Green-emitting phosphors and devices thereof
A device including an LED light source optically coupled to a green-emitting U 6+ -doped phosphor having a composition selected from the group consisting of U 6+ -doped phosphate-vanadate phosphors, U 6+ -doped halide phosphors, U 6+ -doped oxyhalide phosphors, U 6+ -doped silicate-germanate phosphors, U 6+ -doped alkali earth oxide phosphors, and combinations thereof, is presented. The U 6+ -doped phosphate-vanadate phosphors are selected from the group consisting of compositions of formulas (A1)-(A12). The U 6+ -doped halide phosphors are selected from the group consisting of compositions for formulas (B1)-(B3). The U 6+ -doped oxyhalide phosphors are selected from the group consisting of compositions of formulas (C1)-(C5). The U 6+ -doped silicate-germanate phosphors are selected from the group consisting of compositions of formulas (D1)-(D11). The U 6+ -doped alkali earth oxide phosphors are selected from the group consisting of formulas (E1)-(E11).
1. A device comprising an LED light source optically coupled to a green-emitting U 6+ -doped phosphor selected from the group consisting of U 6+ -doped phosphate-vanadate phosphors, U 6+ -doped halide phosphors, U 6+ -doped oxyhalide phosphors, U 6+ -doped silicate-germanate phosphors, U 6+ -doped alkali earth oxide phosphors, and combinations thereof;
wherein,
the U 6+ -doped phosphate-vanadate phosphors are selected from the group consisting of:
(A2) Ba 2−x [Sr, Ca, Mg] x [P 1−y , V y ] 2 O 7 : U 6+ ; wherein 0≤x≤2, 0≤y≤1, and x≠0 when y=0;
(A3) [Ba, Sr, Ca, Mg] 4 [P, V] 2 O 9 : U 6+ ;
(A4) [Ba, Sr, Ca, Mg] 3 [P, V] 4 O 13 : U 6+ ;
(A5) [Ba, Sr, Ca, Mg] 4 [B, Al, Ga, In][P, V]O 8 : U 6+ ;
(A6) [Ba, Sr, Ca, Mg] 6 [B, Al, Ga, In] 5 [P, V] 5 O 26 : U 6+ ;
(A8) A 2 [Ba, Sr, Ca, Mg][P, V] 2 O 7 : U 6+ ;
(A9) A[Ba, Sr, Ca, Mg][P, V]O 4 : U 6+ ;
(A10) [Ba, Sr, Ca, Mg][P, V] 2 O 6 : U 6+ ;
(A11) [Ba, Sr, Ca, Mg] 3 [B, Al, Ga, In][P, V]O 7 : U 6+ ; and
(A12) [Ba, Sr, Ca, Mg] 10 [P, V] 6 O 25 : U 6+ ;
the U 6+ -doped halide phosphors are selected from the group consisting of:
(B2) A[Ba, Sr, Ca, Mg]X 3 : U 6+ ; and
(B3) [Ba, Sr, Ca, Mg] 2 X 4 : U 6+ ;
the U 6+ -doped oxyhalide phosphors are selected from the group consisting of:
(C1) [Ba, Sr, Ca, Mg] 2 [B, Al, Ga, In]O 3 X: U 6+ ;
(C2) [Ba, Sr, Ca, Mg] 2 [P, V]O 4 X: U 6+ ;
(C4) [Ba, Sr, Ca, Mg] 5 [B, Al, Ga, In] 3 O 9 X: U 6+ ; and
(C5) [Ba, Sr, Ca, Mg] 3 [Si, Ge]O 4 X: U 6+ ;
the U 6+ -doped silicate-germanate phosphors are selected from the group consisting of:
(D1) [Ba, Sr, Ca, Mg] 2 [Si, Ge]O 4 : U 6+ ;
(D2) [Ba, Sr, Ca, Mg] 3 [Si, Ge]O 5 : U 6+ ;
(D3) [Ba, Sr, Ca, Mg] 3 [Si, Ge] 2 O 7 : U 6+ ;
(D4) [Ba, Sr, Ca, Mg][Si, Ge]O 3 : U 6+ ;
(D5) [Ba, Sr, Ca, Mg][B, Al, Ga, In] 2 [Si, Ge] 2 O 8 : U 6+ ;
(D6) [Ba, Sr, Ca, Mg] 2 [B, Al, Ga, In] 2 [Si, Ge]O 7 : U 6+ ;
(D7) [Ba, Sr, Ca, Mg] 3 [B, Al, Ga, In] 6 [Si, Ge] 2 O 16 : U 6+ ;
(D8) [Ba, Sr, Ca, Mg] 3 [B, Al, Ga, In] 2 [Si, Ge]O 8 : U 6+ ;
(D9) [Ba, Sr, Ca, Mg] 11 [B, Al, Ga, In] 2 [Si, Ge] 4 O 22 : U 6+ ;
(D10) [Ba, Sr, Ca, Mg] 3 [B, Al, Ga, In] 10 [Si, Ge]O 20 : U 6+ ; and
(D11) [Ba, Sr, Ca, Mg] 6.5 [B, Al, Ga, In] 11 [Si, Ge] 5 O 33 : U 6+ ; and
the U 6+ -doped alkali earth oxide phosphors are selected from the group consisting of:
(E1) [Ba, Sr, Ca, Mg][B, Al, Ga, In] 4 O 7 : U 6+ ;
(E2) [Ba, Sr, Ca, Mg] 3 [B, Al, Ga, In] 2 O 6 : U 6+ ;
(E3) [Ba, Sr, Ca, Mg][B, Al, Ga, In] 6 O 10 : U 6+ ;
(E4) [Ba, Sr, Ca, Mg][B, Al, Ga, In] 2 O 4 : U 6+ ;
(E5) [Ba, Sr, Ca, Mg] 4 [B, Al, Ga, In] 2 O 7 : U 6+ ;
(E6) [Ba, Sr, Ca, Mg] 12 [B, Al, Ga, In] 14 O 33 : U 6+ ;
(E7) A[Ba, Sr, Ca, Mg][B, Al, Ga, In]O 3 : U 6+ ;
(E9) [Ba, Sr, Ca, Mg] 2 [B, Al, Ga, In, Sc] 2 O 5 : U 6+ ;
(E10) A[Ba, Sr, Ca, Mg] 2 [B, Al, Ga, In] 5 O 10 : U 6+ ; and
(E11) A[Ba, Sr, Ca, Mg] 4 [B, Al, Ga, In] 3 O 9 : U 6+ ;
wherein,
A is Li, Na, K, Rb, Cs, or a combination thereof
X is F, Cl, Br or a combination thereof.
2. A device according to claim 1 , wherein the green-emitting U 6+ -doped phosphor is a U 6+ -doped phosphate-vanadate phosphor selected from the group consisting of:
(A2) Ba 2−x [Sr, Ca, Mg] x [P 1−y , V y ] 2 O 7 : U 6+ ; wherein 0≤x≤2, 0≤y≤1, and x≠0 when y=0;
(A3) [Ba, Sr, Ca, Mg] 4 [P, V] 2 O 9 : U 6+ ;
(A4) [Ba, Sr, Ca, Mg] 3 [P, V] 4 O 13 : U 6+ ;
(A5) [Ba, Sr, Ca, Mg] 4 [B, Al, Ga, In][P, V]O 8 : U 6+ ;
(A6) [Ba, Sr, Ca, Mg] 6 [B, Al, Ga, In] 5 [P, V] 5 O 26 : U 6+ ;
(A8) A 2 [Ba, Sr, Ca, Mg][P, V] 2 O 7 : U 6+ ;
(A9) A[Ba, Sr, Ca, Mg][P, V]O 4 : U 6+ ;
(A10) [Ba, Sr, Ca, Mg][P, V] 2 O 6 : U 6+ ;
(A11) [Ba, Sr, Ca, Mg] 3 [B, Al, Ga, In][P, V]O 7 : U 6+ ; and
(A12) [Ba, Sr, Ca, Mg] 10 [P, V] 6 O 25 : U 6+ .
3. A device according to claim 1 , wherein the green-emitting U 6+ -doped phosphor is a U 6+ -doped halide phosphor selected from the group consisting of:
(B2) A[Ba, Sr, Ca, Mg]X 3 : U 6+ ; and
(B3) [Ba, Sr, Ca, Mg] 2 X 4 : U 6+ .
4. A device according to claim 1 , wherein the green-emitting U 6+ -doped phosphor is a U 6+ -doped oxyhalide phosphor selected from the group consisting of:
(C1) [Ba, Sr, Ca, Mg] 2 [B, Al, Ga, In]O 3 X: U 6+ ;
(C2) [Ba, Sr, Ca, Mg] 2 [P, V]O 4 X: U 6+ ;
(C4) [Ba, Sr, Ca, Mg] 5 [B, Al, Ga, In] 3 O 9 X: U 6+ ; and
(C5) [Ba, Sr, Ca, Mg] 3 [Si, Ge]O 4 X: U 6+ .
5. A device according to claim 1 , wherein the green-emitting U 6+ -doped phosphor is a U 6+ -doped silicate-germanate phosphor selected from the group consisting of:
(D1) [Ba, Sr, Ca, Mg] 2 [Si, Ge]O 4 : U 6+ ;
(D2) [Ba, Sr, Ca, Mg] 3 [Si, Ge]O 5 : U 6+ ;
(D3) [Ba, Sr, Ca, Mg] 3 [Si, Ge] 2 O 7 : U 6+ ;
(D4) [Ba, Sr, Ca, Mg][Si, Ge]O 3 : U 6+ ;
(D5) [Ba, Sr, Ca, Mg][B, Al, Ga, In] 2 [Si, Ge] 2 O 8 : U 6+ ;
(D6) [Ba, Sr, Ca, Mg] 2 [B, Al, Ga, In] 2 [Si, Ge]O 7 : U 6+ ;
(D7) [Ba, Sr, Ca, Mg] 3 [B, Al, Ga, In] 6 [Si, Ge] 2 O 16 : U 6+ ;
(D8) [Ba, Sr, Ca, Mg] 3 [B, Al, Ga, In] 2 [Si, Ge]O 8 : U 6+ ;
(D9) [Ba, Sr, Ca, Mg] ii [B, Al, Ga, In] 2 [Si, Ge] 4 O 22 : U 6+ ;
(D10) [Ba, Sr, Ca, Mg] 3 [B, Al, Ga, In] 10 [Si, Ge]O 20 : U 6+ ; and
(D11) [Ba, Sr, Ca, Mg] 6.5 [B, Al, Ga, In] 11 [Si, Ge] 5 O 33 : U 6+ .
6. A device according to claim 1 , wherein the green-emitting U 6+ -doped phosphor is a U 6+ -doped alkali earth oxide phosphor selected from the group consisting of:
(E1) [Ba, Sr, Ca, Mg][B, Al, Ga, In] 4 O 7 : U 6+ ;
(E2) [Ba, Sr, Ca, Mg] 3 [B, Al, Ga, In] 2 O 6 : U 6+ ;
(E3) [Ba, Sr, Ca, Mg][B, Al, Ga, In] 6 O 10 : U 6+ ;
(E4) [Ba, Sr, Ca, Mg][B, Al, Ga, In] 2 O 4 : U 6+ ;
(E5) [Ba, Sr, Ca, Mg] 4 [B, Al, Ga, In] 2 O 7 : U 6+ ;
(E6) [Ba, Sr, Ca, Mg] 12 [B, Al, Ga, In] 14 O 33 : U 6+ ;
(E7) A[Ba, Sr, Ca, Mg][B, Al, Ga, In]O 3 : U 6+ ;
(E9) [Ba, Sr, Ca, Mg] 2 [B, Al, Ga, In, Sc] 2 O 5 : U 6+ ;
(E10) A[Ba, Sr, Ca, Mg] 2 [B, Al, Ga, In] 5 O 10 : U 6+ ; and
(E11) A[Ba, Sr, Ca, Mg] 4 [B, Al, Ga, In] 3 O 9 : U 6+ .
7. A device according to claim 1 , additionally comprising a 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;
x is an absolute value of a charge of the MF y ion; and
y is 5, 6 or 7.
8. A device according to claim 7 , wherein the phosphor of formula I is K 2 SiF 6 :Mn 4+ .
9. A lighting apparatus comprising the device of claim 1 .
10. A backlight apparatus comprising the device of claim 1 .
11. The backlight apparatus according to claim 10 , wherein the device comprises a green-emitting U 6+ -doped phosphor selected from the group consisting of Sr 3 B 2 O 6 : U 6+ , Ca 3 B 2 O 6 : U 6+ , Ca 10 P 6 O 25 : U 6+ , Sr 10 P 6 O 25 : U 6+ , Sr 4 AlPO 8 : U 6+ , Ba 4 AlPO 8 : U 6+ , Sr 2 SiO 4 : U 6+ , Ca 2 SiO 4 : U 6+ , Sr 3 Al 2 O 6 : U 6+ , Ca 3 Al 2 O 6 : U 6+ , Ca 12 Al 14 O 33 : U 6+ , Ca 2 Al 2 SiO 7 : U 6+ , Ca 2 BO 3 Cl: U 6+ , Ca 2 PO 4 Cl: U 6+ , Sr 5 (BO 3 ) 3 Cl: U 6+ , Ca 2 GeO 4 : U 6+ , Sr 2 GeO 4 : U 6+ , NaCaPO 4 : U 6+ , Ca 3 In 2 O 6 : U 6+ , LiSrBO 3 : U 6+ , LiCaBO 3 : U 6+ , Sr 3 Ga 2 O 6 : U 6+ and LiSr 4 B 3 O 9 : U 6+ .
12. A television comprising the backlight apparatus of claim 10 .
13. A mobile phone comprising the backlight apparatus of claim 10 .
14. A computer monitor comprising the backlight apparatus of claim 10 .
15. A green-emitting U 6+ -doped phosphor, selected from [Ba, Sr, Ca, Mg] 4 [B, Al, Ga, In][P, V]O 8 : U 6+ and [Ba, Sr, Ca, Mg] 6 [B, Al, Ga, V] 5 O 26 : U 6+ .
16. A device comprising an LED light source optically coupled to a green-emitting U 6+ -doped phosphor selected from the group consisting of U 6+ -doped phosphate-vanadate phosphors, U 6+ -doped halide phosphors, U 6+ -doped oxyhalide phosphors, U 6+ -doped silicate-germanate phosphors, U 6+ -doped alkali earth oxide phosphors, and combinations thereof,
wherein the U 6+ -doped phosphate-vanadate phosphors are selected from the group consisting of:
(A2) Ba 2−x [Sr, Ca, Mg] x [P 1−y , V y ] 2 O 7 : U 6+ ; wherein 0≤x≤2, 0≤y≤1, and x≠0 when y=0;
(A3) [Ba, Sr, Ca, Mg] 4 [P, V] 2 O 9 : U 6+ ;
(A4) [Ba, Sr, Ca, Mg] 3 [P, V] 4 O 13 : U 6+ ;
(A5) [Ba, Sr, Ca, Mg] 4 [B, Al, Ga, In][P, V]O 8 : U 6+ ;
(A6) [Ba, Sr, Ca, Mg] 6 [B, Al, Ga, In] 5 [P, V] 5 O 26 : U 6+ ;
(A8) A 2 [Ba, Sr, Ca, Mg][P, V] 2 O 7 : U 6+ ;
(A9) A[Ba, Sr, Ca, Mg][P, V]O 4 : U 6+ ;
(A10) [Ba, Sr, Ca, Mg][P, V] 2 O 6 : U 6+ ;
(A11) [Ba, Sr, Ca, Mg] 3 [B, Al, Ga, In][P, V]O 7 : U 6+ ; and
(A12) [Ba, Sr, Ca, Mg] 10 [P, V] 6 O 25 : U 6+ ;
wherein, A is Li, Na, K, Rb, Cs, or a combination thereof; the U 6+ -doped halide phosphors are selected from the group consisting of:
(B2) A[Ba, Sr, Ca, Mg]X 3 : U 6+ ; and
(B3) [Ba, Sr, Ca, Mg] 2 X 4 : U 6+ ;
wherein, A is Li, Na, K, Rb, Cs, or a combination thereof; and X is F, Cl, Br or a combination thereof; the U 6+ -doped oxyhalide phosphors are selected from the group consisting of:
(C1) [Ba, Sr, Ca, Mg] 2 [B, Al, Ga, In]O 3 X: U 6+ ;
(C2) [Ba, Sr, Ca, Mg] 2 [P, V]O 4 X: U 6+ ;
(C4) [Ba, Sr, Ca, Mg] 5 [B, Al, Ga, In] 3 O 9 X: U 6+ ; and
(C5) [Ba, Sr, Ca, Mg] 3 [Si, Ge]O 4 X: U 6+ ;
wherein X is F, Cl, Br or a combination thereof; and the U 6+ -doped alkali earth oxide phosphors are selected from the group consisting of:
(E1) [Ba, Sr, Ca, Mg][B, Al, Ga, In] 4 O 7 : U 6+ ;
(E2) [Ba, Sr, Ca, Mg] 3 [B, Al, Ga, In] 2 O 6 : U 6+ ;
(E3) [Ba, Sr, Ca, Mg][B, Al, Ga, In] 6 O 10 : U 6+ ;
(E4) [Ba, Sr, Ca, Mg][B, Al, Ga, In] 2 O 4 : U 6+ ;
(E5) [Ba, Sr, Ca, Mg] 4 [B, Al, Ga, In] 2 O 7 : U 6+ ;
(E6) [Ba, Sr, Ca, Mg] 12 [B, Al, Ga, In] 14 O 33 : U 6+ ;
(E7) A[Ba, Sr, Ca, Mg][B, Al, Ga, In]O 3 : U 6+ ;
(E9) [Ba, Sr, Ca, Mg] 2 [B, Al, Ga, In, Sc] 2 O 5 : U 6+ ;
(E10) A[Ba, Sr, Ca, Mg] 2 [B, Al, Ga, In] 5 O 10 : U 6+ ; and
(E11) A[Ba, Sr, Ca, Mg] 4 [B, Al, Ga, In] 3 O 9 : U 6+
wherein, A is Li, Na, K, Rb, Cs, or a combination thereof.
17. The device according to claim 16 , wherein the green-emitting U 6+ -doped phosphor is a U 6+ -doped phosphate-vanadate phosphor.
18. A device according to claim 16 , wherein the green-emitting U 6+ -doped phosphor is a U 6+ -doped halide phosphor.
19. A device according to claim 16 , wherein the green-emitting U 6+ -doped phosphor is a U 6+ -doped oxyhalide phosphor.
20. A device according to claim 16 , wherein the green-emitting U 6+ -doped phosphor is a U 6+ -doped silicate-germanate phosphor selected from the group consisting of:
(D1) [Ba, Sr, Ca, Mg] 2 [Si, Ge]O 4 : U 6+ ;
(D2) [Ba, Sr, Ca, Mg] 3 [Si, Ge]O 5 : U 6+ ;
(D3) [Ba, Sr, Ca, Mg] 3 [Si, Ge] 2 O 7 : U 6+ ;
(D4) [Ba, Sr, Ca, Mg][Si, Ge]O 3 : U 6+ ;
(D5) [Ba, Sr, Ca, Mg][B, Al, Ga, In] 2 [Si, Ge] 2 O 8 : U 6+ ;
(D6) [Ba, Sr, Ca, Mg] 2 [B, Al, Ga, In] 2 [Si, Ge]O 7 : U 6+ ;
(D7) [Ba, Sr, Ca, Mg] 3 [B, Al, Ga, In] 6 [Si, Ge] 2 O 16 : U 6+ ;
(D8) [Ba, Sr, Ca, Mg] 3 [B, Al, Ga, In] 2 [Si, Ge]O 8 : U 6+ ;
(D9) [Ba, Sr, Ca, Mg] 11 [B, Al, Ga, In] 2 [Si, Ge] 4 O 22 : U 6+ ;
(D10) [Ba, Sr, Ca, Mg] 3 [B, Al, Ga, In] 10 [Si, Ge]O 20 : U 6+ ; and
(D11) [Ba, Sr, Ca, Mg] 6.5 [B, Al, Ga, In] 11 [Si, Ge] 5 O 33 : U 6+ .
21. A device according to claim 16 , wherein the green-emitting U 6+ -doped phosphor is a U 6+ -doped alkali earth oxide phosphor.