Phosphors

Abstract

The present invention relates to europium-doped phosphors, to a process for the preparation thereof, and to the use of these compounds as conversion phosphors. The present invention furthermore relates to light-emitting devices which comprise the phosphor according to the invention.

Claims

1. A compound of formula (1):
(EA).sub.1-yMSi.sub.4-xAl.sub.xN.sub.7-xO.sub.x:yEu.sup.2+  formula (1) wherein EA is Mg, Ca, Sr, or Ba or a mixture of two or more of the elements Mg, Ca, Sr and Ba; M is Y, or Lu or a mixture of Y and Lu; 0.004≦x≦3.0; 0<y≦0.25; with the proviso that compounds of formula SrYSi.sub.4-xAl.sub.xN.sub.7-xO.sub.x:y Eu.sup.2+ where 0.004≦x≦1.0 are excluded from the invention.

2. The compound according to claim 1, which is of formula (2),
(Mg.sub.aCa.sub.bSr.sub.cBa.sub.d).sub.1-y(Y.sub.eLu.sub.f)Si.sub.4-xAl.sub.xN.sub.7-xO.sub.x:yEu.sup.2+  formula (2) where x and y have the meanings given for the compound of formula (1) and furthermore: 0≦a≦1; 0≦b≦1; 0≦c≦1; 0≦d≦1; a+b+c+d=1; 0≦e≦1; 0≦f≦1; e+f=1; and at least three of a, b, c, d, e and f are >0.

3. The compound according to claim 1, which is one of formulae (2a) to (2n),
(Mg.sub.aCa.sub.b).sub.1-yYSi.sub.4-xAl.sub.xN.sub.7-xO.sub.x:yEu.sup.2+  formula (2a)
(Mg.sub.aCa.sub.b).sub.1-yLuSi.sub.4-xAl.sub.xN.sub.7-O.sub.x:yEu.sup.2+  formula (2b)
(Mg.sub.aSr.sub.c).sub.1-yYSi.sub.4-zAl.sub.xN.sub.7-xO.sub.x:yEu.sup.2+  formula (2c)
(Mg.sub.aSr.sub.c).sub.1-yLuSi.sub.4-xAl.sub.xN.sub.7-xO.sub.x:yEu.sup.2+  formula (2d)
(Ca.sub.bSr.sub.c).sub.1-yYSi.sub.4-xAl.sub.xN.sub.7-xO.sub.x:yEu.sup.2+  formula (2e)
(Ca.sub.bSr.sub.c).sub.1-yLuSi.sub.4-xAl.sub.xN.sub.7-xO.sub.x:yEu.sup.2+  formula (2f)
(Ca.sub.bBa.sub.d).sub.1-yYSi.sub.4-xAl.sub.xN.sub.7-xO.sub.x:yEu.sup.2+  formula (2g)
(Ca.sub.bBa.sub.d).sub.1-yLuSi.sub.4-xAl.sub.xN.sub.7-xO.sub.x:yEu.sup.2+  formula (2h)
(Sr.sub.cBa.sub.d).sub.1-yYSi.sub.4-xAl.sub.xN.sub.7-xO.sub.x:yEu.sup.2+  formula (2i)
(Sr.sub.cBa.sub.d).sub.1-yLuSi.sub.4-xAl.sub.xN.sub.7-xO.sub.x:yEu.sup.2+  formula (2j)
Mg.sub.1-y(Y.sub.dLU.sub.e)Si.sub.4-xAl.sub.xN.sub.7-xO.sub.x:yEu.sup.2+  formula (2k)
Ca.sub.1-y(Y.sub.eLu.sub.f)Si.sub.4-xAl.sub.xN.sub.7-xO.sub.x:yEu.sup.2+  formula (2l)
Sr.sub.1-y(Y.sub.eLu.sub.f)Si.sub.4-xAl.sub.xN.sub.7-xO.sub.x:yEu.sup.2+  formula (2m)
Ba.sub.1-y(Y.sub.eLu.sub.f)Si.sub.4-xAl.sub.xN.sub.7-xO.sub.x:yEu.sup.2+  formula (2n) where x and y have the meanings given for the compound of formula (1) and furthermore: 0<a≦1; 0<b≦1; 0<c≦1; 0<d≦1; 0<e≦1; 0<f≦1; a+b=1 in formulae (2a) and (2b); a+c=1 in formulae (2c) and (2d); b+c=1 in formulae (2e) and (2f); b+d=1 in formulae (2g) and (2h); c+d=1 in formulae (2i) and (2j); and e+f=1 in formulae (2k) to (2n).

4. The compound according to claim 3, wherein the Mg:Ca, Mg:Sr, Ca:Sr, Ca:Ba or Sr:Ba ratio, based on the molar amounts, in formulae (2a) to (2j) is between 50:1 and 1:50, and the Y:Lu ratio, based on the molar amounts, in the formulae (2k) to (2n) is between 50:1 and 1:50.

5. The compound according to claim 3, wherein the Mg:Ca, Mg:Sr, Ca:Sr, Ca:Ba or Sr:Ba ratio, based on the molar amounts, in formulae (2a) to (2j) is between 10:1 and 1:10, and the Y:Lu ratio, based on the molar amounts, in the formulae (2k) to (2n) is between 5:1 and 1:5.

6. The compound according to claim 1, which is one of formula (3), (4) or (5),
Mg.sub.1-yMSi.sub.4-xAl.sub.xN.sub.7-xO.sub.x:yEu.sup.2+  formula (3)
Ca.sub.1-yMSi.sub.4-xAl.sub.xN.sub.7-xO.sub.x:yEu.sup.2+  formula (4)
Ba.sub.1-yMSi.sub.4-xAl.sub.xN.sub.7-xO.sub.x:yEu.sup.2+  formula (5) where M, x and y have the meanings given for the compound of formula (1).

7. The compound according to claim 1, which is of formula (6),
(EA).sub.1-yLuSi.sub.4-xAl.sub.xN.sub.7-xO.sub.x:yEu.sup.2+  formula (6) where EA, x and y have the meanings given for the compound of formula (1).

8. The compound according to claim 1, wherein 0.5≦x≦2.0.

9. The compound according claim 1, wherein 0<y≦0.20.

10. A process for preparing the compound according to claim 1, comprising: a) preparing a mixture of an Mg, Ca, Sr and/or Ba compound, a Y and/or Lu compound, an Si compound, an Al compound and an Eu compound, where at least one of these compounds is in the form of a nitride and at least one of these compounds is in the form of an oxide; and b) calcining the mixture under non-oxidizing conditions.

11. The compound according to claim 1, which has a coating on its the surface.

12. An emission-converting material comprising at least one compound according to claim 1 and optionally one or more further conversion phosphors.

13. A method for converting light in a light source, comprising achieving said conversion by a conversion phosphor comprising a compound according to claim 1.

14. The compound according to claim 1, wherein 1.3≦x≦1.7.

15. The compound according claim 1, wherein 0.02≦y≦0.16.

16. The compound according to claim 1, which has a metal oxide or a nitride coating on its surface.

17. An emission-converting material comprising at least one compound according to claim 1 and one or more further conversion phosphors.

18. A shaped body or ceramic comprising a compound of formula (1) or an emission-converting material comprising said compound and optionally comprising one or more further conversion phosphors
(EA).sub.1-yMSi.sub.4-xAl.sub.xN.sub.7-xO.sub.x:yEu.sup.2+  formula (1) wherein EA is Mg, Ca, Sr, or Ba or a mixture of two or more of the elements Mg, Ca, Sr and Ba; M is Y, or Lu or a mixture of Y and Lu; 0.004≦x≦3.0; 0<y≦0.25; with the proviso that compounds of formula SrYSi.sub.4-xAl.sub.xN.sub.7-xO.sub.x:y Eu.sup.2+ where 0.004≦x≦1.0 are excluded from the invention.

19. A light source, comprising a primary light source and a at least one compound of formula (1) or an emission-converting material or a shaped body or ceramic comprising said compound and optionally comprising one or more further conversion phosphors
(EA).sub.1-yMSi.sub.4-xAl.sub.xN.sub.7-xO.sub.x:yEu.sup.2+  formula (1) wherein EA is Mg, Ca, Sr, or Ba or a mixture of two or more of the elements Mg, Ca, Sr and Ba; M is Y, or Lu or a mixture of Y and Lu; 0.004≦x≦3.0; 0<y≦0.25; with the proviso that compounds of formula SrYSi.sub.4-xAl.sub.xN.sub.7-x:y Eu.sup.2+ where 0.004≦x≦1.0 are excluded from the invention.

20. A lighting unit comprising at least one light source according to claim 19.

Description

DESCRIPTION OF THE FIGURES

(1) FIG. 1: X-ray powder diffraction pattern of SrLuAl.sub.1.5Si.sub.2.5N.sub.5.5O.sub.1.5:0.5% Eu.sup.2+ from Example 1.

(2) FIG. 2: Reflection spectrum of SrLuAl.sub.1.5Si.sub.2.5N.sub.5.5O.sub.1.5:0.5% Eu.sup.2+ from Example 1 (against BaSO.sub.4 as white standard).

(3) FIG. 3: Excitation spectrum of SrLuAl.sub.1.5Si.sub.2.5N.sub.5.5O.sub.1.5: 0.5% Eu.sup.2+ from Example 1 (λ.sub.em=530 nm).

(4) FIG. 4: Emission spectrum of SrLuAl.sub.1.5Si.sub.2.5N.sub.5.5O.sub.1.5: 0.5% Eu.sup.2+ from Example 1 (λ.sub.ex=410 nm).

(5) FIG. 5: X-ray powder diffraction pattern of SrLuAl.sub.1.5Si.sub.2.5N.sub.5.5O.sub.1.5: 16% Eu.sup.2+ from Example 2.

(6) FIG. 6: Emission spectrum of SrLuAl.sub.1.5Si.sub.2.5N.sub.5.5O.sub.1.5: 6% Eu.sup.2+ from Example 2 (λ.sub.ex=410 nm).

(7) FIG. 7: X-ray powder diffraction pattern of BaLuAl.sub.1.5Si.sub.2.5N.sub.5.5O.sub.1.5: 0.5% Eu.sup.2+ from Example 3.

(8) FIG. 8: Emission spectrum of BaLuAl.sub.1.5Si.sub.2.5N.sub.5.5O.sub.1.5: 0.5% Eu.sup.2+ from Example 3 (λ.sub.ex=410 nm).

(9) FIG. 9: X-ray powder diffraction pattern of BaLuAl.sub.1.5Si.sub.2.5N.sub.5.5O.sub.1.5:16% Eu.sup.2+ from Example 4.

(10) FIG. 10: Emission spectrum of BaLuAl.sub.1.5Si.sub.2.5N.sub.5.5O.sub.1.5: 16% Eu.sup.2+ from Example 4 (λ.sub.ex=410 nm).

(11) FIG. 11: X-ray powder diffraction pattern of Sr.sub.0.9Ca.sub.0.1LuAl.sub.1.5Si.sub.2.5N.sub.5.5O.sub.1.5: 1% Eu.sup.2+ from Example 5.

(12) FIG. 12: Emission spectrum of Sr.sub.0.9Ca.sub.0.1LuAl.sub.1.5Si.sub.2.5N.sub.5.5O.sub.1.5:1% Eu.sup.2+ from Example 5 (λ.sub.ex=410 nm).

(13) FIG. 13: X-ray powder diffraction pattern of Sr.sub.0.9Ba.sub.0.1LuAl.sub.1.5Si.sub.2.5N.sub.5.5O.sub.1.5:1% Eu.sup.2+ from Example 6.

(14) FIG. 14: Emission spectrum of Sr.sub.0.9Ba.sub.0.1LuAl.sub.1.5Si.sub.2.5N.sub.5.5O.sub.1.5:1% Eu.sup.2+ from Example 6 (λ.sub.ex=410 nm).

(15) FIG. 15: X-ray powder diffraction pattern of SrY.sub.0.5Lu.sub.0.5Al.sub.1.5Si.sub.2.5N.sub.5.5O.sub.1.5:1% Eu.sup.2+ from Example 7.

(16) FIG. 16: Emission spectrum of SrY.sub.0.5Lu.sub.0.5Al.sub.1.5Si.sub.2.5N.sub.5.5O.sub.1.5:1% Eu.sup.2+ from Example 7 (λ.sub.ex=410 nm).

(17) FIG. 17: X-ray powder diffraction pattern of SrLu.sub.0.25Y.sub.0.75Al.sub.1.5Si.sub.2.5N.sub.5.5O.sub.1.5:16% Eu.sup.2+ from Example 8.

(18) FIG. 18: Emission spectrum of SrLu.sub.0.25Y.sub.0.75Al.sub.1.5Si.sub.2.5N.sub.5.5O.sub.1.5: 16% Eu.sup.2+ from Example 8 (λ.sub.ex=410 nm).

(19) FIG. 19: X-ray powder diffraction pattern of SrLu.sub.0.5Y.sub.0.5Al.sub.1.5Si.sub.2.5N.sub.5.5O.sub.1.5: 16% Eu.sup.2+ from Example 9.

(20) FIG. 20: Emission spectrum of SrLu.sub.0.5Y.sub.0.5Al.sub.1.5Si.sub.2.5N.sub.5.5O.sub.1.5:16% Eu.sup.2+ from Example 9 (λ.sub.ex=410 nm).

(21) FIG. 21: X-ray powder diffraction pattern of SrLu.sub.0.75Y.sub.0.25Al.sub.1.5Si.sub.2.5N.sub.5.5O.sub.1.5:16% Eu.sup.2+ from Example 10.

(22) FIG. 22: Emission spectrum of SrLu.sub.0.75Y.sub.0.25Al.sub.1.5Si.sub.2.5N.sub.5.5O.sub.1.5:16% Eu.sup.2+ from Example 10 (λ.sub.ex=410 nm).

(23) FIG. 23: X-ray powder diffraction pattern of BaLuAl.sub.1.5Si.sub.2.5N.sub.5.5O.sub.1.5:10% Eu.sup.2+ from Example 11.

(24) FIG. 24: Emission spectrum of BaLuAl.sub.1.5Si.sub.2.5N.sub.5.5O.sub.1.5:10% Eu.sup.2+ from Example 11 (λ.sub.ex=410 nm).

(25) FIG. 25: X-ray powder diffraction pattern of SrLuAl.sub.0.5Si.sub.3.5N.sub.6.5O.sub.0.5:10% Eu.sup.2+ from Example 12.

(26) FIG. 26: Emission spectrum of SrLuAl.sub.0.5Si.sub.3.5N.sub.6.5O.sub.0.5:10% Eu.sup.2+ from Example 12 (λ.sub.ex=410 nm).

(27) FIG. 27: X-ray powder diffraction pattern of BaLuAl.sub.0.5Si.sub.3.5N.sub.6.5O.sub.0.5:10% Eu.sup.2+ from Example 13.

(28) FIG. 28: Emission spectrum of BaLuAl.sub.0.5Si.sub.3.5N.sub.6.5O.sub.0.5:10% Eu.sup.2+ from Example 13 (λ.sub.ex=410 nm).

(29) FIG. 29: X-ray powder diffraction pattern of SrYAl.sub.3SiN.sub.4O.sub.3:10% Eu.sup.2+ from Example 14.

(30) FIG. 30: Emission spectrum of SrYAl.sub.3SiN.sub.4O.sub.3:10% Eu.sup.2+ from Example 14 (λ.sub.ex=410 nm).

(31) FIG. 31: X-ray powder diffraction pattern of SrYAl.sub.1.5Si.sub.2.5N.sub.5.5O.sub.1.5:16% Eu.sup.2+ from Example 15.

(32) FIG. 32: Emission spectrum of SrYAl.sub.1.5Si.sub.2.5N.sub.5.5O.sub.1.5:16% Eu.sup.2+ from Example 15 (λ.sub.ex=410 nm).

(33) FIG. 33: LED spectrum of the LED from Example 17 with the phosphor SrLuAl.sub.1.5Si.sub.2.5N.sub.5.5O.sub.1.5:Eu.sup.2+ (16%).

(34) FIG. 34: LED spectrum of the LED from Example 18 with the phosphor BaLuAl.sub.1.5Si.sub.2.5N.sub.5.5O.sub.1.5:Eu.sup.2+ (16%).

(35) FIG. 35: LED spectrum of the LED from Example 19 with the phosphor Sr.sub.0.84YSi.sub.2.5Al.sub.1.5N.sub.5.5O.sub.1.5:Eu.sup.2+ (16%).

(36) FIG. 36: LED spectrum of the LED from Example 20 with the phosphor Sr.sub.0.9YSiAl.sub.3O.sub.3N.sub.4:Eu.sup.2+ (10%).

(37) FIG. 37: LED spectrum of the LED from Example 21 with the phosphor Sr.sub.0.9LuSi.sub.3.5Al.sub.0.5O.sub.0.5N.sub.6.5:Eu.sup.2+ (10%).

(38) FIG. 38: LED spectrum of the LED from Example 22 with the phosphor Ba.sub.0.9LuSi.sub.3.5Al.sub.0.5O.sub.0.5N.sub.6.5:Eu.sup.2+ (10%).

EXAMPLES

(39) General Procedure for Measurement of the Emission

(40) The powder emission spectra are measured by the following general method: a loose phosphor powder bed having a depth of 5 mm whose surface has been smoothed using a glass plate is irradiated at a wavelength of 450 nm in the integration sphere of an Edinburgh Instruments FL 920 fluorescence spectrometer having a xenon lamp as excitation light source, and the intensity of the emitted fluorescence radiation is measured in a range from 465 nm to 800 nm in 1 nm steps.

Example 1: SrLuAl1.5Si2.5N5.5O1.5:Eu2+ (0.5%)

(41) 0.0175 g (0.11 mmol) of EuN, 2.0326 g (6.99 mmol) of Sr.sub.3N.sub.2, 1.2954 g (31.60 mmol) of AlN, 4.1920 g (10.53 mmol) of Lu.sub.2O.sub.3 and 2.4631 g (17.56 mmol) of Si.sub.3N.sub.4 are mixed thoroughly in an agate mortar in a nitrogen-filled glove box. The resultant mixture of the starting compounds is transferred into a boron nitride boat and calcined at 1600° C. for 8 h in an N.sub.2/H.sub.2 stream (10% forming gas).

Example 2: SrLuAl1.5Si2.5N5.5O1.5:Eu2+ (16%)

(42) 0.5480 g (3.30 mmol) of EuN, 1.6806 g (5.78 mmol) of Sr.sub.3N.sub.2, 1.2687 g (30.95 mmol) of AlN, 4.1057 g (10.32 mmol) of Lu.sub.2O.sub.3 and 2.4124 g (17.20 mmol) of Si.sub.3N.sub.4 are mixed thoroughly in an agate mortar in a nitrogen-filled glove box. The resultant mixture of the starting compounds is transferred into a boron nitride boat and calcined at 1600° C. for 8 h in an N.sub.2/H.sub.2 stream (10% forming gas).

Example 3: BaLuAl1.5Si2.5N5.5O1.5:Eu2+ (0.5%)

(43) 0.0158 g (0.095 mmol) of EuN, 2.7845 g (6.33 mmol) of Ba.sub.3N.sub.2, 1.1731 g (28.62 mmol) of AlN, 3.7964 g (9.54 mmol) of Lu.sub.2O.sub.3 and 2.2306 g (15.90 mmol) of Si.sub.3N.sub.4 are mixed thoroughly in an agate mortar in a nitrogen-filled glove box. The resultant mixture of the starting compounds is transferred into a boron nitride boat and calcined at 1600° C. for 8 h in an N.sub.2/H.sub.2 stream (10% forming gas).

Example 4: BaLuAl1.5Si2.5N5.5O1.5:Eu2+ (16%)

(44) 0.5045 g (3.04 mmol) of EuN, 2.3406 g (5.32 mmol) of Ba.sub.3N.sub.2, 1.1681 g (28.50 mmol) of AlN, 3.7800 g (9.50 mmol) of Lu.sub.2O.sub.3 and 2.2210 g (15.83 mmol) of Si.sub.3N.sub.4 are mixed thoroughly in an agate mortar in a nitrogen-filled glove box. The resultant mixture of the starting compounds is transferred into a boron nitride boat and calcined at 1600° C. for 8 h in an N.sub.2/H.sub.2 stream (10% forming gas).

Example 5: Sr0.9Ca0.1LuAl1.5Si2.5N5.5O1.5:Eu2+ (1%)

(45) 0.0353 g (0.21 mmol) of EuN, 1.8352 g (6.31 mmol) of Sr.sub.3N.sub.2, 0.1051 g (0.71 mmol) of Ca.sub.3N.sub.2, 1.3076 g (31.90 mmol) of AlN, 4.2315 g (10.63 mmol) of Lu.sub.2O.sub.3 and 2.4863 g (17.72 mmol) of Si.sub.3N.sub.4 are mixed thoroughly in an agate mortar in a nitrogen-filled glove box. The resultant mixture of the starting compounds is transferred into a boron nitride boat and calcined at 1600° C. for 8 h in an N.sub.2/H.sub.2 stream (10% forming gas).

Example 6: Sr0.9Ba0.1LuAl1.5Si2.5N5.5O1.5: Eu2+ (1%)

(46) 0.0346 g (0.21 mmol) of EuN, 1.7980 g (6.18 mmol) of Sr.sub.3N.sub.2, 0.3056 g (0.69 mmol) of Ba.sub.3N.sub.2, 1.2811 g (31.25 mmol) of AlN, 4.1458 g (10.42 mmol) of Lu.sub.2O.sub.3 and 2.4359 g (17.36 mmol) of Si.sub.3N.sub.4 are mixed thoroughly in an agate mortar in a nitrogen-filled glove box. The resultant mixture of the starting compounds is transferred into a boron nitride boat and calcined at 1600° C. for 8 h in an N.sub.2/H.sub.2 stream (10% forming gas).

Example 7: SrY0.5Lu0.5Al1.5Si2.5N5.5O1.5:Eu2+ (1%)

(47) 0.0384 g (0.23 mmol) of EuN, 2.2223 g (7.64 mmol) of Sr.sub.3N.sub.2, 1.4235 g (34.73 mmol) of AlN, 1.3070 g (5.79 mmol) of Y.sub.2O.sub.3, 2.3032 g (5.79 mmol) of Lu.sub.2O.sub.3 and 2.7066 g (19.29 mmol) of Si.sub.3N.sub.4 are mixed thoroughly in an agate mortar in a nitrogen-filled glove box. The resultant mixture of the starting compounds is transferred into a boron nitride boat and calcined at 1600° C. for 8 h in an N.sub.2/H.sub.2 stream (10% forming gas).

Example 8: SrLu0.25Y0.75Al1.5Si2.5N5.5O1.5:16% Eu2+

(48) 0.3793 g (2.29 mmol) of EuN, 1.1633 g (3.02 mmol) of Sr.sub.3N.sub.2, 0.8782 g (21.43 mmol) of AlN, 0.7105 g (1.79 mmol) of Lu.sub.2O.sub.3, 1.2095 g (5.36 mmol) of Y.sub.2O.sub.3 and 1.6698 g (11.90 mmol) of Si.sub.3N.sub.4 are ground intimately together in a mortar. The resultant mixture of the starting compounds is transferred into a boron nitride boat and calcined at 1600° C. for 8 h in an N.sub.2/H.sub.2 stream (10% forming gas). All manipulations of the starting materials are carried out in an N.sub.2-filled glove box.

Example 9: SrLu0.5Lu0.5Al1.5Si2.5N5.5O1.5:16% Eu2+

(49) 0.1897 g (1.14 mmol) of EuN, 0.5817 g (2.00 mmol) of Sr.sub.3N.sub.2, 0.4391 g (10.71 mmol) of AlN, 1.3552 g (3.41 mmol) of Lu.sub.2O.sub.3, 0.6048 g (2.68 mmol) of Y.sub.2O.sub.3 and 0.8349 g (5.95 mmol) of Si.sub.3N.sub.4 are ground intimately together in a mortar. The resultant mixture of the starting compounds is transferred into a boron nitride boat and calcined at 1600° C. for 8 h in an N.sub.2/H.sub.2 stream (10% forming gas). All manipulations of the starting materials are carried out in an N.sub.2-filled glove box.

Example 10: SrLu0.75Y0.25Al1.5Si2.5N5.5O1.5:16% Eu2+

(50) 0.3441 g (2.07 mmol) of EuN, 1.0552 g (3.63 mmol) of Sr.sub.3N.sub.2, 0.7966 g (19.43 mmol) of AlN, 1.9334 g (4.86 mmol) of Lu.sub.2O.sub.3, 0.3657 g (1.62 mmol) of Y.sub.2O.sub.3 and 1.5146 g (10.80 mmol) of Si.sub.3N.sub.4 are ground intimately together in a mortar. The resultant mixture of the starting compounds is transferred into a boron nitride boat and calcined at 1600° C. for 8 h in an N.sub.2/H.sub.2 stream (10% forming gas). All manipulations of the starting materials are carried out in an N.sub.2-filled glove box.

Example 11: BaLuAl1.5Si2.5N5.5O1.5:10% Eu2+

(51) 0.0948 g (0.57 mmol) of EuN, 0.7536 g (1.71 mmol) of Ba.sub.3N.sub.2, 0.3510 g (8.56 mmol) of AlN, 1.1359 g (2.85 mmol) of Lu.sub.2O.sub.3 and 0.6674 g (4.76 mmol) of Si.sub.3N.sub.4 are ground intimately together in a mortar. The resultant mixture of the starting compounds is transferred into a boron nitride boat and calcined at 1600° C. for 8 h in an N.sub.2/H.sub.2 stream (10% forming gas). All manipulations of the starting materials are carried out in an N.sub.2-filled glove box.

Example 12: SrLuAl0.5Si3.5N6.5O0.5:10% Eu2+

(52) 0.1384 g (0.83 mmol) of EuN, 0.7274 g (6.70 mmol) of Sr.sub.3N.sub.2, 0.1708 g (4.17 mmol) of AlN, 0.5173 g (1.30 mmol) of Lu.sub.2O.sub.3, 1.2661 g (6.70 mmol) of LuN and 1.3643 g (9.73 mmol) of Si.sub.3N.sub.4 are ground intimately together in a mortar. The resultant mixture of the starting compounds is transferred into a boron nitride boat and calcined at 1600° C. for 8 h in an N.sub.2/H.sub.2 stream (10% forming gas). All manipulations of the starting materials are carried out in an N.sub.2-filled glove box.

Example 13: BaLuAl0.5Si3.5N6.5O0.5:10% Eu2+

(53) 0.1266 g (0.76 mmol) of EuN, 1.0065 g (2.29 mmol) of Ba.sub.3N.sub.2, 0.1563 g (3.81 mmol) of AlN, 0.0504 g (1.27 mmol) of Lu.sub.2O.sub.3, 1.0261 g (5.43 mmol) of LuN and 1.2479 g (8.91 mmol) of Si.sub.3N.sub.4 are ground intimately together in a mortar. The resultant mixture of the starting compounds is transferred into a boron nitride boat and calcined at 1600° C. for 8 h in an N.sub.2/H.sub.2 stream (10% forming gas). All manipulations of the starting materials are carried out in an N.sub.2-filled glove box.

Example 14: SrYAl3SiN4O3:10% Eu2+

(54) 0.1676 g (1.01 mmol) of EuN, 0.8814 g (3.03 mmol) of Sr.sub.3N.sub.2, 1.2420 g (30.30 mmol) of AlN, 1.1404 g (5.05 mmol) of Y.sub.2O.sub.3, 0.4552 g (7.58 mmol) of SiO.sub.2 and 0.1181 g (0.84 mmol) of Si.sub.3N.sub.4 are ground intimately together in a mortar. The resultant mixture of the starting compounds is transferred into a boron nitride boat and calcined at 1600° C. for 8 h in an N.sub.2/H.sub.2 stream (10% forming gas). All manipulations of the starting materials are carried out in an N.sub.2-filled glove box.

Example 15: SrYAl1.5Si2.5N5.5O1.5:16% Eu2+

(55) 0.3998 g (2.41 mmol) of EuN, 1.2261 g (4.22 mmol) of Sr.sub.3N.sub.2, 0.9256 g (22.58 mmol) of AlN, 1.6998 g (7.53 mmol) of Y.sub.2O.sub.3 and 1.7600 g (12.55 mmol) of Si.sub.3N.sub.4 are ground intimately together in a mortar. The resultant mixture of the starting compounds is transferred into a boron nitride boat and calcined at 1600° C. for 8 h in an N.sub.2/H.sub.2 stream (10% forming gas). All manipulations of the starting materials are carried out in an N.sub.2-filled glove box.

(56) In the case of all compounds from Examples 1 to 15, the X-ray powder diffraction patterns confirm that the compounds indicated are formed in phase-pure form.

Example 16: Measurement of the Luminescence Properties of the Phosphors from Examples 1 to 15

(57) The luminescence properties of the compounds from Examples 1 to 15 are measured in order to determine the suitability of these compounds as phosphors for phosphor-converted LEDs. The results are summarised in Table 1. To this end, the luminescence quantum yield QA, the lumen equivalent LE, the colour point of the emission in CIE 1931 x/y colour coordinates, and for some samples the thermal quenching TQ are determined. The thermal quenching TQ is the temperature at which the intensity of the luminescence has dropped to half compared with the luminescence intensity extrapolated to 0 K.

(58) TABLE-US-00002 TABLE 1 Luminescence properties of the phosphors according to the invention Colour Example Composition QA LE point TQ 2 Sr.sub.0.84LuSi.sub.2.5Al.sub.1.5O.sub.1.5N.sub.5.5:Eu.sup.2+ (16%) 32% 456 lm/W x: 0.373 331 K y: 0.557 4 Ba.sub.0.84LuSi.sub.2.5Al.sub.1.5O.sub.1.5N.sub.5.5:Eu.sup.2+ 47% 464 lm/W x: 0.332 (16%) y: 0.582 5 Sr.sub.0.89Ca.sub.0.10LuSi.sub.2.5Al.sub.1.5O.sub.1.5N.sub.5.5:Eu.sup.2+ 32% 438 lm/W x: 0.338 342 K (1%) y: 0.560 6 Sr.sub.0.89Ba.sub.0.10LuSi.sub.2.5Al.sub.1.5O.sub.1.5N.sub.5.5:Eu.sup.2+ 48% 438 lm/W x: 0.319 372 K (1%) y: 0.562 7 Sr.sub.0.99Y.sub.0.50Lu.sub.0.50Si.sub.2.5Al.sub.1.5O.sub.1.5N.sub.5.5:Eu.sup.2+ 29% 428 lm/W x: 0.365 (1%) y: 0.554 8 Sr.sub.0.84Y.sub.0.75Lu.sub.0.25Si.sub.2.5Al.sub.1.5O.sub.1.5N.sub.5.5:Eu.sup.2+ 19% 396 lm/W x: 0.432 (16%) y: 0.526 9 Sr.sub.0.84Y.sub.0.50Lu.sub.0.50Si.sub.2.5Al.sub.1.5O.sub.1.5N.sub.5.5:Eu.sup.2+ 21% 409 lm/W x: 0.415 (16%) y: 0.535 10 Sr.sub.0.84Y.sub.0.25Lu.sub.0.75Si.sub.2.5Al.sub.1.5O.sub.1.5N.sub.5.5:Eu.sup.2+ 28% 463 lm/W x: 0.337 (16%) y: 0.569 11 Ba.sub.0.90LuSi.sub.2.5Al.sub.1.5O.sub.1.5N.sub.5.5:Eu.sup.2+ 41% 450 lm/W x: 0.307 390 K (10%) y: 0.568 12 Sr.sub.0.90LuSi.sub.3.5Al.sub.0.5O.sub.0.5N.sub.6.5:Eu.sup.2+ (10%) 32% 435 lm/W x: 0.346 339 K y: 0.550 13 Ba.sub.0.90LuSi.sub.3.5Al.sub.0.5O.sub.0.5N.sub.6.5:Eu.sup.2+ 19% 439 lm/W x: 0.307 320 K (10%) y: 0.559 14 Sr.sub.0.90YSiAl.sub.3O.sub.3N.sub.4:Eu.sup.2+ (10%) 28% 437 lm/W x: 0.352 338 K y: 0.552 15 Sr.sub.0.84YSi.sub.2.5Al.sub.1.5O.sub.1.5N.sub.5.5:Eu.sup.2+ (16%) 13% 415 lm/W x: 0.447 271 K y: 0.519

Example 17

Production of a Pc-LED Using a Phosphor of the Composition SrLuAl1.5Si2.5N5.5O1.5:Eu2+ (16%)

(59) 1.28 g of the phosphor having the composition SrLuAl.sub.1.5Si.sub.2.5N.sub.5.5O.sub.1.5: Eu.sup.2+ (16%) from Example 2 are mixed with 8.72 g of an optically transparent silicone and subsequently mixed homogeneously in a planetary centrifugal mixer, so that the phosphor concentration in the overall composition is 12.8% by weight. The silicone/phosphor mixture obtained in this way is applied to the chip of a blue semiconductor LED with the aid of an automatic dispenser and cured with supply of heat. The blue semiconductor LEDs used for the LED characterisation in the present example have an emission wavelength of 450 nm and are operated at a current strength of 350 mA. The photometric characterisation of the LED is carried out using an Instrument Systems CAS 140 spectrometer and an ISP 250 integration sphere connected thereto. The LED is characterised via the determination of the wavelength-dependent spectral power density. The spectrum obtained in this way of the light emitted by the LED is used to calculate the colour point coordinates CIE x and y.

Example 18: Production of a Pc-LED Using a Phosphor of the Composition BaLuAl1.5Si2.5N5.5O1.5:Eu2+ (16%)

(60) 0.95 g of the phosphor having the composition BaLuAl.sub.1.5Si.sub.2.5N.sub.5.5O.sub.1.5:Eu.sup.2+ (16%) from Example 4 are mixed with 9.05 g of an optically transparent silicone and subsequently mixed homogeneously in a planetary centrifugal mixer, so that the phosphor concentration in the overall composition is 9.5% by weight. The silicone/phosphor mixture obtained in this way is applied to the chip of a near-UV semiconductor LED with the aid of an automatic dispenser and cured with supply of heat. The near-UV semiconductor LEDs used for the LED characterisation in the present example have an emission wavelength of 395 nm and are operated at a current strength of 350 mA. The photometric characterisation of the LED is carried out using an Instrument Systems CAS 140 spectrometer and an ISP 250 integration sphere connected thereto. The LED is characterised via the determination of the wavelength-dependent spectral power density. The spectrum obtained in this way of the light emitted by the LED is used to calculate the colour point coordinates CIE x and y.

Example 19: Production of a Pc-LED Using a Phosphor of the Composition Sr0.84YSi2.5Al1.5N5.5O1.5:Eu2+ (16%)

(61) 1.5 g of the phosphor having the composition Sr.sub.0.84YSi.sub.2.5Al.sub.1.5N.sub.5.5O.sub.1.5: Eu.sup.2+ (16%) from Example 15 are weighed out, mixed with 8.5 g of an optically transparent silicone and subsequently mixed homogeneously in a planetary centrifugal mixer, so that the phosphor concentration in the overall composition is 15% by weight. The silicone/phosphor mixture obtained in this way is applied to the chip of a near-UV semiconductor LED with the aid of an automatic dispenser and cured with supply of heat. The near-UV semiconductor LEDs used for the LED characterisation in the present example have an emission wavelength of 395 nm and are operated at a current strength of 350 mA. The photometric characterisation of the LED is carried out using an Instrument Systems CAS 140 spectrometer and an ISP 250 integration sphere connected thereto. The LED is characterised via the determination of the wavelength-dependent spectral power density. The spectrum obtained in this way of the light emitted by the LED is used to calculate the colour point coordinates CIE x and y.

Example 20: Production of a Pc-LED Using a Phosphor of the Composition Sr0.9YSiAl3O3N4: Eu2+ (10%)

(62) 1.5 g of the phosphor having the composition Sr.sub.0.9YSiAl.sub.3O.sub.3N.sub.4: Eu.sup.2+ (10%) from Example 14 are weighed out, mixed with 8.5 g of an optically transparent silicone and subsequently mixed homogeneously in a planetary centrifugal mixer, so that the phosphor concentration in the overall composition is 15% by weight. The silicone/phosphor mixture obtained in this way is applied to the chip of a near-UV semiconductor LED with the aid of an automatic dispenser and cured with supply of heat. The near-UV semiconductor LEDs used for the LED characterisation in the present example have an emission wavelength of 395 nm and are operated at a current strength of 350 mA. The photometric characterisation of the LED is carried out using an Instrument Systems CAS 140 spectrometer and an ISP 250 integration sphere connected thereto. The LED is characterised via the determination of the wavelength-dependent spectral power density. The spectrum obtained in this way of the light emitted by the LED is used to calculate the colour point coordinates CIE x and y.

Example 21: Production of a Pc-LED Using a Phosphor of the Composition Sr0.9LuSi3.5Al0.5O0.5N6.5:Eu2+ (10%)

(63) 1.5 g of the phosphor having the composition Sr.sub.0.9LuSi.sub.3.5Al.sub.0.5O.sub.0.5N.sub.6.5:Eu.sup.2+ (10%) from Example 12 are weighed out, mixed with 8.5 g of an optically transparent silicone and subsequently mixed homogeneously in a planetary centrifugal mixer, so that the phosphor concentration in the overall composition is 15% by weight. The silicone/phosphor mixture obtained in this way is applied to the chip of a near-UV semiconductor LED with the aid of an automatic dispenser and cured with supply of heat. The near-UV semiconductor LEDs used for the LED characterisation in the present example have an emission wavelength of 395 nm and are operated at a current strength of 350 mA. The photometric characterisation of the LED is carried out using an Instrument Systems CAS 140 spectrometer and an ISP 250 integration sphere connected thereto. The LED is characterised via the determination of the wavelength-dependent spectral power density. The spectrum obtained in this way of the light emitted by the LED is used to calculate the colour point coordinates CIE x and y.

Example 22: Production of a Pc-LED Using a Phosphor of the Composition Ba0.9LuSi3.5Al0.5O0.5N6.5: Eu2+ (10%)

(64) 1.5 g of the phosphor having the composition Ba.sub.0.9LuSi.sub.3.5Al.sub.0.5O.sub.0.5N.sub.6.5:Eu.sup.2+ (10%) from Example 13 are weighed out, mixed with 8.5 g of an optically transparent silicone and subsequently mixed homogeneously in a planetary centrifugal mixer, so that the phosphor concentration in the overall composition is 15% by weight. The silicone/phosphor mixture obtained in this way is applied to the chip of a near-UV semiconductor LED with the aid of an automatic dispenser and cured with supply of heat. The near-UV semiconductor LEDs used for the LED characterisation in the present example have an emission wavelength of 395 nm and are operated at a current strength of 350 mA. The photometric characterisation of the LED is carried out using an Instrument Systems CAS 140 spectrometer and an ISP 250 integration sphere connected thereto. The LED is characterised via the determination of the wavelength-dependent spectral power density. The spectrum obtained in this way of the light emitted by the LED is used to calculate the colour point coordinates CIE x and y.