Process for preparing red-emitting phosphors
View Patent ↗A process for preparing a Mn 4+ doped phosphor of formula I A x [MF y ]:Mn +4 I includes combining in an acidic solution, an A + cation, an anion of formula MF y , and a Mn n+ source comprising a fluoromanganese compound, precipitating a Mn n+ containing phosphor precursor from the acidic solution, and contacting the Mn n+ containing phosphor precursor with a fluorine-containing oxidizing agent in gaseous form, at an elevated temperature, to form the Mn 4+ doped phosphor; 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; x is the absolute value of the charge of the [MFy] ion; y is 5, 6 or 7; and n is 2 or 3.
1. A process for preparing a Mn 4+ doped phosphor of formula I,
A x [MF y ]:Mn +4 I
the process comprising combining an A + cation, an anion of formula MF y , and a Mn n+ source comprising a fluoromanganese compound in an acidic solution;
precipitating a Mn n+ containing phosphor precursor from the acidic solution; and
contacting the Mn n+ containing phosphor precursor with a fluorine-containing oxidizing agent in gaseous form, at an elevated temperature, to form the Mn 4+ doped phosphor;
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;
x is 1, 2, or 3, and is the absolute value of the charge of the [MF y ] ion;
y is 5, 6 or 7; and
n is 2 or 3.
2. A process according to claim 1 , additionally comprising combining a fluoride or bifluoride anion, or a combination thereof, with the A+ cation, the anion of formula MF y , and the Mn n+ source.
3. A process according to claim 1 , wherein the Mn 4+ doped phosphor is K 2 SiF 6 :Mn 4+ .
4. A process according to claim 1 , wherein the anion of formula [MF y ] is SiF 6 .
5. A process according to claim 1 , wherein the A+ cation is derived from KF, KHF 2 , or a combination thereof.
6. A process according to claim 1 , wherein the Mn n+ source is selected from K 2 MnF 5 .H 2 O, KMnF 4 , K 2 MnF 4 , KMnF 3 , MnF 2 , MnF 3 , and combinations thereof.
7. A process according to claim 1 , wherein the Mn n+ source is K 2 MnF 5 .H 2 O.
8. A process according to claim 1 , wherein the acidic solution is aqueous fluorosilicic acid.
9. A process according to claim 1 , wherein the fluorine-containing oxidizing agent is F 2 .
10. A process according to claim 1 , wherein the step of contacting the Mn n+ containing phosphor precursor with the fluorine-containing oxidizing agent additionally comprises contacting the Mn n+ containing phosphor precursor with the fluorine-containing oxidizing agent and a compound of formula AX, where X is F, Cl, Br, I, HF 2 , or a combination thereof.
11. A process according to claim 1 , comprising
combining a solution comprising fluorosilicic acid and the Mn n+ source with a potassium fluoride compound selected from KF, KHF 2 , and combinations thereof;
precipitating a Mn n+ containing phosphor precursor; and
exposing the Mn n+ containing phosphor precursor to an atmosphere comprising at least 20% fluorine gas at an elevated temperature, to form the Mn 4+ doped phosphor;
wherein the Mn n+ source comprises a potassium fluoromanganese compound selected from K 2 MnF 5 .H 2 O, KMnF 4 , MnF 3 , and combinations thereof.
12. A process according to claim 1 , treating the phosphor in particulate form with a saturated solution of a composition of formula II in aqueous hydrofluoric acid
A x [MF y ] II.
13. A process for preparing a Mn 4+ doped phosphor, the process comprising
combining an A + cation, an anion of formula MF y , and a Mn n+ source comprising a fluoromanganese compound in an acidic solution;
precipitating a Mn n+ containing phosphor precursor from the acidic solution; and
contacting the Mn n+ containing phosphor precursor with a fluorine-containing oxidizing agent in gaseous form, at an elevated temperature, to form the Mn 4+ doped phosphor; wherein the Mn 4+ doped phosphor is selected from the group consisting of
(A) A 2 [MF 5 ]:Mn 4+ , where M is selected from Al, Ga, In, and combinations thereof;
(B) A 3 [MF 6 ]:Mn 4+ , where M is selected from Al, Ga, In, and combinations thereof;
(C) Zn 2 [MF 7 ]:Mn 4+ , where M is selected from Al, Ga, In, and combinations thereof;
(D) A[In 2 F 7 ]:Mn 4+ ;
(E) A 2 [MF 6 ]:Mn 4+ , where M is selected from Ge, Si, Sn, Ti, Zr, and combinations thereof;
(F) E[MF 6 ]:Mn 4+ , where E is selected from Mg, Ca, Sr, Ba, Zn, and combinations thereof; and where M is selected from Ge, Si, Sn, Ti, Zr, and combinations thereof;
(G) Ba 0.65 Zr 0.35 F 2.70 :Mn 4+ ; and
(H) A 3 [ZrF 7 ]:Mn 4+ ; and
A is Li, Na, K, Rb, Cs, or a combination thereof.
14. A process according to claim 13 , wherein the acidic solution is aqueous fluorosilicic acid.
15. A process according to claim 13 , wherein the fluorine-containing oxidizing agent is F 2 .