Green light emitting phosphor and device thereof

Abstract

The invention relates to a green emitting phosphor and a device thereof. A green light emitting phosphor selected from the group consisting of [Ba1-a-bSraCab] x [Mg, Zn] y (UO2) z ([P, V] O4) 2 (x + y + z) / 3 wherein 0 < = a < = 1, 0 < = b < = 1, 0.75 < = x < = 1.25, 0.75 < = y < = 1.25, 0.75 < = z < = 1.25; and [Ba, Sr, Ca, Mg, Zn] p (UO2) q [P, V] rO (2p + 2q + 5r) / 2, where 2.5 < = p < = 3.5, 1.75 < = q < = 2.25, 3.5 < = r < = 4.5.

Description

This application is a divisional application of the invention patent application with the application date of April 13, 2021, application number 202180042076.9, and invention name “Green light emitting phosphor and device thereof”.

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application is a non-provisional application and claims priority to U.S. Provisional Patent Application Serial No. 63 / 009,800, “GREEN-EMITTING PHOSPHORS AND DEVICES THEREOF,” filed on April 14, 2020, and U.S. Provisional Patent Application Serial No. 63 / 073,391, “GREEN-EMITTING PHOSPHORS AND DEVICES THEREOF,” filed on September 1, 2020, each of which is incorporated herein by reference in its entirety. Background Art

[0002] The subject matter described herein relates generally to phosphors and devices and, more particularly, to green light emitting phosphors.

[0003] Current display device technology relies on liquid crystal displays (LCDs), one of the most widely used flat panel displays in industrial and residential applications. However, next generation devices will have low power consumption, compact size and high brightness, requiring improved color gamut.

[0004] LED packages used in displays are based on a combination of a blue LED, a green phosphor, and a red phosphor. The color gamut is largely determined by the choice of phosphor. Red phosphor K2SiF6:Mn 4+ It has a peak characterized by a full width at half maximum (FWHM) of 6 to 8 nm and produces high color reproducibility corresponding to the relative intensity of the emission peak. Green phosphor β-SiAlON:Eu 2+ With a full width at half maximum of 46 to 52 nm and a peak wavelength of 534 to 540 nm, its color is not pure green but green-yellow. Therefore, there is also a need for new green-light emitting phosphors that efficiently absorb blue radiation, provide high quantum efficiency, and have improved color rendering. Summary of the invention

[0005] Briefly, in one aspect, a green light emitting phosphor is provided. The green light emitting phosphor is selected from [Ba 1-a- b Sr a Ca b ] x [Mg, Zn] y (UO2) z ([P,V]O4) 2(x+y+z) / 3, where 0≤a≤1, 0≤b≤1, 0.75≤x≤1.25, 0.75≤y≤1.25 and 0.75≤z≤1.25; and [Ba, Sr, Ca, Mg, Zn] p (UO2) q [P,V] r O (2p+2q+5r) / 2 , where 2.5≤p≤3.5, 1.75≤q≤2.25 and 3.5≤r≤4.5.

[0006] In another aspect, a phosphor composition is provided. The phosphor composition comprises a green light emitting phosphor and a red light emitting phosphor; wherein the green light emitting phosphor is selected from [Ba 1-a-b Sr a Ca b ] x [Mg, Zn] y (UO2) z ([P,V]O4) 2(x+y+z) / 3 , where 0≤a≤1, 0≤b≤1, 0.75≤x≤1.25, 0.75≤y≤1.25 and 0.75≤z≤1.25; and [Ba, Sr, Ca, Mg, Zn] p (UO2) q [P,V] r O (2p+2q+5r) / 2 , wherein 2.5≤p≤3.5, 1.75≤q≤2.25 and 3.5≤r≤4.5; and the red light emitting phosphor is selected from [Ba, Sr, Ca]2Si5N8:Eu 2+ ;[Ca,Sr]AlSiN3:Eu 2+ ;[Ba,Sr,Ca]LiAl3N4:Eu 2+ ;[Sr,Ca,Mg]S:Eu 2+ and the phosphor of formula I: A x MF y :Mn 4+ (I), wherein A is Li, Na, K, Rb, Cs or a combination thereof, M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Hf, Y, La, Nb, Ta, Bi, Gd or a combination thereof, and x is MF y The absolute value of the charge of the ion, and y is 5, 6 or 7.

[0007] In yet another aspect, an apparatus is provided that includes an LED light source radiatively and / or optically coupled to a green light emitting phosphor. The green light emitting phosphor is selected from [Ba 1-a-b Sr a Ca b ] x [Mg, Zn] y(UO2) z ([P,V]O4) 2(x+y+z) / 3 , where 0≤a≤1, 0≤b≤1, 0.75≤x≤1.25, 0.75≤y≤1.25, 0.75≤z≤1.25; and [Ba, Sr, Ca, Mg, Zn] p (UO2) q [P,V] r O (2p+2q+5r) / 2 , where 2.5≤p≤3.5, 1.75≤q≤2.25 and 3.5≤r≤4.5. BRIEF DESCRIPTION OF THE DRAWINGS

[0008] These and other features, aspects, and advantages of the present disclosure will be better understood when the following detailed description is read with reference to the accompanying drawings, in which like characters refer to like parts throughout the drawings, and in which: Figure 1 is a schematic cross-sectional view of a device according to one embodiment of the present disclosure; Figure 2 is a schematic cross-sectional view of a lighting device according to an embodiment of the present disclosure; Figure 3 is a schematic cross-sectional view of a lighting device according to another embodiment of the present disclosure; Figure 4 is a cross-sectional side perspective view of a lighting device according to one embodiment of the present disclosure; Figure 5 is a schematic perspective view of a surface mount device (SMD) according to one embodiment of the present disclosure; Figure 6 shows the crystal structure of BaMgUO2(PO4)2, as determined by x-ray diffraction (XRD) analysis; Figure 7 The XRD powder pattern of BaMgUO2(PO4)2 is shown; Figure 8 The excitation spectrum (dashed line) and emission spectrum (solid line) of a green light emitting phosphor of formula BaMgUO2(PO4)2 are shown; Fig. 9 shows the crystal structure of BaZnUO2(PO4)2, as determined by x-ray diffraction (XRD) analysis; Fig.10 The XRD powder pattern of BaZnUO2(PO4)2 is shown; Fig.11 The excitation spectrum (dashed line) and emission spectrum (solid line) of a green light emitting phosphor of formula BaZnUO2(PO4)2 are shown; Fig.12The crystal structure of Ba3(PO4)2(UO2)2P2O7 is shown, as determined by x-ray diffraction (XRD) analysis; Fig.13 The XRD powder pattern of Ba3(PO4)2(UO2)2P2O7 is shown; Fig.14 The excitation spectrum (dashed line) and emission spectrum (solid line) of a green light emitting phosphor of formula Ba3(PO4)2(UO2)2P2O7 are shown; Fig.15 shows the crystal structure of γ-Ba2UO2(PO4)2, as determined by x-ray diffraction (XRD) analysis; Fig.16 The XRD powder pattern of γ-Ba2UO2(PO4)2 is shown; Fig.17 The excitation spectrum (dashed line) and emission spectrum (solid line) of a green-light-emitting phosphor of formula γ-Ba2UO2(PO4)2 are shown; Fig.18 The emission spectrum of the green light emitting phosphor of formula γ-Ba2UO2(PO4)2 at 30K is shown; Fig.19 The emission spectrum of the green light emitting phosphor of formula Ba2Sr(PO4)2(UO2)2P2O7 is shown; Fig. 20 The emission spectrum of a green light emitting phosphor of formula BaSr2(PO4)2(UO2)2P2O7 is shown; Fig.21 The emission spectrum of the green light emitting phosphor of formula Sr3(PO4)2(UO2)2P2O7 is shown; Fig. 22 The emission spectrum of the green light emitting phosphor of formula Ca3(PO4)2(UO2)2P2O7 is shown; Fig.23 The emission spectrum of a green light emitting phosphor of formula BaMg2(PO4)2(UO2)2P2O7 is shown; Fig.24 The emission spectrum of a green light emitting phosphor of formula Ba2Mg(PO4)2(UO2)2P2O7 is shown; Fig.25 The emission spectrum of the formula Ba2UO2(VO4)2 is shown; Fig.26 shows co-doping with Eu 3+ The emission spectrum of γ-Ba2UO2(PO4)2 at room temperature; Fig.27AIt is a spectrum plot of the emission wavelength (nm) versus the emission intensity of Ba3(PO4)2(UO2)2P2O7; Fig.27B It is doped with Eu 3+ Spectrum of the emission wavelength (nm) versus the emission intensity of Ba3(PO4)2(UO2)2P2O7; Fig.28A It is the spectrum of emission wavelength (nm) of BaZnUO2(PO4)2 compared with emission intensity; Fig.28B It is doped with Eu 3+ Spectrum of the emission wavelength (nm) of BaZnUO2(PO4)2 versus the emission intensity; Fig.29A It is a spectrum plot of emission wavelength (nm) versus emission intensity of γ-Ba2UO2(PO4)2; Fig.29B It is doped with Eu 3+ Spectrum of emission wavelength (nm) versus emission intensity of γ-Ba2UO2(PO4)2; Unless otherwise specified, the drawings provided herein are intended to illustrate the features of the embodiments of the present disclosure. These features are believed to be applicable to a wide range of systems including one or more embodiments of the present disclosure. Therefore, the drawings are not intended to include all conventional features required for implementing the embodiments disclosed herein known to those of ordinary skill in the art. DETAILED DESCRIPTION

[0009] In the following specification and claims, reference will be made to a number of terms which shall be defined to have the following meanings.

[0010] The singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise.

[0011] As used throughout the specification and claims, approximate language may be used to modify any quantitative representation that is permissible to vary without causing a change in the basic function to which it is associated. Therefore, values ​​modified by one or more terms such as "about," "substantially," and "approximately" are not limited to the exact values ​​specified. In at least some cases, approximate language may correspond to the precision of the instrument used to measure the value. Here and throughout the specification and claims, range boundaries may be combined and / or interchanged, and unless the context or language indicates otherwise, such a range is determined and includes all subranges contained therein. All references are incorporated herein by reference.

[0012] The square brackets in the formula indicate that at least one of the elements in the brackets is present in the phosphor material, and any combination of two or more of them may be present, subject to the stoichiometry of the composition. For example, the formula [Ca, Sr, Ba] 3MgSi2O8:Eu 2+ ,Mn 2+ Contains at least one of Ca, Sr or Ba or any combination of two or more of Ca, Sr or Ba. Examples include Ca3MgSi2O8:Eu 2+ ,Mn 2+ ;Sr3MgSi2O8:Eu 2+ ,Mn 2+ ; or Ba3MgSi2O8:Eu 2+ ,Mn 2+ . A formula with an activator after a colon ":" indicates that the phosphor composition is doped with an activator. A formula showing more than one activator separated by "," after a colon ":" indicates that the phosphor composition is doped with any one activator or both activators. For example, the formula [Ca, Sr, Ba] 3MgSi2O8:Eu 2+ ,Mn 2+ Covering [Ca,Sr,Ba]3MgSi2O8:Eu 2+ 、[Ca,Sr,Ba]3MgSi2O8:Mn 2+ or [Ca,Sr,Ba]3MgSi2O8:Eu 2+ and Mn 2+ .

[0013] The green-emitting phosphors disclosed herein absorb radiation in the near-UV or blue region (wavelength range between about 400nm and 470nm) and emit in a narrowband, with the main emission peak concentrated in the wavelength range between 500nm and 550nm, particularly about 510nm to about 530nm, more particularly about 515nm to about 525nm. These phosphors can be used in display applications. The color gamut of a display incorporating a narrowband green-emitting phosphor (which can be measured according to NTSC, DCI-P3, Adobe or BT2020 standards) can be significantly improved relative to a phosphor with relatively broadband emission.

[0014] In some embodiments, the phosphor contains phosphate / vanadate groups and has the formula [Ba 1-a-b Sr a Ca b ] x [Mg, Zn] y (UO2) z ([P,V)]O4) 2(x+y+z) / 3, wherein 0≤a≤1, 0≤b≤1, 0.75≤x≤1.25, 0.75≤y≤1.25, 0.75≤z≤1.25. In some embodiments, one or more additional activator ions may be present, such as Mn 2+ , Mn 4+ 、Ce 3+ Cr 3+ 、Eu 2+ or Eu 3+ In particular, the phosphor contains phosphate groups and has the formula [Ba x [Mg, Zn] y (UO2) z [PO4] 2(x+y+z) / 3 Particular examples include Ba[Mg,Zn]UO2(PO4)2, more particularly BaMgUO2(PO4)2 and BaZnUO2(PO4)2.

[0015] In other embodiments, the phosphor contains [P,V]2O7 groups in addition to phosphate / vanadate groups and has the formula [Ba,Sr,Ca,Mg,Zn] p (UO2) q [P,V] r O (2p+2q+5r) / 2 , wherein 2.5≤p≤3.5, 1.75≤q≤2.25, 3.5≤r≤4.5. In some embodiments, one or more additional activator ions may be present, such as Mn 2+ , Mn 4+ 、Ce 3+ Cr 3+ 、Eu 2+ or Eu 3+ In particular, the phosphor contains phosphate and pyrophosphate groups and has the formula Ba p (UO2) q P r O (2p+2q+5r) / 2 Specific examples include Ba3(PO4)2(UO2)2P2O7 and γ-Ba2UO2(PO4)2 (γ-Ba2UO2(PO4)2).

[0016] In one embodiment, the phosphor can be Ba2Sr(PO4)2(UO2)2P2O7, BaMgUO2(PO4)2, BaZnUO2(PO4)2, Ba3(PO4)2(UO2)2P2O7, γ-Ba2UO2(PO4)2, BaSr2(PO4)2(UO2)2P2O7, Sr3(PO4)2(UO2)2P2O7, Ca3(PO4)2(UO2)2P2O7, BaMg2(PO4)2(UO2)2P2O7, Ba2Mg(PO4)2(UO2)2P2O7, Ba2UO2(VO4)2, or γ-Ba2UO2(PO4)2:Eu 3+ .

[0017] The phosphors of the present disclosure can be characterized as uranium-doped or U-doped because U 6+ The ion is part of the emitting species. The term "U-doped" usually means that a relatively small number of uranium atoms have been substituted in the host lattice. In many compounds, uranium is present as uranyl ions (UO2). 2+ Because the uranyl ion is characterized by linear OUO bonding, there is usually an upper limit to the substitution that can be achieved, which is on the order of several mole percent relative to the site being substituted. 2+ When ions, M 2 + and (UO2) 2+ There are size restrictions between the centers, which may produce host lattice strains and / or compensating defects in the host lattice. 6+ Concentration quenching of emission generally occurs before complete substitution is achieved. In contrast, the phosphors of the present disclosure contain UO2 species as part of the host lattice and in an amount relative to the presence of M 2+ The uranyl ions are included in a concentration of up to about 40 mole % of the total moles of cations.

[0018] The phosphor of the present disclosure can be produced by firing a mixture of precursors in an oxidizing atmosphere. Non-limiting examples of suitable precursors include suitable metal oxides, hydroxides, alkoxides, carbonates, nitrates, aluminates, silicates, citrates, oxalates, carboxylates, tartrates, stearates, nitrites, peroxides, phosphates, pyrophosphates and combinations thereof. Materials suitable for use as precursors include, but are not limited to, BaCO3, BaHPO4, Ba3(PO4)2, Ba2P2O7, Ba2Zn(PO4)2, BaZnP2O7, Ba(OH)2, Ba(C2O4), Ba(C2H3O2)2, Ba3(C6H5O7)2, Ba(NO3)2, CaCO3, Eu2O3, Mg(C2O4), Mg(C2H3O2)2, Mg(C6H6O7), MgCO3, MgO, Mg(OH)2, Mg3(PO4)2, Mg2P2O7, Mg2Ba(PO4)2, MgHPO4, Mg(NO3)2, NH4MgPO4, (NH4)2HP O4, NH4VO3, SrCO3, Zn(C2O4), Zn(C2H3O2)2, Zn3(C6H5O7)2, ZnCO3, ZnO, Zn(OH)2, Zn3(PO4)2, Zn2P2O7, Zn2Ba(PO4)2, ZnHPO4, Zn(NO3)2, NH4ZnPO4, UO2, UO2(NO3)2, (UO2)2P2O7, (UO2)3(PO4)2, NH4(UO2)PO4, UO2CO3, UO2(C2H3O2)2, UO2(C2O4), H(UO2)PO4, UO2(OH)2 and ZnUO2(C2H3O2)4 and various hydrates. For example, the exemplary phosphor BaMgUO2(PO4)2 can be produced by mixing a suitable amount of BaCO3, MgO and UO2 with a suitable amount of (NH4)2HPO4 and then firing the mixture under an air atmosphere. In another example, an exemplary gamma uranyl barium phosphate or gamma uranyl barium orthophosphate (γ-Ba2UO2(PO4)2) can be produced by mixing a stoichiometric amount of BaHPO4 and UO2 with an excess of (NH4)2HPO4(DAP) and then firing the mixture under an air atmosphere. The precursor can be in solid form or in solution. Non-limiting examples of solvents include water, ethanol, acetone and isopropanol, and suitability depends primarily on the solubility of the precursor in the solvent. After firing, the phosphor can be milled to break up any agglomerates that may have formed during the firing procedure.

[0019] The starting material mixture for producing the phosphor may also include one or more low melting temperature flux materials, such as boric acid, borate compounds such as lithium tetraborate, alkali metal phosphates, and combinations thereof. Non-limiting examples include (NH4)2HPO4(DAP), Li3PO4, Na3PO4, NaBO3-H2O, Li2B4O7, K4P2O7, Na4P2O7, H3BO3, and B2O3. The flux may reduce the firing temperature and / or shorten the firing time of the phosphor. If a flux is used, it may be desirable to wash the final phosphor product with a suitable solvent to remove any residual soluble impurities that may be derived from the flux.

[0020] The samples are usually fired in air, but since uranium is in its highest oxidation state (U 6+ ), so it can also be fired in O2 or other wet or dry oxidizing atmospheres, including at a temperature between about 900°C and about 1300°C, especially between about 1000°C and about 1200°C, at an oxygen partial pressure above one atmosphere, for a time sufficient to convert the mixture into a phosphor. The required firing time can be in the range of about one to twenty hours, depending on the amount of the mixture being fired, the degree of contact between the solid and the atmospheric gas, and the degree of mixing when the mixture is fired or heated. The mixture can be brought to the final temperature quickly and maintained at the final temperature, or the mixture can be heated to the final temperature at a lower rate, such as about 2°C / minute to about 200°C / minute.

[0021] In addition to the green light emitting phosphor, the phosphor composition according to the present disclosure may further include a red light emitting phosphor of Formula I: x MF y :Mn 4+ (I), wherein A is Li, Na, K, Rb, Cs or a combination thereof, M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Hf, Y, La, Nb, Ta, Bi, Gd or a combination thereof, and x is MF y The absolute value of the charge of the ion, and y is 5, 6 or 7. In one embodiment, the red light emitting phosphor of Formula I is A2(MF6):Mn 4+ , wherein A is Li, Na, K, Rb, Cs or a combination thereof; and M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Hf, Y, La, Nb, Ta, Bi, Gd or a combination thereof. In particular, the red light emitting phosphor may be K2SiF6:Mn 4+The red-light emitting phosphor of the formula is radiatively and / or optically coupled to an LED light source. Phosphors of formula I are described in US 7,497,973 and US 8,906,724 and related patents assigned to General Electric Company. Examples of red-light emitting phosphors of formula I include K2(TiF6):Mn 4+ 、K2(SnF6):Mn 4+ 、Cs2(TiF6):Mn 4+ 、Rb2(TiF6):Mn 4+ 、Cs2(SiF6):Mn 4+ 、Rb2(SiF6):Mn 4+ 、Na2(SiF6):Mn 4+ 、Na2(TiF6):Mn 4+ 、Na2(ZrF6):Mn 4+ 、K3(ZrF7):Mn 4+ 、K3(BiF7):Mn 4+ 、K3(YF7):Mn 4+ 、K3(LaF7):Mn 4+、 K3(GdF7):Mn 4+、 K3(NbF7):Mn 4+ or K3(TaF7):Mn 4+ In certain embodiments, the phosphor of Formula I is K2SiF6:Mn 4+ .

[0022] In addition to the green-emitting phosphor and optionally the red-emitting Mn of formula I 4+ In addition to the doped phosphor, the phosphor composition according to the present disclosure may also include one or more other luminescent materials. Additional luminescent materials such as blue, yellow, red, orange or other colored phosphors may be used in the phosphor composition to customize the whiteness of the generated light and produce a specific spectral power distribution.

[0023] In addition to green and red emitting phosphors, phosphors suitable for use in the phosphor composition include, but are not limited to: ((Sr 1-z [Ca,Ba,Mg,Zn] z ) 1-(x+w) [Li,Na,K,Rb] w Ce x )3(Al 1-y Si y ) 4+y+3(x-w) F 1-y-3(x-w) ,0 <x≤0.10,0≤y≤0.5,0≤z≤0.5,0≤w≤x;[Ca,Ce]3Sc2Si3O12 (CaSiG); [Sr, Ca, Ba]3Al 1-x Si x O 4+ x F 1-x :Ce 3+ (SASOF)); [Ba, Sr, Ca]5(PO4)3[Cl, F, Br, OH]:Eu 2+ ,Mn 2+ ; [Ba, Sr, Ca]BPO5:Eu 2+ ,Mn 2 + ; [Sr, Ca] 10 (PO4)6*vB2O3:Eu 2+ (where 0 < v ≤ 1); Sr2Si3O8*2SrCl2:Eu 2+ ; [Ca, Sr, Ba]3MgSi2O8:Eu 2+ ,Mn 2+ ; BaAl8O 13 :Eu 2+ ; 2SrO*0.84P2O5*0.16B2O3:Eu 2+ ; [Ba, Sr, Ca]MgAl 10 O 17 :Eu 2+ ,Mn 2+ ; [Ba, Sr, Ca]Al2O4:Eu 2+ ; [Y, Gd, Lu, Sc, La]BO3:Ce 3+ ,Tb 3+ ; ZnS:Cu + ,Cl - ; ZnS:Cu + ,Al 3+ ; ZnS:Ag + ,Cl - ; ZnS:Ag + ,Al 3+ ; [Ba, Sr, Ca]2Si 1-n O 4-2n :Eu 2+ (where 0 ≤ n ≤ 0.2); [Ba, Sr, Ca]2[Mg, Zn]Si2O7:Eu 2+ ; [Sr, Ca, Ba][Al, Ga, In]2S4:Eu 2+ ; [Y, Gd, Tb, La, Sm, Pr, Lu]3[Al, Ga] 5-a O 12-3 / 2a :Ce 3 +(where 0 ≤ a ≤ 0.5); [Ca,Sr]8[Mg,Zn](SiO4)4Cl2:Eu 2+ ,Mn 2+ ; Na2Gd2B2O7:Ce 3+ ,Tb 3+ ; [Sr,Ca,Ba,Mg,Zn]2P2O7:Eu 2+ ,Mn 2+ ; [Gd,Y,Lu,La]2O3:Eu 3+ ,Bi 3+ ; [Gd,Y,Lu,La]2O2S:Eu 3+ ,Bi 3+ ; [Gd,Y,Lu,La]VO4:Eu 3+ ,Bi 3+ ; [Ca,Sr,Mg]S:Eu 2+ ,Ce 3+ ; SrY2S4:Eu 2+ ; CaLa2S4:Ce 3+ ; [Ba,Sr,Ca]MgP2O7:Eu 2+ ,Mn 2+ ; [Y,Lu]2WO6:Eu 3+ ,Mo 6+ ; [Ba,Sr,Ca] b Si g N m :Eu 2+ (where 2b + 4g = 3m); Ca3(SiO4)Cl2:Eu 2+ ; [Lu,Sc,Y,Tb] 2-u-v Ce v Ca 1+u Li w Mg 2-w P w [Si,Ge] 3-w O 12-u / 2 (where 0.5 ≤ u ≤ 1, 0 < v ≤ 0.1, and 0 ≤ w ≤ 0.2); [Y,Lu,Gd] 2-m [Y,Lu,Gd]Ca m Si4N 6+m C 1-m :Ce 3+ ,(where 0 ≤ m ≤ 0.5); [Lu,Ca,Li,Mg,Y], α-SiAlON doped with Eu 2+ and / or Ce 3+ ; Sr(LiAl3N4):Eu 2+ ,[Ca,Sr,Ba]SiO2N2:Eu 2+ ,Ce 3+ ;β-SiAlON:Eu 2+ ;3.5MgO*0.5MgF2*GeO2:Mn 4+ ;Ca 1-c-f Ce c Eu f Al 1+c Si 1-c N3, (where 0≤c≤0.2, 0≤f≤0.2); Ca 1-h-r Ce h Eu r Al 1-h (Mg, Zn) h SiN3, (where 0≤h≤0.2, 0≤r≤0.2); Ca 1-2s-t Ce s [Li,Na] s Eu t AlSiN3, (where 0≤s≤0.2, 0≤t≤0.2, s+t>0); [Sr,Ca]AlSiN3:Eu 2+ ,Ce 3+ and Li2CaSiO4:Eu 2+ .

[0024] In a particular embodiment, the additional phosphors include: [Y, Gd, Lu, Tb]3[Al, Ga]5O 12 :Ce 3+ 、β-SiAlON:Eu 2+ 、[Sr,Ca,Ba][Ga,Al]2S4:Eu 2+ 、[Li,Ca]α-SiAlON:Eu 2+ 、[Ba,Sr,Ca]2Si5N8:Eu 2+ 、[Ca,Sr]AlSiN3:Eu 2+ 、[Ba,Sr,Ca]LiAl3N4:Eu 2+ and [Sr,Ca,Mg]S:Eu 2+ .

[0025] The ratio of each individual phosphor in the phosphor composition can vary depending on the characteristics of the desired light output. The relative proportions of the individual phosphors in various phosphor compositions can be adjusted so that when their emissions are blended and employed in a device such as a lighting fixture, visible light having predetermined x and y values ​​on the CIE chromaticity diagram is produced.

[0026] Other additional luminescent materials suitable for use in the phosphor composition may include electroluminescent polymers such as polyfluorenes, preferably poly(9,9-dioctylfluorene) 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 luminescent layer may include a blue, yellow, orange, green or red phosphorescent dye or metal complex, quantum dot material or a combination thereof. Materials suitable for use as phosphorescent dyes include, but are not limited to, tris(1-phenylisoquinoline)iridium(III) (red dye), tris(2-phenylpyridine)iridium (green dye) and bis(2-(4,6-difluorophenyl)pyridino-N,C2)iridium(III) (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. Exemplary quantum dot materials are based on CdSe, ZnS or InP, including but not limited to core / shell luminescent nanocrystals such as CdSe / ZnS, InP / ZnS, PbSe / PbS, CdSe / CdS, CdTe / CdS or CdTe / ZnS. Other examples of quantum dot materials include halide perovskite quantum dots such as CsPbX3, wherein X is Cl, Br, I or a combination thereof. All of these semiconductor quantum dots can also have a suitable shell or coating for passivation and / or environmental protection.

[0027] An apparatus according to the present disclosure includes one or more LED light sources radiatively and / or optically coupled to a green light emitting phosphor. Figure 1A device 10 according to one embodiment of the present disclosure is shown. The device 10 includes an LED light source 12 and a phosphor composition 14 including a green light emitting phosphor of the present disclosure. The LED light source 12 can be a UV or blue light emitting LED. In some embodiments, the LED light source 12 generates blue light in a wavelength range of about 440 nm to about 460 nm. In the device 10, the phosphor composition 14 including a green light emitting phosphor as described herein is coupled to the LED light source 12 in a radiation manner and / or optically coupled. Radiative coupling or optical coupling means that radiation from the LED light source 12 can excite the phosphor composition 14, and the phosphor composition 14 can emit light in response to the excitation by the radiation. The phosphor composition 14 can be disposed on a portion or part of the LED light source 12, or remotely located at a distance from the LED light source 12.

[0028] The general discussion of the example LED light sources discussed herein is directed to light sources based on inorganic LEDs. However, as used herein, the term is intended to cover all LED light sources such as semiconductor laser diodes (LDs), organic light emitting diodes (OLEDs), or a mixture of LEDs and LDs. In addition, the LED light source may be a miniLED or microLED, which can be used in self-emissive displays. Furthermore, it should be understood that, unless otherwise stated, the LED light source may be replaced, supplemented, or enhanced by another radiation source, and any reference to semiconductors, semiconductor LEDs, or LED chips represents only any suitable radiation source, including but not limited to LDs and OLEDs. In some embodiments, the phosphor composition 14 further includes a red light emitting phosphor of formula I, particularly K2SiF6:Mn 4+ .

[0029] The phosphor composition 14 can be present in any form, such as a powder, a glass, or a composite, such as a phosphor-polymer composite or a phosphor-glass composite. In addition, the phosphor composition 14 can be used as a layer, a sheet, a strip, dispersed particles, or a combination thereof. In some embodiments, the phosphor composition 14 includes a green light emitting phosphor in the form of a glass. In some of these embodiments, the device 10 may include a phosphor composition 14 in the form of a phosphor wheel (not shown). The phosphor wheel may include a green light emitting phosphor embedded in glass. Phosphor wheels and related devices are described in WO2017 / 196779.

[0030] Figure 2A lighting device or lamp 20 according to some embodiments is illustrated. The lighting device 20 includes an LED chip 22 and leads 24 electrically connected to the LED chip 22. The leads 24 may include thin wires supported by a thicker lead frame 26, or the leads 24 may include self-supporting electrodes and the lead frame may be omitted. The leads 24 provide current to the LED chip 22 and thus cause it to emit radiation.

[0031] A layer 30 of a phosphor composition including a green light emitting phosphor is disposed on the surface of the LED chip 22. The phosphor layer 30 may be disposed by any suitable method, for example, using a slurry made by mixing silicone with the phosphor composition. In one such method, a silicone slurry in which the phosphor composition particles are randomly suspended is placed around the LED chip 22. This method is only an example of possible locations for the phosphor layer 30 and the LED chip 22. The phosphor layer 30 may be applied over or directly on the light emitting surface of the LED chip 22 by coating and drying the slurry over the LED chip 22. The light emitted by the LED chip 22 is mixed with the light emitted by the phosphor composition to produce the desired emission.

[0032] Continue to refer Figure 2 , the LED chip 22 can be encapsulated in a housing 28. The housing 28 can be formed of, for example, glass or plastic. The LED chip 22 can be surrounded by an encapsulation material 32. The encapsulation material 32 can be a low temperature glass or a polymer or resin known in the art, such as an epoxy resin, silicone, epoxy-silicone resin, acrylate or a combination thereof. In an alternative embodiment, the lighting device 20 can include only the encapsulation material 32 without the housing 28. Both the housing 28 and the encapsulation material 32 should be transparent to allow light to be transmitted through these components.

[0033] In such Figure 3 In some embodiments illustrated in FIG. 1 , the green light emitting phosphor of the phosphor composition 33 is dispersed in the encapsulating material 32, rather than as Figure 2 33 is formed directly on the LED chip 22. The phosphor composition 33 can be dispersed within a portion of the encapsulation material 32 or throughout the entire volume of the encapsulation material 32. The blue light emitted by the LED chip 22 is mixed with the light emitted by the phosphor composition 33, and the mixed light is transmitted out of the lighting device 20.

[0034] In yet another embodiment, a layer 34 of a phosphor composition including a green light emitting phosphor is applied to a surface of the housing 28 rather than being formed over the LED chip 22, such as Figure 4As shown, the phosphor layer 34 is coated on the inner surface 29 of the housing 28, but if desired, the phosphor layer 34 can be coated on the outer surface of the housing 28. The phosphor layer 34 can be coated on the entire surface of the housing 28 or only on the top portion of the inner surface 29 of the housing 28. The UV / blue light emitted by the LED chip 22 is mixed with the light emitted by the phosphor layer 34, and the mixed light is transmitted. Of course, the phosphor composition can be located in any two or all three locations (such as Figure 2-4 ) or in any other suitable location, such as separate from the housing 28 or integrated into the LED chip 22.

[0035] In any of the above structures, the lighting device 20 ( Figure 2-4 ) may also include a plurality of scattering particles (not shown) embedded in the encapsulation material 32. The scattering particles may include, for example, aluminum oxide, silicon dioxide, zirconium oxide, or titanium dioxide. The scattering particles effectively scatter the directional light emitted from the LED chip 22, preferably with negligible absorption.

[0036] Some embodiments include a surface mounted device (SMD) type light emitting diode 50, such as Figure 5 , for backlighting applications. The SMD is of the "side-emitting type" and has a light emission window 52 on the protrusion of the light guide member 54. The SMD package may include an LED chip as defined above and a phosphor composition including a green light emitting phosphor as described herein.

[0037] The device of the present disclosure includes lighting and display equipment for general lighting and display applications. Examples of display equipment include liquid crystal display (LCD) backlight units, televisions, computer monitors, laptops, mobile phones, smart phones, tablet computers and other handheld devices. In the case where the display is a backlight unit, the green light emitting phosphor can be incorporated in a sheet or strip that is coupled to an LED light source in a radiation manner and / or optically coupled, as described in U.S. Patent Application Publication No. 2017 / 0254943. Examples of other devices include colored lamps, plasma screens, xenon excitation lamps, UV excitation marking systems, automotive headlights, home and theater projectors, laser pumping devices and point sensors.

[0038] By using the phosphor compositions described herein, a device can be provided that produces white light for display applications (e.g., LCD backlight units) having a high color gamut and high brightness. Alternatively, a device can be provided that produces white light for general lighting having high brightness and high CRI values ​​for a wide range of color temperatures of interest (2500K to 10000K). The list of these applications is intended to be exemplary only and not exhaustive.

[0039] Although specific features of various embodiments of the present disclosure may be shown in some drawings and not in other drawings, this is for convenience only. According to the principles of the present disclosure, any feature of the drawings may be referenced and / or claimed in combination with any feature of any other drawings. Example

[0040] Example 1: Preparation of BaMgUO2(PO4)2 Stoichiometric amounts of BaCO3, MgO, UO2, and (NH4)2HPO4 (DAP) were weighed into a Nalgene bottle and ball milled for two hours. After the mixture was thoroughly blended, the powder was transferred to an alumina crucible and fired at 500°C to decompose the DAP. The fired blend was then transferred back to the Nalgene bottle and milled for another two hours. After the second milling, the powder was transferred back to the alumina crucible and fired at 1000-1100°C. After firing, a yellow powder with the composition of BaMgUO2(PO4)2 was obtained.

[0041] The crystal structure of the material was analyzed and shown in Figure 6 The XRD powder pattern is shown in Figure 7 The crystallographic data are shown in Table 1. The emission spectrum (solid line) and excitation spectrum (dashed line) of BaMgUO2(PO4)2 are shown in Table 1. Figure 8 Shown in.

[0042] Example 2: Preparation of BaZnUO2(PO4)2 Stoichiometric amounts of BaCO3, ZnO, UO2, and (NH4)2HPO4 (DAP) were weighed into a Nalgene bottle and ball milled for two hours. After the mixture was thoroughly blended, the powder was transferred to an alumina crucible and fired at 500°C to decompose the DAP. The fired blend was then transferred back to the Nalgene bottle and milled for another two hours. After the second milling, the powder was transferred back to the alumina crucible and fired at 1000-1100°C. After firing, a yellow powder with the composition of BaZnUO2(PO4)2 was obtained.

[0043] The crystal structure of the material was analyzed and shown in Fig. 9 The XRD powder pattern is shown in Fig.10 The crystallographic data are shown in Table 1. The emission spectrum (solid line) and excitation spectrum (dashed line) of BaZnUO2(PO4)2 are shown in Table 1. Fig.11 Shown in.

[0044] Example 3: Preparation of Ba3(PO4)2(UO2)2P2O7 Stoichiometric amounts of BaCO3, UO2, and (NH4)2HPO4 (DAP) were weighed into a Nalgene bottle and ball milled for two hours. After the mixture was thoroughly blended, the powder was transferred to an alumina crucible and fired at 500°C to decompose the DAP. The fired blend was then transferred back to the Nalgene bottle and milled for another two hours. After the second milling, the powder was transferred back to the alumina crucible and fired at 1000-1100°C. A yellow body color powder was obtained after firing.

[0045] The crystal structure of the material was analyzed and shown in Fig.12 The XRD powder pattern is shown in Fig.13 The crystallographic data are shown in Table 1. The emission spectrum (solid line) and excitation spectrum (dashed line) of Ba3(PO4)2(UO2)2P2O7 are shown in Table 1. Fig.14 Shown in.

[0046] Example 4: Preparation of γ-Ba2UO2(PO4) Stoichiometric amounts of BaHPO4, UO2 and 5% excess of (NH4)2HPO4 (DAP) were weighed into a Nalgene bottle and ball milled for two hours. After the mixture was thoroughly blended, the powder was transferred to an alumina crucible and fired at 1100°C to decompose the DAP. The fired blend was then transferred back to the Nalgene bottle and milled for another two hours. After the second milling, the powder was transferred back to the alumina crucible and fired at 1200°C. A yellow body color powder was obtained after firing.

[0047] The crystal structure of the material was analyzed and shown in Fig.15 The XRD powder pattern is shown in Fig.16 The crystallographic data are shown in Table 1. The emission spectrum (solid line) and excitation spectrum (dashed line) of γ-Ba2UO2(PO4)2 are shown in Fig.17 The emission spectrum of γ-Ba2UO2(PO4)2 at 30K is shown in Fig.18 Shown in.

[0048] Example 5: Preparation of Ba3(PO4)2(UO2)2P2O7 BaCl2·2H2O (8.2001 g, 33.5686 mmol) and UO2(NO3)2·6H2O (2.9746 g, 5.9239 mmol) were added to a 250 mL beaker containing a large stirring bar, followed by 137 mL of deionized water. The starting mixture exhibited a Ba to UO2 molar ratio of 85 / 15. The mixture was stirred at room temperature until homogeneous. To the stirring solution was added a deionized aqueous solution of ammonium hydrogen phosphate (11.12 mL, 3.5516 M, 39.4938 mmol) via a syringe pump at room temperature over 15 minutes. The mixture was stirred for an additional 5 minutes and then filtered on a Buchner funnel. The pale yellow powder was washed with deionized water (3×75 mL), stirring the product before each wash. The Ba / UO2 hydrogen phosphate intermediate (9.1059 g) was dried at room temperature.

[0049] The hydrogen phosphate intermediate (2.23 g) was fired in an alumina crucible at 1050° C. Single crystal x-ray diffraction analysis showed that the heat treated product contained Ba3(PO4)2(UO2)2P2O7.

[0050] Example 6: Preparation of Ba3(PO4)2(UO2)2P2O7 Stoichiometric amounts of Ba3(PO4)2, UO2(NO3)2-6H2O and DAP were blended in a Nalgene bottle with 20 mL of deionized (DI) H2O and ball milled (with yttria stabilized zirconia, YSZ media) for two hours. After blending, the mixture was filtered and dried to eliminate excess water. Once dried, the powder was crushed and placed in an alumina crucible and fired at 1000°C-1100°C in air for 5 hours. A yellow body color powder was obtained after firing.

[0051] Example 7: Preparation of Ba3(PO4)2(UO2)2P2O7 γ-Ba2UO2(PO4)2, (UO2)3(PO4)2-4H2O and DAP were blended in a Nalgene bottle and ball milled (with YSZ media) for two hours. After the mixture was thoroughly blended, the powder was transferred to an alumina crucible and fired at 1100°C for 5 hours. After firing, a yellow body color powder was obtained. The phosphor material produced a yellow body color after being excited at 450nm. Fig.14 The same emission spectra are shown in .

[0052] Example 8: Preparation of Ba3(PO4)2(UO2)2P2O7 γ-Ba2UO2(PO4)2, UO2 and DAP were blended in a Nalgene bottle and ball milled (with YSZ media) for two hours. After the mixture was thoroughly blended, the powder was transferred to an alumina crucible and fired at 1100°C for 5 hours. After firing, a yellow body color powder was obtained. The phosphor material produced a yellow body color after being excited at 450nm. Fig.14 The same emission spectra are shown in .

[0053] Example 9: Preparation of Ba2Sr(PO4)2(UO2)2P2O7 Stoichiometric amounts of BaCO3, SrCO3 and UO2 were blended with (NH4)2HPO4(DAP) (5% excess) in a Nalgene bottle and ball milled (with YSZ media) for two hours. After the mixture was thoroughly blended, the powder was transferred to an alumina crucible and fired at 500°C for 5 hours. After firing, the powder was blended again for 2 hours and fired at 1000°C-1100°C in air for 5 hours. After firing, a yellow body color powder was obtained. The emission spectrum after excitation at 450nm is Fig.19 Shown in.

[0054] Example 10: Preparation of BaSr2(PO4)2(UO2)2P2O7 Stoichiometric amounts of BaCO3, SrCO3 and UO2 were blended with (NH4)2HPO4(DAP) (5% excess) in a Nalgene bottle and ball milled (with YSZ media) for two hours. After the mixture was thoroughly blended, the powder was transferred to an alumina crucible and fired at 500°C for 5 hours. After firing, the powder was blended again for 2 hours and fired at 1000°C-1100°C in air for 5 hours. After firing, a yellow body color powder was obtained. The emission spectrum after excitation at 450nm is Fig. 20 Shown in.

[0055] Example 11: Preparation of Sr3(PO4)2(UO2)2P2O7 Stoichiometric amounts of SrCO3 and UO2 were blended with (NH4)2HPO4 (DAP) (5% excess) in a Nalgene bottle and ball milled (with YSZ media) for two hours. After the mixture was thoroughly blended, the powder was transferred to an alumina crucible and fired at 500°C for 5 hours. After firing, the powder was blended again for 2 hours and fired at 1000°C-1100°C in air for 5 hours. After firing, a yellow body color powder was obtained. The emission spectrum after excitation at 450nm is Fig.21 Shown in.

[0056] Example 12: Preparation of Ca3(PO4)2(UO2)2P2O7 Stoichiometric amounts of CaCO3 and UO2 were blended with (NH4)2HPO4 (DAP) (5% excess) in a Nalgene bottle and ball milled (with YSZ media) for two hours. After the mixture was thoroughly blended, the powder was transferred to an alumina crucible and fired at 500°C for 5 hours. After firing, the powder was blended again for 2 hours and fired at 1000°C-1100°C in air for 5 hours. After firing, a yellow body color powder was obtained. The emission spectrum after excitation at 450nm is Fig. 22 Shown in.

[0057] Example 13: Preparation of BaMg2(PO4)2(UO2)2P2O7 Stoichiometric amounts of BaCO3, MgO and UO2 were blended with (NH4)2HPO4 (DAP) (5% excess) in a Nalgene bottle and ball milled (with YSZ media) for two hours. After the mixture was thoroughly blended, the powder was transferred to an alumina crucible and fired at 500°C for 5 hours. After firing, the powder was blended again for 2 hours and fired at 1000°C-1100°C in air for 5 hours. After firing, a yellow body color powder was obtained. The emission spectrum after excitation at 450nm is Fig.23 Shown in.

[0058] Example 14: Preparation of Ba2Mg(PO4)2(UO2)2P2O7 Stoichiometric amounts of BaCO3, MgO and UO2 were blended with (NH4)2HPO4 (DAP) (5% excess) in a Nalgene bottle and ball milled (with YSZ media) for two hours. After the mixture was thoroughly blended, the powder was transferred to an alumina crucible and fired at 500°C for 5 hours. After firing, the powder was blended again for 2 hours and fired at 1000°C-1100°C in air for 5 hours. After firing, a yellow body color powder was obtained. The emission spectrum after excitation at 450nm is Fig.24 Shown in.

[0059] Example 15: Preparation of Ba2UO2(VO4)2 Stoichiometric amounts of BaCO3, NH4VO3 and UO2 were blended in a Nalgene bottle and ball milled (with YSZ media) for two hours. After the mixture was thoroughly blended, the powder was transferred to an alumina crucible and fired at 500°C for 5 hours. After firing, the powder was blended again for 2 hours and fired at 1000°C-1100°C in air for 5 hours. After firing, a yellow body color powder was obtained. The emission spectrum after excitation at 450nm is Fig.25 Shown in.

[0060] Example 16: γ-Ba2UO2(PO4)2:Eu 3+ Preparation Stoichiometric amounts of BaCO3, UO2, Eu2O3 and (NH4)2HPO4 (DAP) (5% excess) were blended in a Nalgene bottle and ball milled (with YSZ media) for two hours. After the mixture was thoroughly blended, the powder was transferred to an alumina crucible and fired at 500°C for 5 hours. After firing, the powder was blended again for 2 hours and fired at 1100°C-1200°C in air for 5 hours. After firing, a yellow body color powder was obtained. The emission spectrum after excitation at 450nm at room temperature was Fig.26 Shown in.

[0061] Example 17: Color Gamut Coverage of Phosphor Blends Using a 450nm blue LED through a standard LCD color filter and PFS (K2SiF6:Mn 4+ ) spectrum, and calculate the blending simulation using (u,v) or (x,y) color space. The color filter (CF) group and the optical density of the CF group remain unchanged, so that the modeling results only show the effect of changing the green phosphor. The blending ratio of LED to green and red phosphors is changed so that the emission output after optical superposition and the color filter group is at the same D65 color point, and then the color gamut area coverage is calculated. The results are shown in Table 2.

[0062] Example 18: Preparation of Ba3(PO4)2(UO2)2P2O7 phosphor and co-doped Ba3(PO4)2(UO2)2P2O7 phosphor material BaHPO4, BaCO3, HUO2PO4-4H2O and DAP were weighed in a molar ratio of 2:1:2:0.05 and then placed in a Nalgene bottle with zirconium oxide medium and ball milled for 2 hours. After the mixture was fully blended, the powder was transferred to an alumina crucible and fired at 1100°C for 5 hours. After firing, a yellow body color powder was obtained. The emission spectrum of Ba3(PO4)2(UO2)2P2O7 is shown in Fig.27A .

[0063] In order to prepare 3+ Ba3(PO4)2(UO2)2P2O7 was prepared by the same procedure as above except that 0.005Eu2O3 was added and the amount of BaCO3 was adjusted to 0.995. After firing, a yellow body color powder was obtained. 3+ The emission spectrum of Ba3(PO4)2(UO2)2P2O7 is shown in Fig.27B .

[0064] Example 19: Preparation of BaZnUO2(PO4)2 phosphor and co-doped BaZnUO2(PO4)2 phosphor materials BaHPO4, HUO2PO4-4H2O, ZnO and DAP were weighed in a molar ratio of 1:1:1:0.05 and then placed in a Nalgene bottle with zirconium oxide medium and ball milled for 2 hours. After the mixture was fully blended, the powder was transferred to an alumina crucible and fired at 1050°C for 5 hours under flowing humid air. After firing, a yellow body color powder was obtained. The emission spectrum of BaZnUO2(PO4)2 is shown in Fig.28A .

[0065] In order to prepare 3+ BaZnUO2(PO4)2 was prepared by the same procedure as above except that 0.005Eu2O3 was used instead of BaHPO4. After firing, a yellow powder was obtained. 3+ The emission spectrum of BaZnUO2(PO4)2 is shown in Fig.28B .

[0066] Example 20 Preparation of γ-Ba2UO2(PO4)2 and co-doped phosphorescent materials To prepare γ-Ba2UO2(PO4)2, BaHPO4, UO2 and DAP were weighed in a molar ratio of 2:1:0.05 and then placed in a Nalgene bottle with zirconia media and ball milled for two hours. After the mixture was fully blended, the powder was transferred to an alumina crucible and fired in air at 1100°C for 5 hours. After firing, a yellow body color powder was obtained. The emission spectrum of γ-Ba2UO2(PO4)2 is shown in Fig.29A .

[0067] In order to prepare 3+ γ-Ba2UO2(PO4)2, BaHPO4, UO2, DAP and Eu2O3 were weighed in a molar ratio of 1.99:1:0.05:0.005, and then placed in a Nalgene bottle with zirconium oxide medium and ball milled for 2 hours. After the mixture was fully blended, the powder was transferred to an alumina crucible and fired in air at 1100°C for 5 hours. After firing, a yellow body color powder was obtained. Doped with Eu 3+ The emission spectrum of γ-Ba2UO2(PO4)2 is shown in Fig.29B middle.

[0068] 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 embodiments that occur to those skilled in the art. Such other embodiments 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 language of the claims.

Claims

1. A green light emitting phosphor, the green light emitting phosphor is selected from: [Ba 1-a-b Sr a Ca b ] x [Mg,Zn] y (UO2) z ([P,V]O4) 2(x+y+z) / 3 , where 0≤a≤1, 0≤b≤1, 0.75≤x≤1.25, 0.75≤y≤1.25 and 0.75≤z≤1.25; and [Ba,Sr,Ca,Mg,Zn] p (UO2) q [P,V] r O (2p+2q+5r) / 2 , Wherein 2.5≤p≤3.5, 1.75≤q≤2.25 and 3.5≤r≤4.5, wherein when the formula is Ba2UO2(PO4)2, the phosphor is γ-Ba2UO2(PO4)2.

2. The green light emitting phosphor according to claim 1, wherein the green light emitting phosphor has the formula [Ba 1-a-b Sr a Ca b ] x [Mg,Zn] y (UO2) z ([P,V]O4) 2(x+y+z) / 3 , Among them, 0≤a≤1, 0≤b≤1, 0.75≤x≤1.25, 0.75≤y≤1.25, and 0.75≤z≤1.

25.

3. The green light emitting phosphor according to claim 1, wherein the green light emitting phosphor has the formula [Ba x [Mg, Zn] y (UO2) z [PO4] 2(x+y+z) / 3 , where 0.75≤x≤1.25, 0.75≤y≤1.25, and 0.75≤z≤1.

25.

4. The green light emitting phosphor of claim 1, having the formula Ba[Mg,Zn]UO2(PO4)2.

5. The green light emitting phosphor of claim 1, having the formula BaMgUO2(PO4)2.

6. The green light emitting phosphor of claim 1, having the formula BaZnUO2(PO4)2.

7. The green light emitting phosphor of claim 1, wherein the green light emitting phosphor has the formula [Ba,Sr,Ca,Mg,Zn] p (UO2) q [P,V] r O (2p+2q+5r) / 2 , Among them, 2.5≤p≤3.5, 1.75≤q≤2.25, and 3.5≤r≤4.

5.

8. The green light emitting phosphor of claim 1, having the formula Ba p (UO2) q P r O (2p+2q+5r) / 2 , Among them, 2.5≤p≤3.5, 1.75≤q≤2.25, and 3.5≤r≤4.

5.

9. The green light emitting phosphor of claim 1, having the formula Ba3(PO4)2(UO2)2P2O7.

10. The green light emitting phosphor of claim 1, having the formula γ-Ba2UO2(PO4)2.

11. The green light emitting phosphor according to claim 10, wherein γ-Ba2UO2(PO4)2 is co-doped with Eu 3+ .

12. A green light emitting phosphor according to claim 1, wherein the phosphor has a formula selected from the following: Ba2Sr(PO4)2(UO2)2P2O7, BaSr2(PO4)2(UO2)2P2O7, Sr3(PO4)2(UO2)2P2O7, Ca3(PO4)2(UO2)2P2O7, BaMg2(PO4)2(UO2)2P2O7, Ba2Mg(PO4)2(UO2)2P2O7 and Ba2UO2(VO4)2.

13. The green light emitting phosphor of claim 1, wherein the phosphor is co-doped with Eu 3+ .

14. A phosphor composition comprising a green light emitting phosphor and a red light emitting phosphor, wherein the green light emitting phosphor is selected from: [Ba 1-a-b Sr a Ca b ] x [Mg,Zn] y (UO2) z ([P,V]O4) 2(x+y+z) / 3 , where 0≤a≤1, 0≤b≤1, 0.75≤x≤1.25, 0.75≤y≤1.25 and 0.75≤z≤1.25; and [Ba,Sr,Ca,Mg,Zn] p (UO2) q [P,V] r O (2p+2q+5r) / 2 , wherein 2.5≤p≤3.5, 1.75≤q≤2.25 and 3.5≤r≤4.5, wherein when the formula is Ba2UO2(PO4)2, the phosphor is γ-Ba2UO2(PO4)2; and The red light emitting phosphor is selected from: [Ba,Sr,Ca]2Si5N8:Eu 2+ ; [Ca,Sr]AlSiN3:I 2+ ; [Ba,Sr,Ca]LiAl3N4:Iu 2+ ; [Sr,Ca,Mg]S:Eu 2+ ;and Phosphor of formula I IN x MF y :Mn 4+ I in A is Li, Na, K, Rb, Cs or a combination thereof; M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Hf, Y, La, Nb, Ta, Bi, Gd or a combination thereof; x is MF y the absolute value of the ion's charge; and y is 5, 6, or 7.

15. The phosphor composition according to claim 14, wherein the phosphor of formula I is K2SiF6:Mn 4+ or Na2SiF6:Mn 4+ .

16. A device comprising an LED light source radiatively and / or optically coupled to a green light emitting phosphor selected from: [Ba 1-a-b Sr a Ca b ] x [Mg,Zn] y (UO2) z ([P,V]O4] 2(x+y+z) / 3 , where 0≤a≤1, 0≤b≤1, 0.75≤x≤1.25, 0.75≤y≤1.25 and 0.75≤z≤1.25; and [Ba,Sr,Ca,Mg,Zn] p (UO2) q [P,V] r O (2p+2q+5r) / 2 , Wherein 2.5≤p≤3.5, 1.75≤q≤2.25 and 3.5≤r≤4.5, wherein when the formula is Ba2UO2(PO4)2, the phosphor is γ-Ba2UO2(PO4)2.

17. The device of claim 16, further comprising a red light emitting phosphor selected from: (Ba,Sr,Ca)2Si5N8:Eu 2+ ; (Ca,Sr)AlSiN3:Iu 2+ ; (Ba,Sr,Ca)LiAl3N4:Iu 2+ ; (Sr,Ca,Mg)S:Eu 2+ ;and Phosphor of formula I IN x MF y :Mn 4+ I in A is Li, Na, K, Rb, Cs or a combination thereof; M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Hf, Y, La, Nb, Ta, Bi, Gd or a combination thereof; x is MF y the absolute value of the ion's charge; and y is 5, 6, or 7.

18. The device according to claim 17, wherein the phosphor of formula I is K2SiF6:Mn 4+ or Na2SiF6:Mn 4+ .

19. The device of claim 16 or 17, further comprising a quantum dot material.

20. The device according to any one of claims 16 to 18, wherein the LED light source is a mini LED or a micro LED.

21. The device of any one of claims 16 to 18, wherein the LED light source is a UV or blue light emitting LED.

22. The device of claim 19, wherein the quantum dot material comprises halide perovskite quantum dots.

23. A lighting device comprising the apparatus according to any one of claims 16 to 18.

24. A display device comprising the apparatus according to any one of claims 16 to 18.

25. A television set comprising a device according to any one of claims 16 to 18.

26. A mobile phone comprising a device according to any one of claims 16 to 18.

27. A computer monitor comprising a device according to any one of claims 16 to 18.

28. A tablet computer comprising the device according to any one of claims 16 to 18.

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