliability, the Mn4+doped phosphor of Formula I may be at least partially coated with surface coatings to enhance stability of the phosphor particles and resist aggregation by modifying the surface of the particles and increase the zeta potential of the particles. In one embodiment, the surface coatings comprise at least one of hydrophobic coating, metal fluoride coating, and / or organic coating. In one embodiment, the surface coatings comprise a hydrophobic coating. In one embodiment, the surface coatings may be a metal fluoride coating and / or an organic coating. In one embodiment, the red-emitting phosphors based on complex fluoride materials activated by Mn4+phosphors are at least partially coated with a metal fluoride, which increases positive Zeta potential and reduces agglomeration. In one embodiment, the metal fluoride coating includes MgF2, CaF2, SrF2, BaF2, AgF, ZnF2, AIF3 or a combination thereof. In another embodiment, the metal fluoride coating is in an amount from about 0.1 wt% to about 10 wt%. In another embodiment, the metal fluoride coating is present in an amount from about 0.1 wt% to about 5 wt%. In anotherembodiment, the metal fluoride coating is present from about 0.3 wt% to about 3 wt%. Metal fluoride coated red-emitting phosphors based on complex fluoride materials activated by Mn4+are prepared as described in WO 2018 / 093832, US Publication No. 2018 / 0163126 and US Publication No. 2020 / 0369956, the entire contents of each of which are incorporated herein by reference.

[0073] The phosphor material may include additional phosphors, such as an Yttrium Aluminum Garnet phosphor (YAG). The ratio of powders (YAG: PFS) may be tuned to reach a desired color point. The phosphor material may include additional phosphors, such as rare earth Garnet phosphors. The rare earth elements include Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu. In one embodiment, the rare earth Garnet phosphor is an yttrium aluminum garnet phosphor (YAG). The ratio of the rare earth garnet phosphors to Mn4+doped phosphor may be tuned to reach a desired color point, further embodiments, the phosphor blend of Mn4+doped phosphor and rare earth garnet phosphor has a high percentage of the rare earth Garnet phosphor. In some embodiments, the rare earth Garnet phosphor may be present in the phosphor blend in an amount of about 60 wt% to about 90 wt% and the Mn4+doped phosphor may be present from about 40 wt% to about 10 wt%. In another embodiment, the rare earth Garnet phosphor may be present in the phosphor blend in an amount of about 80 wt% to about 99.9 wt%. Additionally, the Mn4+doped phosphor may be present in the phosphor material in an amount of about 20 wt% to about 0.1 wt%. In some embodiments, the rare earth Garnet phosphor may be present in the phosphor material in an amount of about 90 wt% to about 99.9 wt%. Additionally, the Mn4+doped phosphor may be present in the phosphor material in an amount of about 10 wt% to about 0.1 wt%. In some embodiments, the rare earth Garnet phosphor may be present in the phosphor material in an amount of about 95 wt% to about 99.9 wt%. Additionally, the Mn4+doped phosphor may be present in the phosphor material in an amount of about 5 wt% to about 0.1 wt%. The wt% of the phosphor material is based on the total weight of the phosphor blend of the rare earth garnet phosphor and the Mn4+doped phosphor. In some embodiments, the rare earth Garnet phosphor comprises YAG and the Mn4+doped phosphor comprises PFS. In another embodiment, the luminescent material comprises yttrium aluminum garnet (YAG) and K2SiF6:Mn4+(PFS).

[0074] In some embodiments, the phosphor material may be a red-emitting phosphor based on complex fluoride materials activated by Mn4+.

[0075] The phosphor material may include one or more other luminescent materials. Additional luminescent materials, such as blue, yellow, red, orange, or other color phosphorsmay be used in the phosphor material to customize the white color of the resulting light and produce specific spectral power distributions.

[0076] Suitable phosphors for use in the phosphor material , include, but are not limited to: ((Sri-z[Ca,Ba,Mg,Zn]z)i-(X+w)[Li,Na,K,Rb]wCex)3(Ali-ySiy)O4+y+3(x-w)Fi-y-3(X-w), 0<x<0.10, 0<y<0.5, 0<z<0.5, 0<w<x; [Ca,Ce]3Sc2Si30i2 (CaSiG); [Sr,Ca,Ba]3Ali-xSixO4+xFi-x:Ce3+(SASOF)); [Ba,Sr,Ca]5(PO4)3[Cl,F,Br,OH]:Eu2+,Mn2+; [Ba,Sr,Ca]BPO5:Eu2+,Mn2+;[Sr,Ca]io(P04)e*vB203:Eu2+(wherein 0<v<l); Sr2Si3O8*2SrC12:Eu2+;[Ca,Sr,Ba]3MgSi2O8:Eu2+,Mn2+; BaAl8Oi3:Eu2+; 2SrO*0.84P2O5*0.16B2O3:Eu2+;[Ba,Sr,Ca]MgAli0Oi7:Eu2+,Mn2+; [Ba,Sr,Ca]Al2O4:Eu2+; [Y,Gd,Lu,Sc,La]BO3:Ce3+,Tb3+; ZnS:Cu+,Cl-; ZnS:Cu+,Al3+; ZnS:Ag+,CF; ZnS:Ag+,Al3+; [Ba,Sr,Ca]2Sii-nO4-2n:Eu2+(wherein 0<n<0.2); [Ba,Sr,Ca]2[Mg,Zn]Si2O7:Eu2+; [Sr,Ca,Ba][Al,Ga,In]2S4:Eu2+;[Y,Gd,Tb,La,Sm,Pr,Lu]3[Al,Ga]5-aOi2-3 / 2a:Ce3+(wherein 0<a<0.5); [Ca,Sr]8[Mg,Zn](SiO4)4C12:Eu2+,Mn2+; Na2Gd2B2O7:Ce3+,Tb3+; [Sr,Ca,Ba,Mg,Zn]2P2O7:Eu2+,Mn2+; [Gd,Y,Lu,La]2O3:Eu3+,Bi3+; [Gd,Y,Lu,La]2O2S:Eu3+,Bi3+; [Gd,Y,Lu,La]VO4:Eu3+,Bi3+; [Ca,Sr,Mg]S:Eu2+,Ce3+; SrY2S4:Eu2+; CaLa2S4:Ce3+;[Ba,Sr,Ca]MgP2O7:Eu2+,Mn2+; [Y,Lu]2WOe:Eu3+,Mo6+; [Ba,Sr,Ca]bSigNm:Eu2+(wherein 2b+4g=3m); Ca3(SiO4)C12:Eu2+; [Lu,Sc,Y,Tb]2-u-vCevCai+uLiwMg2-wPw[Si,Ge]3-wOi2-u / 2 (where 0.5<u<l, 0<v<0.1, and 0<w<0.2); [Y,Lu,Gd]2-m [Y,Lu,Gd]CamSi4N6+mCi-m:Ce3+, (wherein 0<m<0.5); [Lu,Ca,Li,Mg,Y], alpha-SiAlON doped with Eu2+and / or Ce3+; Sr(LiAl3N4):Eu2+, [Ca,Sr,Ba]SiO2N2:Eu2+,Ce3+; beta-SiA10N:Eu2+;3.5MgO*0.5MgF2*GeO2:Mn4+; Cai-c-fCecEufAli+cSii-cN3, (where 0<c<0.2, 0<f<0.2);Cai-h-rCehEurAli-h(Mg,Zn)hSiN3, (where 0<h<0.2, 0<r<0.2); Cai-2s-tCes[Li,Na]sEutAlSiN3, (where 0<s<0.2, 0<t<0.2, s+t>0); [Sr, Ca]AlSiNs: and Eu2+,Ce3+, Li2CaSiO4:Eu2+.

[0077] In particular embodiments, additional phosphors include: [Y,Gd,Lu,Tb]3[Al,Ga]50i2:Ce3+, P-SiA10N:Eu2+, [Sr,Ca,Ba][Ga,Al]2S4:Eu2+, [Li,Ca]a- SiA10N:Eu2+, [Ba,Sr,Ca]2Si5N8:Eu2+, [Ca,Sr]AlSiN3:Eu2+, [Ba,Sr,Ca]LiAl3N4:Eu2+, [Sr,Ca,Mg]S:Eu2+, and [Ba,Sr,Ca]2Si2O4:Eu2+.

[0078] Other additional luminescent materials suitable for use in the molding material may include electroluminescent polymers such as polyfluorenes, preferably poly(9,9-dioctyl fluorene) and copolymers thereof, such as poly(9,9'-dioctylfluorene-co-bis-N,N'-(4- butylphenyl)diphenylamine) (F8-TFB); poly(vinylcarbazole) and polyphenylenevinylene and their derivatives. In addition, the light emitting layer may include a blue, yellow, orange, green or red phosphorescent dye or metal complex, a quantum dot material, or a combination thereof. Materials suitable for use as the phosphorescent dye include, but are not limited to,tri s(l -phenylisoquinoline) iridium (III) (red dye), tris(2-phenylpyridine) iridium (green dye) and iridium (III) bis(2-(4,6-difluorephenyl)pyridinato-N,C2) (blue dye). Commercially available fluorescent and phosphorescent metal complexes from ADS (American Dyes Source, Inc.) may also be used. ADS green dyes include ADS060GE, ADS061GE, ADS063GE, and ADS066GE, ADS078GE, and ADS090GE. ADS blue dyes include ADS064BE, ADS065BE, and ADS070BE. ADS red dyes include ADS067RE, ADS068RE, ADS069RE, ADS075RE, ADS076RE, ADS067RE, and ADS077RE.

[0079] The ratio of each of the individual phosphors and other luminescent materials in the molding material may vary depending on the characteristics of the desired light output. The relative proportions of the individual phosphors and other luminescent materials in the various molding materials may be adjusted such that when their emissions are blended and employed in a device, for example a lighting apparatus, there is produced visible light of predetermined x and y values on the CIE chromaticity diagram.

[0080] In one embodiment, the phosphor material may be present in the molded article in an amount of about 0.1 wt% to about 80 wt%. In one embodiment, the phosphor is present in an amount of about 5 wt% to about 75 wt%. In one embodiment, the phosphor is present in an amount of about 10 wt% to about 60 wt%. In one embodiment, the phosphor is present in an amount of about 50 wt% to about 70 wt%. The weight % is based on total weight of the molding material.

[0081] In one embodiment, the at least one resin may be present in the molding material in an amount up to about 95 wt%. In one embodiment, the at least one resin may be present in an amount up to 90 wt%. In one embodiment, the at least one resin may be present in an amount up to 85 wt%. In one embodiment, the at least one resin may be present in an amount up to 80 wt%. In one embodiment, the at least one resin may be present in an amount up to 75 wt%. In another embodiment, the at least one resin may be present in an amount up to about 70 wt%. In another embodiment, the at least one resin may be present in an amount from about 5 wt% to about 75 wt%. In another embodiment, the at least one resin is present in an amount of from about 10 wt% to about 70 wt%. In another embodiment, the at least one resin is present from about 20 wt% to about 50 wt%. The weight % is based on total weight of the molding material.

[0082] The molding material may include one or more solvents to further optimize the molding material properties. The amount of solvent, solvent polarity, and solvent vapor pressure can aid in making a stable material that meets viscosity, wettability, and optical density criteria of the molding material. The solvent may be present in an amount effectivefor dissolving the phosphor material and for adjusting the molding material to a desired viscosity.

[0083] Additional additives may be added to the molding material to further tailor the molding material properties, such as adhesion or cohesion, light scattering, evaporation rate, stability, shelf life, etc.

[0084] Additives may be added to the molding material in an amount of from about 5 wt% to about 20 wt%, based on the weight of the molding material.

[0085] In one embodiment, the molded article includes a phosphor material dispersed within the resin. In one embodiment, the resin comprises PMMA, polycarbonate, and / or PET. In some embodiment the molded article includes a narrow-band emission phosphor (e.g., PFS or NFS) in a polymer matrix. In some embodiments, the molded article includes phosphors with micron or sub-micron particle sizes. In other embodiments, the molded article includes nano-sized particles.

[0086] In one embodiment, the phosphor material may be present in the molded article in an amount of about 0.1 wt% to about 80 wt%. In one embodiment, the phosphor is present in an amount of about 5 wt% to about 75 wt%. In one embodiment, the phosphor is present in an amount of about 10 wt% to about 60 wt%. In one embodiment, the phosphor is present in an amount of about 50 wt% to about 70 wt%. The weight % is based on total weight of the molding material.

[0087] In one embodiment, the at least one resin may be present in the molding material in an amount up to about 95 wt%. In one embodiment, the at least one resin may be present in an amount up to 90 wt%. In one embodiment, the at least one resin may be present in an amount up to 85 wt%. In one embodiment, the at least one resin may be present in an amount up to 80 wt%. In one embodiment, the at least one resin may be present in an amount up to 75 wt%. In another embodiment, the at least one resin may be present in an amount up to about 70 wt%. In another embodiment, the at least one resin may be present in an amount from about 5 wt% to about 75 wt%. In another embodiment, the at least one resin is present in an amount of from about 10 wt% to about 70 wt%. In another embodiment, the at least one resin is present from about 20 wt% to about 50 wt%. The weight % is based on total weight of the molding material.

[0088] The molded article may include any suitable further additive or other component known in the art that facilitates the device. Additives may be added to the molded article in an amount of from about 5 wt% to about 20 wt%, based on the weight of the molded article. In one embodiment, the molded article includes scattering agents, such as titanium dioxide,aluminum oxide (AI2O3), zirconium oxide, indium tin oxide, cerium oxide, tantalum oxide, zinc oxide, magnesium fluoride (MgF2), calcium fluoride (CaF2), strontium fluoride (SrF2), barium fluoride (BaF2), silver fluoride (AgF), aluminum fluoride (AIF3) or combinations thereof. In some embodiments, the scattering aid is ZrCL or TiCL nanoparticles. Scattering agents provide an increased effective path length for the blue light and increase blue light absorption in the molded article.

[0089] The molded articles may have any desirable thickness. For molded articles including Mn4+doped phosphors having formula I and optically coupled and / or radiationally connected to a blue LED, thicker molded articles may provide improved blue to red conversion. For thinner molded articles, it is preferrable to include Mn4+doped phosphors with small particle sizes and having a Mn content of at least 1.4 wt%.

[0090] In one embodiment, a plastic layer or film may be placed on the excitation side of the molded article to change optical properties or improve reliability. For example, the plastic layer or film can act as a protective layer and protect the component from oxygen or moisture, can improve excitation source light (e.g., provide an anti -refl ection layer), create a more diffuse excitation source entering the molded color conversion part, and / or provide a more uniform phosphor emission light exiting the molded article. In one embodiment, the plastic layer or film has a low refractive index. The plastic layer or film may include polyethylene terephthalate (PET) or PVDF.

[0091] Devices according to the present disclosure include an LED light source radiationally connected and / or optically coupled to a molded article. In one embodiment, the molded article includes at least one resin and at least one phosphor material.

[0092] FIGs. 1 A-1E show a device 10, according to various embodiments of the present disclosure. Referring to FIG. 1 A, the device 10 includes an LED light source 12 and a molded article 14. The LED light source 12 may be a UV or blue emitting LED. In some embodiments, the LED light source 12 produces blue light in a wavelength range from about 380 nm to about 460 nm. In the device 10, the molded article 14 is radiationally coupled and / or optically coupled to the LED light source 12. Radiationally connected or coupled or optically coupled means that radiation from the LED light source 12 is able to excite the molded article 14, and the molded article 14 is able to emit light in response to the excitation by the radiation. The molded article 14 may be disposed on a part or portion of the LED light source 12 or located remotely at a distance from the LED light source 12. Light may travel from the LED light source 12 through the molded article 14.

[0093] FIG. IB shows an exemplary embodiment where the molded article 14 is in physical contact with LED light source 12. In other embodiments, the molded article 14 is remote from the LED light source 12. The LED light source 12 is disposed on a reflective layer 16. The reflective layer 16 reflects light from the LED light source 12 toward the LED light source and the molded article 14. The reflective layer 16 may be any material suitable for reflecting light. In one embodiment, the reflective layer 16 may be a metallic layer, such as aluminum, silver, silver alloys or aluminum alloys.

[0094] FIG. 1C shows an exemplary embodiment where the molded article 14 is disposed on the LED light source 12. An encapsulant or barrier layer 18 is disposed on the molded article 14. The encapsulant or barrier layer 18 may be a low temperature glass, or a polymer or resin known in the art, for example, an epoxy, silicone, epoxy-silicone, acrylate or a combination thereof. The encapsulant or barrier layer 18 should be transparent to allow light to be transmitted through those elements.

[0095] FIG. ID shows an exemplary embodiment where the LED light source is depicted as an array of LED light sources 12. In some embodiments, the LED light sources 12 are mini-LEDs or micro-LEDs.

[0096] FIG. IE shows an exemplary embodiment where the molded article 14 is located remotely from the LED light source 12, which is depicted as an array of LED light sources 12.

[0097] The general discussion of the example LED light source discussed herein is directed toward an inorganic LED based light source. Many white LEDs are based on blue or UV emitting GalnN chips. In addition to inorganic LED light sources, the term LED light source is meant to encompass all LED light sources, such as semiconductor laser diodes (LD), organic light emitting diodes (OLED) or a hybrid of LED and LD. Further, it should be understood that the LED light source may be replaced, supplemented or augmented by another radiation source unless otherwise noted and that any reference to semiconductor, semiconductor LED, or LED chip is merely representative of any appropriate radiation source, including, but not limited to, LDs and OLEDs.

[0098] The molded article 14 may be formed using compression molding or injection molding. The molding material used in the compression molding or injection molding may comprise at least one optically active material, such as a phosphor. The at least one optically active material may be present in any form such as powder, glass, or composite e.g., phosphor-polymer composite or phosphor-glass composite. Further, the molded article 14 may comprise a layer, sheet, disc, or a combination thereof. In some of these embodiments,the device 10 may include the molded article 14 in form of a phosphor wheel (not shown). The phosphor wheel may include the phosphor embedded in a glass. A phosphor wheel and related devices are described in WO 2017 / 196779.

[0099] In one embodiment, the molding material further comprises at least one resin. For example, in one embodiment the at least one resin comprises PMMA, polycarbonate, and / or PET. In a further embodiment, the molding material comprises the phosphor material dispersed within the at least one resin. In one embodiment, the raw molding material (e.g., the molding material before it is heated or processed in any way) is in the form of pellets, granules, casts, and / or the like.

[0100] The molded article is optically coupled or radiationally connected to an LED light source. In one embodiment, a white light blend may be obtained by blending the red phosphor material and the green phosphor material with an LED light source, such as a blue or UV LED.

[0101] FIG. 2 illustrates a lighting apparatus 20 or lamp, in accordance with some embodiments. The lighting apparatus 20 includes an LED chip 22 and leads 24 electrically attached to the LED chip 22. The leads 24 may comprise thin wires supported by a thicker lead frame(s) 26 or the leads 24 may comprise self-supported electrodes and the lead frame may be omitted. The leads 24 provide current to LED chip 22 and thus cause it to emit radiation.

[0102] A molded article 30 is optically coupled and / or radiationally connected to LED chip 22. In one embodiment, molded article 30 is located remotely from LED chip 22. In other embodiments, molded article 30 is in physical contact with LED chip 22. The molded article 30 may be formed by any appropriate method, for example, compression molding or injection molding. The light emitted by the LED chip 22 mixes with the light emitted by the molded article to produce desired emission.

[0103] With continued reference to FIG. 3, the LED chip 22 may be encapsulated within an envelope 28. The envelope 28 may be formed of, for example glass or plastic. The LED chip 22 may be enclosed by an encapsulant material 32. The encapsulant material 32 may be a low temperature glass, or a polymer or resin known in the art, for example, an epoxy, silicone, epoxy-silicone, acrylate or a combination thereof. In an alternative embodiment, the lighting apparatus 20 may only include the encapsulant material 32 without the envelope 28. Both the envelope 28 and the encapsulant material 32 should be transparent to allow light to be transmitted through those elements.

[0104] In some embodiments as illustrated in FIG. 3, the molded article 30 encapsulates the LED chip 22, instead of being formed directly on the LED chip 22, as shown in FIG. 4. The molded article 30 may comprise a phosphor material 36 interspersed within at least one resin and / or an encapsulant material. Blue light or UV light emitted by the LED chip 22 mixes with the light emitted by the molded article 30, and the mixed light transmits out from the lighting apparatus 20.

[0105] In yet another embodiment, the molded article 34 comprises a layer which is coated onto a surface of the envelope 28, instead of being located over the LED chip 22, as illustrated in FIG. 4. As shown, the molded article 34 is coated on an inside surface 29 of the envelope 28, although the molded article 34 may be coated on an outside surface of the envelope 28, if desired. The molded article 34 may be coated on the entire surface of the envelope 28 or only a top portion of the inside surface 29 of the envelope 28. The UV or blue light emitted by the LED chip 22 mixes with the light emitted by the molded article 34, and the mixed light transmits out. Of course, the molded article may be located in any two or all three locations (as shown in FIGs. 2-4) or in any other suitable location, such as separately from the envelope 28, remote or integrated into the LED chip 22, etc. In one embodiment, the molded article 34 may be located remotely from the LED chip 22. In another embodiment, the molded article 34 may be disposed on the LED chip 22.

[0106] In some embodiments, the molded article may be a single layer or multi-layered. In some embodiments, the molded article is a multi-layered structure where each layer of the multi-layered structure includes at least one phosphor material. In another embodiment, a device structure includes a molded article on an LED chip. In another embodiment, a device structure includes a molded article on an LED chip and a remote molded article including a phosphor material.

[0107] In any of the above structures illustrated in FIGs. 1-4, the lighting apparatus 20 may also include a plurality of scattering particles (not shown), which are embedded in the encapsulant material 32. The scattering particles may comprise, for example, alumina, silica, zirconia, or titania. The scattering particles effectively scatter the directional light emitted from the LED chip 22, preferably with a negligible amount of absorption.

[0108] By use of the phosphor materials described herein, devices can be provided producing white light for illumination having high luminosity and high CRI values for a wide range of color temperatures of interest (e.g., 2000 K to 10,000 K).

[0109] In one embodiment, the device includes a molded article having at least one side with a reflectivity of greater than 20%. FIG. 5 shows a device 100 according to oneembodiment of the present disclosure. Device 100 includes a molded article 104 having a first side 103 and a second side 105. Device 100 also includes a light source 106 located remotely from the molded article 104.

[0110] In one embodiment, the first side 103 and / or the second side 105 of the molded article 104 has a reflectivity greater than 20%. In one embodiment the first side 103 and / or the second side 105 of the molded article 104 includes a specular material. Specular materials have a reflectivity of at least 80% of visible or UV light and may include metals, such as aluminum, aluminum alloys, chromium, gold, nickel, silver or silver alloys. In one embodiment, the first side 103 and / or the second side 105 of the molded article 104 includes a metal selected from aluminum, aluminum alloys, chromium, gold, nickel, silver or silver alloys.[OHl] In some embodiments, at least one side of the molded article 104 has at least 20% reflectivity of UV or visible electromagnetic emissions. In another embodiment, at least one side of the molded article 104 has at least 30% reflectivity, at least 40% reflectivity or at least 50% reflectivity of UV or visible electromagnetic emissions. In another embodiment, at least one side of the molded article 104 has a reflectivity of at least about 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90% or at least 95%. In another embodiment, at least one side of the molded article 104 has a reflectivity from about 20% to 100%. In another embodiment, at least one side of the molded article 104 has a reflectivity from about 30% to 100% or from about 40% to 100%. In another embodiment, at least one side of the molded article 104 has a reflectivity from about 50% to 100%. In another embodiment, tat least one side of the molded article 104 has a reflectivity from about 60% to 100%. In another embodiment, at least one side of the molded article 104 has a reflectivity from about 70% to 100%. In another embodiment, at least one side of the molded article 104 has a reflectivity from about 80% to 100%. In another embodiment, at least one side of the molded article 104 has a reflectivity from about 90% to 100%.

[0112] The remote light source 106 is optically coupled and / or radiati onally connected to the molded article 104 and irradiates the molded article 104 through at least the first side 103 of the molded article 104. The blue or UV light from the light source travels in an attenuated manner through the molded article 104 and can be absorbed by the phosphor material and / or other luminescent material within the molded article 104. Light that is not absorbed may contact the second side 105 of the molded article 104 having a reflectivity of at least 20%, which will reflect a portion of the blue or UV light back through the molded article 104 where the blue or UV light again travels through the molded article 104 where itcan illuminate luminescent materials, such as phosphor material, that are present before exiting the molded article 104. Radiance emitted from excited phosphor material, can be emitted in any direction and some light may exit the molded article 104 at the second side 105, which will reflect at least 20% of the light back through the molded article 104 where it can emerge from the first side 103 of the molded article 104. Increasing the pathways for the UV or blue light through the color conversion component improves blue absorbance and phosphor emission intensity.

[0113] FIG. 6 shows a device 200 according to another embodiment of the present disclosure. Device 200 includes a molded article 204 having a first side 203 and a second side 205 and a reflective layer 206 located on the second side 205 of the molded article 204.

[0114] In some embodiments, the reflective layer 206 has at least 20% reflectivity of UV or visible electromagnetic emissions. In another embodiment, the reflective layer 206 has at least 30% reflectivity, at least 40% reflectivity or at least 50% reflectivity of UV or visible electromagnetic emissions. In another embodiment, the reflective layer 206 has a reflectivity of at least about 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90% or at least 95%. In another embodiment, the reflective layer 206 has a reflectivity from about 20% to 100%. In another embodiment, the reflective layer 206 has a reflectivity from about 30% to 100% or from about 40% to 100%. In another embodiment, the reflective layer 206 has a reflectivity from about 50% to 100%. In another embodiment, the reflective layer 206 has a reflectivity from about 60% to 100%. In another embodiment, the reflective layer 206 has a reflectivity from about 70% to 100%. In another embodiment, the reflective layer 206 has a reflectivity from about 80% to 100%. In another embodiment, the reflective layer 206 has a reflectivity from about 90% to 100%.

[0115] Reflective layer 206 may be a specular material or a diffuse reflective material with scattering agents. In some embodiments, reflective layer 206 may be a metallic layer, such as aluminum, aluminum alloys, chromium, gold, nickel, silver or silver alloys. In another embodiment, the reflective layer 206 may include a paint that is applied to the second side 205 of the molded article 204 where the paint includes scattering agents, such as barium sulfate (BaSCU), titanium dioxide (TiO?) or zirconium dioxide (ZrCh).

[0116] Device 200 also includes a light source 208 located remotely from the molded article 204. The remote light source 208 is optically coupled and / or radiationally connected to at least the first side 203 of the molded article 204 and irradiates the molded article 204 through the first side 203 of the molded article 204. The blue or UV light from the light source travels in an attenuated manner through the molded article 204 and can be absorbed byphosphor materials and / or other luminescent materials that may be present within the molded article 204. Light that is not absorbed may pass through the molded article 204 and contact reflective layer 206. The reflective layer 206 will reflect a portion of the blue or UV light back through the molded article 204 where the blue or UV light again travels through molded article 204 where it can illuminate phosphor material or other luminescent materials that are present before exiting the molded article 204.

[0117] Radiance emitted from excited phosphor material, can be emitted in any direction and some of the light may exit the molded article 204 at the second side 205. Light exiting the second side 205 of the molded article 204 will contact reflective layer 206, which will reflect at least a portion of the light back through the molded article 204 where it can emerge from the first side 203 of the molded article 204.

[0118] In one aspect, an article comprising the device as previously described is provided. Generally, the device may be included in any suitable article known in the art that facilitates the use of the device.

[0119] Devices of the present disclosure include lighting and display apparatuses for general illumination applications. Examples of such devices include chromatic lamps, xenon excitation lamps, UV excitation marking systems, automotive headlamps, automotive taillights, an aircraft light, an aircraft part, theatre projectors, laser pumped devices, and / or point sensors. The foregoing list is meant to be merely exemplary and not exhaustive.

[0120] In some embodiments, an automotive tail-light having reflective geometry is provided. The automotive tail-light includes at least one LED light source and a molded article comprising a phosphor material, the molded article having a first side and a second side. The at least one LED light source is located remotely from the molded article, wherein the LED light source is optically coupled and / or radiationally connected to at least the first side of the molded article. The molded article is formed from a molding material. The molding material comprises at least one resin and at least one phosphor material. The at least one phosphor material comprises a Mn4+doped phosphor of formula I,Ax[MFy]:Mn4+I where A is Li, Na, K, Rb, Cs, NEL, or a combination thereof; M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd, or a combination thereof; x is the absolute value of the charge of the [MFy] ion; and y is 5, 6 or 7. The at least one resin comprises PMMA, PET, and / or polycarbonate.

[0121] In some embodiments, the article is selected from the group consisting of an illumination device, a lighting apparatus, chromatic lamps, solid state lighting products, transportation displays, xenon excitation lamps, UV excitation marking systems, home and theater projections, laser pumped devices, point sensors, an automotive or aviation light, and automotive or aviation part, an automotive tail-light, an automotive headlamp, and combinations thereof. The list of these applications is meant to be merely exemplary and not exhaustive.

[0122] In one embodiment, the molded article is formed using a compression molding process. FIGs. 7A and 7B are schematic diagrams of a compression mold 700 during a compression molding process. More particularly, FIG. 7A shows the compression mold 700 in an open position and FIG. 7B shows the compression mold 700 in a closed position. In the embodiment illustrated in FIGs. 7A and 7B, mold 700 includes a first component 702 and a second component 704, however, mold 700 may include more or less components to achieve the desired effect. In one embodiment, mold 700 may further include one or more overflow grooves (not shown) for capturing excess molding material.

[0123] In the embodiment illustrated in FIG. 7 A, a molding material 710 is placed in an open, heated cavity 712 of mold 700. In one embodiment, the molding material 710 is be preheated before it is placed in the cavity 712. In one embodiment, the molding material, before any processing, is in a pellet or granular form. However, before processing, the molding material may be in various other forms. In some embodiments, the molding material is cast before the compression molding process. The molding material 710 includes at least one resin (e.g., PMMA, polycarbonate, and / or PET) and at least one optically active material (e.g., a phosphor material such as PFS and / or YAG).

[0124] After the molding material is placed in the cavity, 712, the mold 700 is then closed (e.g., by a top force, plug member, or the like), as illustrated in FIG. 7B. Pressure is applied to force the material into contact with all areas of the cavity 712 of mold 700. In one embodiment, heat is also applied. The pressure and / or heat is maintained until the molding material is cured. In this way, molding material conforms to the shape of the cavity 712 of the mold 700 to produce a molded article 720. In one embodiment, the process further comprises removing excess molding material from the molded article.

[0125] The cavity 712, and therefore the molded article, may comprise a variety of shapes and / or geometries, including but not limited to circular shape, a rectangular shape, or any other desired shape and / or geometry. For example, the molded article 720 of FIG. 7B is adisc shape. The molded article 720 may then be radiationally coupled and / or optically coupled to an LED light source (e.g., as shown in FIGs. 1 A-6 and 9-11).

[0126] In the embodiment illustrated in FIGs. 7A and 7B, the mold 700 includes a cavity 712 in which a molding material 710 may be placed. However, the mold 700 may include a plurality of mold cavities and / or a plurality of molds may be used. For example, FIGs. 8 A and 8B illustrate a mold 800 including a plurality of cavities 812, 814, 816 in which molding material 810 can be placed. The molding material 810 includes at least one resin (e.g., PMMA, polycarbonate, PET, or the like) and at least one optically active material (e.g., a phosphor material such as PFS and / or YAG). The mold 800 includes a first mold article 802 and a second mold article 804.

[0127] The mold articles that are produced using the materials and processes disclosed above may be used in various devices, such as those illustrated in FIGs. 1A-6 and 9-11.

[0128] FIG. 9 illustrates a device 900 including an LED light source 902 optically coupled and / or radiationally connected to a molded article 904 in a transmissive geometry. In one embodiment, the molded article 904 is located remotely from the LED light source 902, as shown in FIG. 9. In another embodiment, the molded article 903 is in physical contact with the LED light source 902. In one embodiment, the LED light source 902 comprises a blue or UV LED. The molded article 904 is formed using any of the processes described above, and is formed from a molding material comprising at least one phosphor (e.g., PFS and / or YAG) and at least one resin (e.g., PMMA, polycarbonate, and / or PET). The molded article 904 includes a first side 906 and a second side 908.

[0129] LED light source 902 irradiates the molded article 904 through the second side 908 of the molded article 904. The blue or UV light from the LED light source travels in an attenuated manner through the molded article 904 and can be absorbed by the phosphor material and / or other luminescent material within the molded article 904. Radiance emitted from excited phosphor material is emitted at the first side 906 of the molded article 904.

[0130] FIG. 10 illustrates a device 1000 including an LED light source 1002 optically coupled and / or radiationally connected to a molded article 1004 in a reflective geometry. In one embodiment, the molded article 1004 is located remotely from the LED light source 1002. In one embodiment, the LED light source 1002 comprises a blue or UV LED. The molded article 1004 is formed using any of the processes described above, and is formed from a molding material comprising at least one phosphor (e.g., PFS and / or YAG) and at least one resin (e.g., PMMA, polycarbonate, and / or PET). The molded article 1004 includes a first side 1006 and a second side 1008.

[0131] In one embodiment, at least one side of the molded article 1004 has a reflectivity greater than 20%. In one embodiment, the first side 1006 and / or the second side 1008 of the molded article 1004 has a reflectivity greater than 20%. In one embodiment, the first side 1006, the second side 1008 and / or at least some other portion of the molded article 1004 includes a specular material. Specular materials have a reflectivity of at least 80% of visible or UV light and may include metals, such as aluminum, aluminum alloys, chromium, gold, nickel, silver or silver alloys. In one embodiment, the second side 1008 of the molded article 1004 includes a metal selected from aluminum, aluminum alloys, chromium, gold, nickel, silver or silver alloys.

[0132] In some embodiments, at least one side of the molded article 1004 has at least 20% reflectivity of UV or visible electromagnetic emissions. In another embodiment, at least one side of the molded article 1004 has at least 30% reflectivity, at least 40% reflectivity or at least 50% reflectivity of UV or visible electromagnetic emissions. In another embodiment, at least one side of the molded article 1004 has a reflectivity of at least about 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90% or at least 95%. In another embodiment, at least one side of the molded article 1004 has a reflectivity from about 20% to 100%. In another embodiment, at least one side of the molded article 1004 has a reflectivity from about 30% to 100% or from about 40% to 100%. In another embodiment, at least one side of the molded article 1004 has a reflectivity from about 50% to 100%. In another embodiment, tat least one side of the molded article 1004 has a reflectivity from about 60% to 100%. In another embodiment, at least one side of the molded article 1004 has a reflectivity from about 70% to 100%. In another embodiment, at least one side of the molded article 1004 has a reflectivity from about 80% to 100%. In another embodiment, at least one side of the molded article 1004 has a reflectivity from about 90% to 100%.

[0133] The remote light source 1002 is optically coupled and / or radiati onally connected to the molded article 1004 and irradiates the molded article 1004 through at least the first side 1006 of the molded article 104. The blue or UV light from the light source travels in an attenuated manner through the molded article 1004 and can be absorbed by the phosphor material and / or other luminescent material within the molded article 1004. Light that is not absorbed may contact the first side 1006 and / or the second side 1008 of the molded article 1004 having a reflectivity of at least 20%, which will reflect a portion of the blue or UV light back through the molded article 1004 where the blue or UV light again travels through the molded article 1004 where it can illuminate luminescent materials, such as phosphor material, that are present before exiting the molded article 1004. Radiance emitted fromexcited phosphor material, can be emitted in any direction and some light may exit the molded article 1004 at the second side 1008, which will reflect at least 20% of the light back through the molded article 104 where it can emerge from the first side 1006 of the molded article 1004. Increasing the pathways for the UV or blue light through the color conversion component improves blue absorbance and phosphor emission intensity. Additionally, or alternatively, device 1000 may include a reflective layer located on the second side 1008 of molded article 1004 (see e.g., FIG. 6). Light that is not absorbed may pass through the molded article 1004 and contact the reflective layer. The reflective layer will reflect a portion of the blue or UV light back through the molded article 1004 where the blue or UV light again travels through molded article 1004 where it can illuminate phosphor material or other luminescent materials that are present before exiting the molded article 1004.

[0134] In some embodiments, the reflective layer has at least 20% reflectivity of UV or visible electromagnetic emissions. In another embodiment, the reflective layer has at least 30% reflectivity, at least 40% reflectivity or at least 50% reflectivity of UV or visible electromagnetic emissions. In another embodiment, the reflective layer has a reflectivity of at least about 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90% or at least 95%. In another embodiment, the reflective layer has a reflectivity from about 20% to 100%. In another embodiment, the reflective layer has a reflectivity from about 30% to 100% or from about 40% to 100%. In another embodiment, the reflective layer has a reflectivity from about 50% to 100%. In another embodiment, the reflective layer has a reflectivity from about 60% to 100%. In another embodiment, the reflective layer has a reflectivity from about 70% to 100%. In another embodiment, the reflective layer has a reflectivity from about 80% to 100%. In another embodiment, the reflective layer has a reflectivity from about 90% to 100%.

[0135] FIG. 11 illustrates a device 1100 including an LED light source 1102 optically coupled and / or radiati onally connected to a molded article 1104 in an edge-lit geometry. In one embodiment, the molded article 1104 is located remotely from the LED light source 1002, as shown in FIG. 11. In another embodiment, the molded article 1104 is in physical contact with LED light source 1002. In one embodiment, the LED light source 1102 comprises a blue or UV LED. The molded article 1104 is formed using any of the processes described above, and is formed from a molding material comprising at least one phosphor (e.g., PFS and / or YAG) and at least one resin (e.g., PMMA, polycarbonate, and / or PET). The molded article 1104 includes a first side 1106, a second side 1108, and a third side 1110.

[0136] In one embodiment, at least one side of the molded article 1104 has a reflectivity greater than 20%. In one embodiment, the second side 1108 of the molded article 1104 has a reflectivity greater than 20%. In one embodiment, at least the second side 1108 of the molded article 1104 includes a specular material. Specular materials have a reflectivity of at least 80% of visible or UV light and may include metals, such as aluminum, aluminum alloys, chromium, gold, nickel, silver or silver alloys. In one embodiment, the second side 1108 of the molded article 1104 includes a metal selected from aluminum, aluminum alloys, chromium, gold, nickel, silver or silver alloys.

[0137] In some embodiments, at least one side of the molded article 1104 has at least 20% reflectivity of UV or visible electromagnetic emissions. In another embodiment, at least one side of the molded article 1104 has at least 30% reflectivity, at least 40% reflectivity or at least 50% reflectivity of UV or visible electromagnetic emissions. In another embodiment, at least one side of the molded article 1104 has a reflectivity of at least about 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90% or at least 95%. In another embodiment, at least one side of the molded article 1104 has a reflectivity from about 20% to 100%. In another embodiment, at least one side of the molded article 1004 has a reflectivity from about 30% to 100% or from about 40% to 100%. In another embodiment, at least one side of the molded article 1104 has a reflectivity from about 50% to 100%. In another embodiment, tat least one side of the molded article 1104 has a reflectivity from about 60% to 100%. In another embodiment, at least one side of the molded article 1104 has a reflectivity from about 70% to 100%. In another embodiment, at least one side of the molded article 1104 has a reflectivity from about 80% to 100%. In another embodiment, at least one side of the molded article 1104 has a reflectivity from about 90% to 100%.

[0138] The remote light source 1102 is optically coupled and / or radiati onally connected to the molded article 1104 and irradiates the molded article 1104 through at least the third side 1110 of the molded article 1104. The blue or UV light from the light source travels in an attenuated manner through the molded article 1104 and can be absorbed by the phosphor material and / or other luminescent material within the molded article 1104. Light that is not absorbed may contact the second side 1108 of the molded article 1104 having a reflectivity of at least 20%, which will reflect a portion of the blue or UV light back through the molded article 1104 where the blue or UV light again travels through the molded article 1104 where it can illuminate luminescent materials, such as phosphor material, that are present before exiting the molded article 1104. Radiance emitted from excited phosphor material, can be emitted in any direction and some light may exit the molded article 1104 at the second side1108, which will reflect at least 20% of the light back through the molded article 1104 where it can emerge from the first side 1106 of the molded article 1104. Increasing the pathways for the UV or blue light through the color conversion component improves blue absorbance and phosphor emission intensity. Additionally, or alternatively, device 1100 may include a reflective layer located on the second side 1108 of molded article 1104. Light that is not absorbed may pass through the molded article 1104 and contact the reflective layer. The reflective layer will reflect a portion of the blue or UV light back through the molded article 1104 where the blue or UV light again travels through molded article 1104 where it can illuminate phosphor material or other luminescent materials that are present before exiting the molded article 1104.

[0139] In some embodiments, the reflective layer has at least 20% reflectivity of UV or visible electromagnetic emissions. In another embodiment, the reflective layer has at least 30% reflectivity, at least 40% reflectivity or at least 50% reflectivity of UV or visible electromagnetic emissions. In another embodiment, the reflective layer has a reflectivity of at least about 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90% or at least 95%. In another embodiment, the reflective layer has a reflectivity from about 20% to 100%. In another embodiment, the reflective layer has a reflectivity from about 30% to 100% or from about 40% to 100%. In another embodiment, the reflective layer has a reflectivity from about 50% to 100%. In another embodiment, the reflective layer has a reflectivity from about 60% to 100%. In another embodiment, the reflective layer has a reflectivity from about 70% to 100%. In another embodiment, the reflective layer has a reflectivity from about 80% to 100%. In another embodiment, the reflective layer has a reflectivity from about 90% to 100%.

[0140] FIGs. 12A-12B are schematic diagrams of another compression mold 1200 during a compression molding process. More particularly, FIG. 12A shows the compression mold 1200 in an open position and FIG.12B shows the compression mold 1200 in a closed position. In the embodiment illustrated in FIGs. 12A and 12B, mold 1200 includes a first component 1202 and a second component 1204, however, mold 1200 may include more or less components. In one embodiment, mold 1200 may further include one or more overflow grooves (not shown) for capturing excess molding material.

[0141] In the embodiment illustrated in FIG. 12A, a molding material 1210 is placed in an open, heated cavity 1212 of mold 1200. In one embodiment, the molding material 1210 is be preheated before it is placed in the cavity 1212. In one embodiment, the molding material, before any processing, is in a pellet, granular, and / or cast form. However, before processing,the molding material may be in various other forms. The molding material 1210 includes at least one resin (e.g., PMMA, polycarbonate, and / or PET) and at least one optically active material (e.g., a phosphor material such as PFS and / or YAG).

[0142] After the molding material is placed in the cavity, 1212, the mold 1200 is then closed (e.g., by a top force, plug member, or the like), as illustrated in FIG. 12B. Pressure is applied to force the material into contact with all areas of the cavity 1212 of mold 1200. In one embodiment, heat is also applied. The pressure and / or heat is maintained until the molding material is cured. In this way, molding material conforms to the shape of the cavity 1212 of the mold 1200 to produce a molded article 1220. In one embodiment, the process further comprises removing excess molding material from the resulting component.

[0143] The cavity 1212, and therefore the resulting molded article, may comprise a variety of shapes and / or geometries, including but not limited to circular shape, a rectangular shape, or any other desired shape and / or geometry. For example, the molded article 1220 includes a curved surface 1222. In some embodiments, the molded article can include a plurality of curved surfaces. In one embodiment, the molded article includes one or more areas that are free of the optically active material. For example, in one embodiment, the molded article 1220 includes a first area 1224 in which no optically active material is present and a second area 1226 in which at least one optically active material is present (e.g., a phosphor material such as PFS and / or YAG). In one embodiment, such as the embodiment illustrated in FIG. 12C, the first area 1224 in which no optically active material is present is comprised of a transparent resin. Additionally, or alternatively, the first area 1224 in which no optically active material is present is adjacent to one or more curved surfaces. In this way, the first area 1224 may act as a lens. In some embodiments, the molded article may comprise a plurality of areas in which no optically active material is present. The areas with different characteristics (e.g., with at least one optically active material, without an optically active material) may be achieved by using a plurality of different molding materials. Additionally, the mold may include a plurality of different cavities in which the different molding materials are placed. The molded article 720 may then be radiationally coupled and / or optically coupled to an LED light source (e.g., as shown in FIGs. 1 A-6 and 9-11).

[0144] In the embodiment illustrated in FIGs. 12A and 12B, the mold 1200 includes a cavity 1212 in which a molding material 1210 may be placed. However, the mold 1200 may include a plurality of mold cavities and / or a plurality of molds may be used.

[0145] Molded articles in accordance with the present disclosure may also be produced using injection molding. FIGs. 13A-13C are schematic diagrams of an injection moldmachine 1300 during an injection molding process. More particularly, FIG. 13A shows the injection mold machine 1300 while a molding material 1310 is fed into a heated barrel 1330 which is heated via one or more heaters 1332. The molding material may be in pellet, granular, cast, and / or any other form. The molding material 1310 includes at least one resin (e.g., PMMA, polycarbonate, and / or PET) and at least one optically active material (e.g., a phosphor material such as PFS and / or YAG).

[0146] The heated barrel 1330 includes a helical screw 1334 which forces the molding material into one or more cavities 1342 of a mold 1340, as shown in FIG. 13B. Mold 1340 remains closed until the molding material cools and hardens to the configuration of the cavity 1342 to form a molded article 1320, as shown in FIG. 13C.

[0147] The cavity 1212, and therefore the resulting molded article, may comprise a variety of shapes and / or geometries, including but not limited to circular shape, a rectangular shape, or any other desired shape and / or geometry. The molded article 1220 may then be radiationally coupled and / or optically coupled to an LED light source (e.g., as shown in FIGs. 1A-6 and 9-11).

[0148] In the embodiment illustrated in FIGs. 13 A and 13B, the mold 1340 includes a cavity 1342 in which a molding material 1310 may be placed. However, the mold 1340 may include a plurality of mold cavities and / or a plurality of molds may be used.

[0149] In one embodiment, a two-shot mold may be used. Two-shot, double-shot, or multi-shot molds are designed to “overmold” (e.g., two or more components are molded over top of one another). In one embodiment, the injection molding machine includes a plurality of injection units. By using a two-shot mold, two separate material may be incorporated into one molded article. For example, a first shot may be used to inject a first molding material into the mold and a second shot may be used to inject a second molding material into the mold. The first molding material may include at least one optically active material (e.g., a phosphor such as PFS and / or YAG) and the second molding material may be free of an optically active material. In one embodiment, the second molding material may comprise a transparent resin and may be used to act as a lens.

[0150] In embodiments in accordance with the present disclosure, the molding material described above with regards to FIGs. 7A-13B includes at least one resin and at least one phosphor material. In one embodiment, the at least one resin comprises PMMA, polycarbonate, and / or PET. In one embodiment, the molding material further comprises at least one solvent. In one embodiment, the at least one optically active material includes a Mn4+doped phosphor of formula I,Ax[MFy]:Mn4+I where A is Li, Na, K, Rb, Cs, NH4, or a combination thereof; M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd, or a combination thereof; x is the absolute value of the charge of the [MFy] ion; and y is 5, 6 or 7. In one embodiment, the phosphor material has a D50 particle size of less than 15 microns. In another embodiment, the phosphor material has a D50 particle size of more than 15 microns. In one embodiment, the phosphor material further comprises an additional phosphor, such as YAG. The resulting molded articles maintain the properties of the phosphor material. In this way, molded articles are formed in an efficient, reproducible, and cost-effective manner. Further, using compression molding to form the color conversion components helps avoid some of the drawbacks with conventional techniques for forming optically active components, such as air bubbles.EXAMPLES

[0151] Mix and compression molding process

[0152] PFS powder was added to PMMA powder and shaken for about 1 minute. The resulting power was added to a rheology disc mold. Using a tetrahedron press, the powder was pressed under 4,000 lbs. for 5 minutes at 160 °C. The mold was then removed and placed into the cold press side of the tetrahedron press under 4,000 lbs. until the mold temperature reached 80 °C. The mold was removed and placed into a room temperature carver pressure. Using a brass cylinder, the part was pressed out of the mold and parts were removed, bagged, and labeled. The loading of the PFS in PMMA ranged from 10% to 40%. PMMA only was also molded under the same conditions as a blank comparison.

[0153] Cast and compression molding process

[0154] PMMA was obtained and reported to have a molecular weight of 102,000 g / mol. Chloroform and toluene of high purity were also obtained. Solvents were dried on a molecular sieve before use. Polymer solutions were cast on AU4G aluminum discs and the solvent was evaporated at room temperature over 48 hours. After evaporation, solid components were obtained. The solid components were then inserted into the rheology disc mold and pressed at 160 °C for PMMA, 200 °C for polycarbonate, and 216 °C for PET. The mold was then removed at placed into a room temperature carver pressure. Using a brass cylinder, the parts were pressed out of the mold and the parts were removed, bagged, and labeled.

[0155] Polycarbonate was dissolved in chloroform at 12.5 wt% in a glass jar to form a clear solution. Approximately 16 grams of the solution was poured into each of 3 vials and PFS powder was added to reach the wt% of PFS to polymer indicated. The powder was incorporated first by gently stirring with a spatula then by rolling for several days at 10 RPM. The suspension was poured into aluminum tins and allowed to dry first at room temperature overnight, then at 60 °C in a vacuum over for 24 hours.

[0156] A first batch of PMMA molded articles were prepared using the same process, except the PMMA solution was 33 wt% in 80 / 20 toluene / chloroform and the mass solution in each vial was approximately 6 grams. After rolling over a few days, the PFS samples at 30 wt% and 60 wt% were significantly browned.

[0157] A second batch of PMMA molded articles were prepared by diluting the vial further with 10 grams of chloroform and skipping the rolling step. The PFS dispersed well in a short period of time. The mold was placed in a vacuum oven to remove bubbles and raised to temperature slowly.

[0158] In some cases, the parts that were cast and compression molded produced more uniform (e.g., homogeneous) and bright parts than the parts that were mixed then compression molded.

[0159] Table 1 details KSF powder configuration for two KSF samples: 68 type and 841 type.Table 1 : KSF powder characterization

[0160] Table 2 details relative brightness percent and photoluminescent decay times measured for 30 molded parts formed in accordance with the disclosed materials and processes in a reflective geometry. For each sample, Table 2 details the type of KSF sample (e.g., 68 type KSF or 841 type KSF), KSF wt%, resin type, process type (e.g., mix followed by compression molding or cast followed by compression molding), and compression molding instrument temperature (e.g., barrel mold temperature). PMMA parts were compression molded with compression molding instrument temperatures at about 400 °F,while polycarbonate parts were molded with compression molding instrument temperatures at about 500 °F.Table 2: Molded KSF parts in reflective geometry

[0161] As shown in Table 2, both 841 and 68 type KSF formed compression molded parts when compression molding instrument was heated up to about 500 °F without degradation of KSF phosphor. This was an unexpected result, as the high temperatures and / or high pressure was expected to degrade the phosphor. Part 30, which is part 16 placed in boiling water for about 1 hour, shows what a degraded part looks like. A significant drop in brightness and photoluminescent decay time was observed in part 30. More particularly, part 30 showed a drop in brightness from about 33.8% to about 6.8% and a significant drop in photoluminescent decay time. None of the compression molded articles with KSF demonstrated a brightness and / or photoluminescent decay time similar to that of a degraded part (e.g., part 30).

[0162] Parts 28 and 29 were formed from silicone and processed under much gentler conditions than the other parts. More particularly, parts 28 and 29 were formed using instruments heated to 90 °C (about 194 °F) as compared to 400 °F and 500 °F. Parts 28 and 29 show similar photoluminescent decay times and brightness compared to the other molded parts formed under more extreme conditions.

[0163] Table 3 details relative brightness percent and percent transmission of 450nm light (e.g., blue light) measured for molded part samples 6-9 in a transmissive geometry. For each sample, Table 3 details the type of KSF sample (e.g., 68 type KSF or 841 type KSF), KSF wt%, resin type, process type (e.g., mix followed by compression molding or castfollowed by compression molding), and compression molding instrument temperature (e.g., barrel mold temperature).Table 3: Molded KSF parts in transmissive geometry

[0164] As shown in Tables 2 and 3, whether in reflective or transmissive excitation geometry, the brightest parts comprise 30-60 wt% KSF for both particle types (e.g., 68 type KSF and 841 type KSF). Further, the decrease in brightness is less at lower KSF wt% when excited in a transmissive geometry as compared to a reflective geometry.

[0165] As shown in Table 3, minimal blue light is able to pass through the 30 wt% and 60 wt% loaded molded articles. Low KSF loading (e.g., 10 wt% KSF) results in some blue transmission, producing a more magenta color point, which may be desirable in certain applications. A blue reflecting and / or absorbing filter may be used to produce a more red color point.

[0166] In one embodiment, a molded article is formed from a molding material, the molding material comprising at least one phosphor material and at least one resin, and wherein the at least one phosphor material includes a Mn4+doped phosphor of formula I,Ax[MFy]:Mn4+Iwhere A is Li, Na, K, Rb, Cs, NH4, or a combination thereof; M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd, or a combination thereof; x is an absolute value of a charge of the [MFy] ion; and y is 5, 6 or 7.

[0167] In one embodiment, the Mn4+doped phosphor of formula I is present in an amount of about 5 wt% to about 75 wt% based on a weight of the molding material.

[0168] In one embodiment, the Mn4+doped phosphor of formula I is present in an amount of about 10 wt% to about 60 wt% based on a weight of the molding material.

[0169] In one embodiment, the Mn4+doped phosphor of formula I is present in an amount of about 50 wt% to about 70 wt% based on a weight of the molding material.

[0170] In one embodiment, the Mn4+doped phosphor is selected from K2[GeFe]:Mn4+, K2[SiF6]:Mn4+, K2[TiF6]:Mn4+, K2[SnF6]:Mn4+, Cs2[TiF6]:Mn4+, Rb2[TiF6] Mn4+, Cs2[SiF6]:Mn4+, Rb2[SiF6]:Mn4+, Na2[SiF6]:Mn4+, Na2[TiF6]:Mn4+, Na2[ZrF6]:Mn4+, K3[ZrF7]:Mn4+, K3[BiF6] K3[YF6]:Mn4+, K3[LaF6]:Mn4+, K3[GdF6]:Mn4+, K3[NbF7]:Mn4+, and K3[TaF7]:Mn4+.

[0171] In one embodiment, the Mn4+phosphor of formula I is K2SiFe:Mn4+or Na2[SiF6]:Mn4+.

[0172] In one embodiment, the at least one resin comprises at least one of polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), or polycarbonate (PC).

[0173] In one embodiment, the Mn4+phosphor of formula I is at least partially coated with a surface coating, wherein the surface coating comprises at least one of a hydrophobic coating, a metal fluoride coating, or an organic coating.

[0174] In one embodiment, the molding material further comprises at least one solvent.

[0175] In one embodiment, the phosphor material further comprises at least one rare earth containing Garnet phosphor.

[0176] In one embodiment, the at least one rare earth Garnet phosphor comprises Yttrium Aluminum Garnet phosphor (YAG).

[0177] In one embodiment, the molding material further comprises at least one scattering agent.

[0178] In one embodiment, the at least one scattering agent further comprises titanium dioxide, aluminum oxide (A12O3), zirconium oxide, indium tin oxide, cerium oxide, tantalum oxide, zinc oxide, magnesium fluoride (MgF2), calcium fluoride (CaF2), strontium fluoride (SrF2), barium fluoride (BaF2), silver fluoride (AgF), aluminum fluoride (A1F3), or combinations thereof.

[0179] In one embodiment, the at least one phosphor material further includes at least one of [Y,Gd,Tb,La,Sm,Pr,Lu]3[Al,Ga]5-aOi2-3 / 2a:Ce3+(wherein 0<a<0.5); beta-Si A10N:Eu2+; [Sr,Ca,Ba][Al,Ga,In]2S4:Eu2+; alpha-SiAlON doped with Eu2+and / or Ce3+; Cai-h-rCehEurAli. h(Mg,Zn)hSiN3, (where 0<h<0.2, 0<r<0.2); Sr(LiALN4):Eu2+; [Ca,Sr,Mg]S:Eu2+,Ce3+; [Ba,Sr,Ca]bSigNm:Eu2+(wherein 2b+4g=3m); or combinations thereof.

[0180] In one embodiment, the molded article is prepared by compression molding.

[0181] In one embodiment, the molded article is prepared by injection molding.

[0182] In one embodiment, a molded article is formed from a molding material, the molding material comprising at least one phosphor material and at least one resin, and wherein the at least one phosphor material comprises a Mn4+doped phosphor of formula I, wherein the Mn4+ doped phosphor has a D50 particle size less than 15 microns,Ax[MFy]:Mn4+I where A is Li, Na, K, Rb, Cs, NEL, or a combination thereof; M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd, or a combination thereof; x is an absolute value of a charge of the [MFy] ion; and y is 5, 6 or 7.

[0183] In one embodiment, a molded article prepared by making a resin formulation comprising at least one phosphor material, at least one resin, and at least one solvent, wherein the at least one phosphor material comprising a Mn4+doped phosphor of formula I,Ax[MFy]:Mn4+I where A is Li, Na, K, Rb, Cs, NFL, or a combination thereof; M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd, or a combination thereof; x is an absolute value of a charge of the [MFy] ion; and y is 5, 6 or 7, and the resin formulation is cured to form the molded article.

[0184] In one embodiment, a device comprising an LED light source is optically coupled and / or radiationally connected to a molded article, the molded article formed from a molding material, the molding material comprising at least one resin and at least one phosphor material, and wherein the at least one phosphor material comprises a Mn4+doped phosphor of formula I,Ax[MFy]:Mn4+Iwhere A is Li, Na, K, Rb, Cs, NH4, or a combination thereof; M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd, or a combination thereof; x is an absolute value of a charge of the [MFy] ion; and y is 5, 6 or 7.

[0185] In one embodiment, the Mn4+doped phosphor of formula I has a D50 particle size less than 15 microns.

[0186] In one embodiment, the Mn4+doped phosphor of formula I has a D50 particle size greater than or equal to 15 microns.

[0187] In one embodiment, the LED light source is a UV emitting LED or a blue emitting LED.

[0188] In one embodiment, the molded article is in physical contact directly on the LED light source.

[0189] In one embodiment, the molded article is remotely located from the LED light source.

[0190] In one embodiment, the Mn4+doped phosphor of formula I is present in an amount of about 5 wt% to about 75 wt% based on a weight of the molding material.

[0191] In one embodiment, the Mn4+doped phosphor of formula I is present in an amount of about 10 wt% to about 60 wt% based on a weight of the molding material.

[0192] In one embodiment, the Mn4+doped phosphor is selected from K2[GeFe]:Mn4+, K2[SiF6]:Mn4+, K2[TiF6]:Mn4+, K2[SnF6]:Mn4+, Cs2[TiF6]:Mn4+, Rb2[TiF6] Mn4+, Cs2[SiF6]:Mn4+, Rb2[SiF6]:Mn4+, Na2[SiF6]:Mn4+, Na2[TiF6]:Mn4+, Na2[ZrF6]:Mn4+, K3[ZrF7]:Mn4+, K3[BiF6] K3[YF6]:Mn4+, K3[LaF6]:Mn4+, K3[GdF6]:Mn4+, K3[NbF7]:Mn4+, and K3[TaF7]:Mn4+.

[0193] In one embodiment, the Mn4+phosphor of formula I is K2SiFe:Mn4+or Na2[SiF6]:Mn4+.

[0194] In one embodiment, the at least one resin comprises at least one of polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), or polycarbonate (PC).

[0195] In one embodiment, the Mn4+phosphor of formula I is at least partially coated with a surface coating, wherein the surface coating comprises at least one of a hydrophobic coating, a metal fluoride coating, or an organic coating.

[0196] In one embodiment, the molding material further comprises at least one solvent.

[0197] In one embodiment, the phosphor material further comprises at least one rare earth containing Garnet phosphor.

[0198] In one embodiment, the at least one rare earth Garnet phosphor comprises Yttrium Aluminum Garnet phosphor (YAG).

[0199] In one embodiment, the article is selected from the group consisting of an illumination device, a lighting apparatus, an automotive light, an automotive tail-light, an aviation light, and combinations thereof.

[0200] In one embodiment, a device comprises: a molded article having a first side and a second side, wherein the molded article is formed from a molding material, and the molding material comprises at least one resin and at least one phosphor material, an LED light source located remotely from the molded article, wherein the LED light source is optically coupled and / or radiationally connected to at least the first side of the molded article, wherein:(a) at least one of the first side of the molded article or the second side of the molded article has a reflectivity of at least 20%, or(b) the device further comprises a back reflective layer located on the second side of the molded article.

[0201] In one embodiment, light emitted from the LED light source enters through the first side of the molded article.

[0202] In one embodiment, the molded article has a third side connecting the first side of the molded article and the second side of the molded article, wherein the LED light source comprises an edge-lit LED panel, and wherein light emitted from the LED light source enters through the third side of the molded article.

[0203] In one embodiment, the molded article includes at least one transparent region comprising a transparent resin.

[0204] In one embodiment, the at least one transparent region includes one or more curved surfaces.

[0205] In one embodiment, the at least one phosphor material comprises a Mn4+doped phosphor of formula I, wherein the Mn4+doped phosphor has a D50 particle size less than 15 microns,Ax[MFy]:Mn4+I where A is Li, Na, K, Rb, Cs, NEL, or a combination thereof; M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd, or a combination thereof; x is an absolute value of a charge of the [MFy] ion; and y is 5, 6 or 7.

[0206] In one embodiment, the Mn4+phosphor of formula I is K2SiFe:Mn4+or Na2[SiF6]:Mn4+.

[0207] In one embodiment, the at least one resin comprises at least one of polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), or polycarbonate (PC).

[0208] In one embodiment, an article comprises the above-described device, and the article is selected from the group consisting of an illumination device, a lighting apparatus, an automotive light, an automotive tail-light, an aviation light, and combinations thereof.

[0209] In one embodiment, an automotive or aviation light comprises an LED light source optically coupled and / or radiationally connected to a molded article, the molded article is formed from a molding material, the molding material comprising at least one resin and at least one phosphor material, and wherein the at least one phosphor material comprises a Mn4+doped phosphor of formula I,Ax[MFy]:Mn4+I where A is Li, Na, K, Rb, Cs, NFL, or a combination thereof; M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd, or a combination thereof; x is an absolute value of a charge of the [MFy] ion; and y is 5, 6 or 7.

[0210] In one embodiment, the Mn4+phosphor of formula I is IGSiFe Mn4or Na2[SiF6]:Mn4+.

[0211] In one embodiment, the LED light source is a UV emitting LED or a blue emitting LED.

[0212] This written description uses examples to disclose the invention, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. The patentable scope of the invention is defined by the claims, and may include other examples that occur to those skilled in the art. Such other examples are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.

Claims

CLAIMS:What is claimed is:

1. A molded article formed from a molding material, the molding material comprising at least one phosphor material and at least one resin, and wherein the at least one phosphor material includes a Mn4+doped phosphor of formula I,Ax[MFy]:Mn4+I where A is Li, Na, K, Rb, Cs, NH4, or a combination thereof; M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd, or a combination thereof; x is an absolute value of a charge of the [MFy] ion; and y is 5, 6 or 7.

2. The molded article of claim 1, wherein the Mn4+doped phosphor of formula I is present in an amount of about 5 wt% to about 75 wt% based on a weight of the molding material.

3. The molded article of claim 1, wherein the Mn4+doped phosphor of formula I is present in an amount of about 10 wt% to about 60 wt% based on a weight of the molding material.

4. The molded article of claim 1, wherein the Mn4+doped phosphor of formula I is present in an amount of about 50 wt% to about 70 wt% based on a weight of the molding material.

5. The molded article of claim 1, wherein the Mn4+doped phosphor is selected from K2[GeF6]:Mn4+, K2[SiF6]:Mn4+, K2[TiF6]:Mn4+, K2[SnF6]:Mn4+, Cs2[TiF6]:Mn4+, Rb2[TiF6] Mn4+, Cs2[SiF6]:Mn4+, Rb2[SiF6]:Mn4+, Na2[SiF6]:Mn4+, Na2[TiF6]:Mn4+, Na2[ZrF6]:Mn4+, K3[ZrF7]:Mn4+, K3[BiF6] K3[YF6]:Mn4+, K3[LaF6]:Mn4+, K3[GdF6]:Mn4+, K3[NbF7]:Mn4+, and K3[TaF7]:Mn4+.

6. The molded article of claim 1, wherein the Mn4+phosphor of formula I is K2SiF6:Mn4+or Na2[SiF6]:Mn4+.

7. The molded article of claim 1, wherein the at least one resin comprises at least one of polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), or polycarbonate (PC).

8. The molded article of claim 1, wherein the Mn4+phosphor of formula I is at least partially coated with a surface coating, wherein the surface coating comprises at least one of a hydrophobic coating, a metal fluoride coating, or an organic coating.

9. The molded article of claim 1, wherein the molding material further comprises at least one solvent.

10. The molded article of claim 1, wherein the phosphor material further comprises at least one rare earth containing Garnet phosphor.

11. The molded article of claim 10, wherein the at least one rare earth Garnet phosphor comprises Yttrium Aluminum Garnet phosphor (YAG).

12. The molded article of claim 1, wherein the molding material further comprises at least one scattering agent.

13. The molded article of claim 12, wherein the at least one scattering agent further comprises titanium dioxide, aluminum oxide (AI2O3), zirconium oxide, indium tin oxide, cerium oxide, tantalum oxide, zinc oxide, magnesium fluoride (MgF2), calcium fluoride (CaF2), strontium fluoride (SrF2), barium fluoride (BaF2), silver fluoride (AgF), aluminum fluoride (AIF3), or combinations thereof.

14. The molded article of claim 1, wherein the at least one phosphor material further includes at least one of [Y,Gd,Tb,La,Sm,Pr,Lu]3[Al,Ga]5-aOi2-3 / 2a:Ce3+(wherein 0<a<0.5); beta-Si Al ON:Eu2+; [Sr,Ca,Ba][Al,Ga,In]2S4:Eu2+; alpha-SiAlON doped with Eu2+and / or Ce3+; Cai-h-rCehEurAli-h(Mg,Zn)hSiN3, (where 0<h<0.2, 0<r<0.2); Sr(LiAhN4):Eu2+; [Ca,Sr,Mg]S:Eu2+,Ce3+; [Ba,Sr,Ca]bSigNm:Eu2+(wherein 2b+4g=3m); or combinations thereof.

15. The molded article of claim 1, wherein the molded article is prepared by one of compression molding or injection molding.

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