Phosphors and phosphor-converted LEDs
The present invention relates to alkaline earth aluminate phosphors, to a process for the preparation thereof and to the use thereof as conversion phosphors. The present invention also relates to an emission-converting material comprising at least the conversion phosphor according to the invention, and to the use thereof in light sources, in particular pc-LEDs (phosphor converted light emitting devices). The present invention furthermore relates to light sources, in particular pc-LEDs, and to lighting units which comprise a primary light source and the emission-converting material according to the invention.
1. Compound of formula (1a),
(AE) a-d-v D d M 1 b-e M e 2 M 3 v E c-e X x N e+v Formula (1a)
where the following applies to the symbols and indices used:
AE is Ca, Sr, Ba or mixtures thereof;
D is Eu, Mn, Yb, Sm, Ce or mixtures thereof;
M 1 is B, Al, Ga, In, TI, Sc or mixtures thereof;
M 2 is C, Si, Ge, Sn or mixtures thereof;
M 3 is Y, Lu, La or mixtures thereof;
E is O, S, Se, Te or mixtures thereof;
X is F, Cl, Br, I or mixtures thereof;
N is a trivalent nitride ion;
0.65≤a≤1;
0≤v≤0.1a where a is as defined above;
10.667≤b≤11.133;
17.00≤c≤17.35;
0<d≤1;
0≤x≤5;
0≤e≤5;
0.0584≤a/b≤0.0938;
0.0375≤a/c≤0.0588;
2a+3b=2c+x;
with the proviso that x≠0 or v≠0 or e≠0 when AE=Ba and M 1 =Al.
2. The compound according to claim 1 wherein AE is Ba, a mixture of Ba and Sr or a mixture of Ba and Ca, having a maximum of 10 atom-% of Sr or Ca, respectively, with respect to the total content of AE.
3. The compound according to claim 1 wherein D is selected from Eu or a mixture of Eu and Mn, which comprises a maximum of 10 atom-% of Mn with respect to the total amount of AE+Eu+Mn.
4. The compound according to claim 1 wherein M 1 is Al, mixtures of Al with Ga or In, and wherein the total amount of Ga or In, respectively, is ≤10 atom-% of the total amount of M 1 .
5. The compound according to claim 1 , wherein the compound is selected from the compounds of the formulae (2′) to (11′),
(Ba 1-z Sr z ) a-d Eu d M 1 b-e M 2 e E c-e X x N e Formula (2′)
(Ba 1-z Sr z ) a-d (Eu,Mn) d M 1 b-e M 2 e E c-e X x N e Formula (3′)
(Ba 1-z Ca z ) a-d Eu d M 1 b-e M 2 e E c-e X x N e Formula (4′)
(Ba 1-z Ca z ) a-d (Eu,Mn) d M 1 b-e M 2 e E c-e X x N e Formula (5′)
Ba a-d-v Eu d M 1 b-e M 2 e M 3 v E c-e X x N e+v Formula (6′)
Ba a-d-v (Eu,Mn) d M 1 b-e M 2 e M 3 v E c-e X x N e+v Formula (7′)
(AE) a-d-v D d (Al 1-w B w ) b-e M 2 e M 3 v E c-e X x N e+v Formula (8′)
(AE) a-d-v D d (Al 1-w Ga w ) b-e M 2 e M 3 v E c-e X x N e+v Formula (9′)
(AE) a-d-v D d (Al 1-w In w ) b-e M 2 e M 3 v E c-e X x N e+v Formula (10′)
(AE) a-d-v D d (Al 1-w Sc w ) b-e M 2 e M 3 v E c-e X x N e+v Formula (11′)
where the symbols and indices have the meanings given in claim 1 and
0<d≤1;
0≤z≤0.1; and
0≤w≤0.1.
6. The compound according to claim 1 wherein E is O, S or mixtures thereof.
7. The compound according to claim 1 wherein X is F, CI or mixtures thereof, and wherein 0.001≤x≤0.1.
8. The compound according to claim 1 wherein 0.70≤a≤0.80.
9. The compound according to claim 1 , of the formulae (2a′) to (11a′)
(Ba 1-z Sr z ) a-d Eu d M 1 b-e M 2 e O c-e F x N e Formula (2a′)
(Ba 1-z Sr z ) a-d (Eu,Mn) d M 1 b-e M 2 e O c-e F x N e Formula (3a′)
(Ba 1-z Ca z ) a-d Eu d M 1 b-e M 2 e O c-e F x N e Formula (4a′)
(Ba 1-z Ca z ) a-d (Eu,Mn) d M 1 b-e M 2 e O c-e F x N e Formula (5a′)
Ba a-d-v Eu d M 1 b-e M 2 e M 3 v O c-e F x N e+v Formula (6a′)
Ba a-d-v (Eu,Mn) d M 1 b-e M 2 e M 3 v O c-e F x N e+v Formula (7a′)
(AE) a-d-v D d (Al 1-w B w ) b-e M 2 e M 3 v O c-e F x N e+v Formula (8a′)
(AE) a-d-v D d (Al 1-w Ga w ) b-e M 2 e M 3 v O c-e F x N e+v Formula (9a′)
(AE) a-d-v D d (Al 1-w In w ) b-e M 2 e M 3 v O c-e F x N e+v Formula (10a′)
(AE) a-d-v D d (Al 1-w Sc w ) b-e M 2 e M 3 v O c-e F x N e+v Formula (11a′)
where the symbols and indices have the following meanings:
AE is Ba or mixtures of Ba with Ca or Ba with Sr where the maximum amount of Ca or Sr, respectively, is 10 atom-% with respect to the total amount of AE+D;
D is Eu or a mixture of Eu and Mn;
M 1 is B, Al, Ga, In, Sc or mixtures of two thereof;
M 2 is Si, Ge or mixtures thereof;
M 3 is Y, Lu or La;
O is a divalent oxygen anion;
0.70≤a≤0.80;
0≤z≤0.05;
0.03≤d≤0.25;
19.93≤b≤11.067;
17.2≤c≤17.3;
with the proviso that x≠0 or e≠0 when z=0 and M 1 =Al in formulae (2a) to (5a); and
furthermore with the proviso that x≠0 or v≠0 or e≠0 when M 1 =Al in formulae (6a) and (7a);
and furthermore with the proviso that x≠0 or v≠0 or e≠0 when AE=Ba and w=0 in formulae (8a) to (11a).
10. A composition comprising a compound according to claim 1 that is coated.
11. A process for the preparation of a compound according to claim 1 , comprising:
a) preparing a mixture comprising AE, D, M 1 , E, optionally X and/or optionally M 2 and/or M 3 and/or optionally N; and
b) calcining of the mixture at elevated temperature.
12. A light source which comprises at least one primary light source and at least one compound according to claim 1 .
13. The light source according to claim 12 wherein the primary light source is a near-UV or violet LED diode and the light source comprises at least one compound emitting in the blue region of the spectrum, at least one compound emitting in the green region of the spectrum and at least one compound emitting in the orange or red region of the spectrum.
14. A The compound according to claim 1 , functioning as a conversion phosphor emitting light of a longer wavelength than its excitation source wavelength.
15. The compound according to claim 5 wherein E is O, S or mixtures thereof.
16. The compound according to claim 5 wherein X is F, Cl or mixtures thereof, and wherein 0.001≤x≤0.1.
17. The compound according to claim 5 wherein 0.70≤a≤0.80.