Method to enhance phosphor robustness and dispersability and resulting phosphors
Briefly, in one aspect, the present invention relates to processes for producing a stabilized Mn 4+ doped phosphor in solid form and a composition containing such doped phosphor. Such process may include combining a) a solution comprising at least one substance selected from the group consisting of: K 2 HPO 4 , an aluminum phosphate, oxalic acid, phosphoric acid, a surfactant, a chelating agent, or a combination thereof, with b) a Mn 4+ doped phosphor of formula I in solid form, where formula I may be: A x [MF y ]:Mn 4+ . The process can further include isolating the stabilized Mn 4+ doped phosphor in solid form. In formula I, A may be Li, Na, K, Rb, Cs, or a combination thereof. In formula I, M may be Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd, or a combination thereof. In formula I, x is the absolute value of the charge of the [MF y ] ion and y is 5, 6 or 7.
1. A process comprising combining a) a solution comprising at least one substance selected from the group consisting of: K 2 HPO 4 , an aluminum phosphate, oxalic acid, or a combination thereof, and optionally, a surfactant or a chelating agent, with b) a Mn 4+ doped phosphor of formula I in solid form;
A x [MF y ]:Mn 4+ I
and isolating a stabilized Mn 4+ doped phosphor in solid form; wherein A is Li, Na, K, Rb, Cs, 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 [MF y ] ion; y is 5, 6 or 7.
2. The process according to claim 1 , further comprising, prior to combining with the at least one substance, contacting the Mn 4+ doped phosphor of formula I with a fluorine-containing oxidizing agent in gaseous form at an elevated temperature, to form a product phosphor.
3. The process according to claim 1 , wherein M is Si, Ge, Ti, or a combination thereof; A is Na, K, or a combination thereof.
4. The process according to claim 1 , wherein the phosphor of formula I is K 2 SiF 6 :Mn 4+ .
5. The process according to claim 1 , wherein the at least one substance comprises K 2 HPO 4 .
6. The process according to claim 1 , wherein the at least one substance comprises the surfactant and K 2 HPO 4 .
7. The process according to claim 1 , wherein the solution is aqueous and additionally comprises H 2 O 2 .
8. The process according to claim 1 , wherein the solution additionally comprises at least one solvent selected from the group consisting of: 1-octadecene, isonorbornyl acrylate, water, and propylene glycol monomethyl ether acetate.
9. The process according to claim 6 , wherein the surfactant comprises at least one selected from the group consisting of: polyoxyethylene octyl phenyl ether, potassium oleate, polyoxyethylene-polyoxypropylene block copolymer; polyoxyethylene (20) sorbitan monolaurate, poly(acrylic acid sodium salt), and potassium sorbate.
10. A process comprising combining a) a solution comprising at least one substance selected from the group consisting of: K 2 HPO 4 , an aluminum phosphate, oxalic acid, phosphoric acid, or a combination thereof, and optionally, a surfactant or a chelating agent, with b) a Mn 4+ doped phosphor of formula I in solid form:
A x [MF y ]:Mn 4+ I
and isolating a stabilized Mn 4+ doped phosphor in solid form: wherein A is Li, Na, K, Rb, Cs, 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 [MF y ] ion: y is 5, 6 or 7,
wherein the Mn 4+ doped phosphor of formula I comprises a core comprising a phosphor of formula I and a manganese-free composite coating disposed on the core, the manganese-free composite coating comprising a compound of formula III and a metal fluoride selected from the group consisting of calcium fluoride, strontium fluoride, magnesium fluoride, yttrium fluoride, scandium fluoride, lanthanum fluoride, and combinations thereof,
A 1 x [M 1 F y ] (III)
wherein A 1 is H, Li, Na, K, Rb, Cs, or a combination thereof; M 1 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 [M 1 F y ] ion; and y is 5, 6 or 7.
11. A composition comprising a) at least one substance selected from the group consisting of: K 2 HPO 4 , an aluminum phosphate, oxalic acid, or a combination thereof, and b) a Mn 4+ doped 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, Y, La, Nb, Ta, Bi, Gd, or a combination thereof; x is the absolute value of the charge of the [MF y ] ion; y is 5, 6 or 7.
12. The composition according to claim 11 , wherein M is Si, Ge, Ti, or a combination thereof; A is Na, K, or a combination thereof.
13. The composition according to claim 11 , wherein the phosphor of formula I is K 2 SiF 6 :Mn 4+ .
14. The composition according to claim 11 , wherein the at least one substance comprises K 2 HPO 4 and magnesium fluoride.
15. A composition comprising a) at least one substance selected from the group consisting of: K 2 HPO 4 , an aluminum phosphate, oxalic acid, phosphoric acid, or a combination thereof, and b) a Mn 4+ doped 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, Y, La, Nb, Ta, Bi, Gd, or a combination thereof; x is the absolute value of the charge of the [MF y ] ion; y is 5, 6 or 7,
wherein the Mn 4+ doped phosphor of formula I comprises a core comprising a phosphor of formula I and a manganese-free composite coating disposed on the core, the manganese-free composite coating comprising a compound of formula III and a metal fluoride selected from the group consisting of calcium fluoride, strontium fluoride, magnesium fluoride, yttrium fluoride, scandium fluoride, lanthanum fluoride, and combinations thereof,
A 1 x [M 1 F y ] (III)
wherein A 1 is H, Li, Na, K, Rb, Cs, or a combination thereof; M 1 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 [M 1 F y ] ion; and y is 5, 6 or 7.
16. A display device comprising a stabilized Mn 4+ doped phosphor produced by the process according to claim 1 .
17. The display device according to claim 16 , wherein the display device comprises a television, a computer monitor, a cellular or conventional phone, a digital photo frame, a tablet, an automotive display, an e-book reader, an electronic dictionary, a digital camera, an electronic keyboard, or a gaming device.
18. A lighting apparatus comprising a stabilized Mn 4+ doped phosphor produced by the process according to claim 1 .
19. A phosphor composition comprising phosphor particles and comprising, on surfaces of the phosphor particles, at least one surface composition selected from the group consisting of: 1) a composition comprising a phosphorus-containing moiety and a carbon-containing moiety; 2) a composition comprising the phosphorus-containing moiety and a metal fluoride; 3) a composition comprising the phosphorus-containing moiety and the carbon-containing moiety and the metal fluoride; and 4) a composition comprising the phosphorus-containing moiety free of an alkyl phosphate compound, wherein the phosphor particles comprise a Mn 4+ doped 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, Y, La, Nb, Ta, Bi, Gd, or a combination thereof; x is the absolute value of the charge of the [MF y ] ion; y is 5, 6 or 7, and
wherein a D 50 particle size of the phosphor particles before sonication of a suspension containing the particles is no greater than 30 μm and the D 50 particle size of the phosphor particles after sonication is no greater than 20 μm.
20. The phosphor composition according to claim 19 , wherein the metal fluoride comprises magnesium fluoride.
21. The phosphor composition according to claim 19 , wherein the phosphorus-containing moiety comprises a phosphate moiety.
22. The phosphor composition according to claim 19 , wherein the carbon-containing moiety comprises at least one selected from the group consisting of: ethylenediaminetetraacetic acid, polyoxyethylene octyl phenyl ether, potassium oleate, polyoxyethylene-polyoxypropylene block copolymer, polyoxyethylene (20) sorbitan monolaurate, poly(acrylic acid sodium salt), potassium sorbate, and derivatives or salts thereof.
23. The phosphor composition according to claim 19 , wherein the phosphor particles exhibit A) a quantum efficiency after exposure to liquid water for one hour at room temperature that is 50% to 100% of the quantum efficiency exhibited before water exposure or B) a quantum efficiency loss upon exposure to 85% relative humidity at 85 deg C. for 100 hours that is less than 40%.
24. A display device comprising the phosphor composition according to claim 19 .
25. A light emitting diode device being radiationally coupled to and/or comprising the phosphor composition according to claim 19 .
26. The light emitting diode device according to claim 25 , wherein the light emitting diode device is a mini LED or a micro LED.
27. The light emitting diode device according to claim 25 , wherein a) the light emitting diode device comprises an LED chip on which the phosphor composition is deposited and/or b) the composition is in a form of a film.
28. A television comprising the display device of claim 24 .
29. A smartphone comprising the display device of claim 24 .
30. A computer monitor comprising the display device of claim 24 .
31. A tablet comprising the display device of claim 24 .
32. The light emitting diode device according to claim 27 , wherein b) the composition is in a form of a film, the light emitting diode device comprises a semiconductor light source and the film is remote from the semiconductor light source.
33. The light emitting diode device according to claim 27 , wherein b) the composition is in a form of a film and the film further comprises quantum dot material.