Light emitting device and illuminator using the same
View Patent ↗An object of the present invention is to provide a light emitting device having a high emission intensity, and a light emitting device having a high emission intensity and a good color rendering property. The present invention provides a light emitting device which comprises: a first light emitter emitting light of from 350 to 415 nm and a second light emitter emitting visible light by exposure to the light from the first light emitter, wherein said second light emitter comprises a phosphor capable of satisfying any one of the following conditions (i) to (iv): (i) the phosphor comprises: (a) a crystal phase whose Eu concentration providing the maximum emission intensity at any one of excitation wavelengths of from 350 to 415 nm is higher than that providing the maximum emission intensity at an excitation wavelength of 254 nm; and (b) a crystal phase which is activated by Eu having at least 1.1 times the concentration providing the maximum emission intensity at an excitation wavelength of 254 nm and 0.5 to 9 times the concentration providing the maximum emission intensity at an excitation frequency of 400 nm: (ii) the phosphor comprises a crystal phase having an Eu—Eu mean distance, as calculated from the Eu concentration in a crystal matrix, of 4 Å or greater but not greater than 11 Å: (iii) the phosphor has a quantum absorption efficiency α q of 0.8 or greater: (iv) the phosphor has a product α q ·η i of a quantum absorption efficiency α q and an internal quantum efficiency η i of 0.55 or greater.
1. A light emitting device comprising a first light emitter emitting light of from 350 to 415 nm and a second light emitter emitting visible light by exposure to the light from the first light emitter, wherein said second light emitter comprises a phosphor having a crystal phase having a chemical composition of one of the following formula [1]-[4]:
Eu a Sr b M 1 5-a-b (PO 4 ) c X d [1]
(wherein, M 1 represents a metal element other than Eu and Sr, X represents a monovalent anionic group other than PO 4 , a and b stand for numbers satisfying a>0, b≧0, a+b≦5 and at least one of a≧0.1 and b≧3, c stands for a number satisfying 2.7≦c≦3.3, and d stands for a number satisfying 0.9≦d≦1.1, and wherein said other metal element is a divalent metal element and/or, in an amount effective for accelerating crystallization of a complex oxide caused by the diffusion, in solid, of the divalent metal element and emission center Eu 2+ upon sintering, a monovalent-, trivalent-, tetravalent-, pentavalent-, or hexavalent-metal element);
M 2 (e-ex) M 2′ ex Eu f M 3 (g-gy) M 3′ gy M 4 (h-hz) M 4′ (h-hz) O i [2]
(wherein, M 2 represents at least one element selected from the group consisting of Ba, Sr and Ca, M 2′ represents a monovalent element or a divalent metal element (except Ba, Sr, Ca and Eu) having a radius of 0.92 Å or greater in the divalent form upon coordination number 6, M 3 represents at least one element selected from the group consisting of Mg and Zn, M 3′ represents a divalent metal element (except Mg and Zn) having a radius less than 0.92 Å in the divalent form upon coordination number 6, M 4 represents at least one element selected from the group consisting of Al, Ga and Sc, M 4′ represents a trivalent metal element (except Al, Ga and Sc), f stands for a number satisfying 0.11≦f≦0.99, e stands for a number satisfying 0.9≦(e+f)≦1.1, g stands for a number satisfying 0.9≦g≦1.11, h stands for a number satisfying 0≦h11, I stands for a number satisfying 15.3≦i≦18.7, x stands for a number satisfying 0≦x<0.2, y stands for a number satisfying 0≦y<0.2, and z stands for a number satisfying 0≦z<0.2);
M 5 j Eu k M 6 1 M 7 m O n [3]
(wherein, M 5 represents a metal element comprising at least one element selected from the group consisting of Ba, Sr and Ca in a total amount of 90 mol % or greater, M 6 represents a metal element comprising at least one element selected from the group consisting of Mg and Zn in a total amount of 90 mol % or greater, M 7 represents a metal element comprising at least one element selected from the group consisting of Si and Ge in a total amount of 90 mol % or greater, j stands for a number satisfying 2.5≦j≦3.3, k stands for a number satisfying 0.0001≦k≦1.0, l stands for a number satisfying 0.9≦l≦1.1, m stands for a number satisfying 1.8≦m≦2.2 and n stands for a number satisfying 7.2≦n≦8.8, and wherein M 5 and M 6 may each independently include another divalent metal element, and M 7 may include another tetravalent element, and/or, M 5 , M 6 and M 7 may include in an amount effective for accelerating crystallization of a complex oxide caused by the diffusion, in solid, of divalent and tetravalent metal elements and emission center Eu 2+ upon sintering, a monovalent-, trivalent-, pentavalent-, or hexavalent-metal element); and
Eu o M 8 p (PO 4 ) q (BO 3 ) 2-q Z r [4]
(wherein, M 8 represents a metal element which contains Ca and 80 mol % or greater of which is composed of at least one element selected from the group consisting of Ca and Mg; Z represents an anionic group other than PO 4 3− and BO 3 3− ; o stands for a number satisfying 0.003≦o≦2.1, p stands for a number satisfying 2.7≦(o+p)≦3.3, q stands for a number satisfying 1.2≦q≦2 and r stands for a number satisfying 0≦r≦0.1, and wherein M 8 may include another divalent metal element and/or, in an amount effective for accelerating crystallization of a complex oxide caused by the diffusion, in solid, of the divalent metal element and emission center Eu 2+ upon sintering, a monovalent-, trivalent-, tetravalent-, pentavalent-, or hexavalent-metal element).
2. The light emitting device according to claim 1 , wherein the phosphor has formula [1].
3. The light emitting device according to claim 2 , wherein a and b satisfy 0.1≦a<5 and 0.01≦b<5; or 0.0001≦a<5 and 3≦b<5.
4. The light emitting device according to claim 2 , wherein 70 mol % or greater of M 1 is composed of at least one element selected from the group consisting of Ba, Mg, Ca, Zn and Mn.
5. The light emitting device according to claim 2 , wherein 50 mol % or greater of X is composed of Cl.
6. The light emitting device according to claim 2 , wherein a and b satisfy a≦0.1 and b≦3.
7. The light emitting device according to claim 2 , wherein a satisfies a<0.2.
8. The light emitting device according to claim 7 , wherein a satisfies 0.2<a≦3.
9. The light emitting device according to claim 2 , wherein M 1 is composed of at least one element selected from the group consisting of Ba, Mg, Ca, Zn and Mn; and X is composed of Cl.
10. The light emitting device according to claim 2 , wherein M 1 is composed of at least one element selected from the group consisting of Ba, Mg, and Ca; and X is composed of Cl.
11. A light emitting device according to claim 2 , wherein b satisfies b>0.
12. The light emitting device according to claim 1 , wherein the phosphor has formula [2].
13. The light emitting device according to claim 12 , wherein f stands for 0.15≦f≦0.85.
14. The light emitting device according to claim 12 , wherein M 4 represents Al.
15. The light emitting device according to claim 12 , wherein a ratio of Ba to the total of M 2 and M 2′ is 30 mol % or greater and at the same time, a ratio of at least one of Sr and Ca to said total is 20 mol % or greater.
16. The light emitting device according to claim 12 , wherein z stands for 0.
17. The light emitting device according to claim 12 , wherein x and y each stands for 0.
18. The light emitting device according to claim 1 , wherein the phosphor has formula [3].
19. The light emitting device according to claim 18 , wherein a proportion of the total amounts of Ba, Sr and Ca in M 5 , a proportion of the total amounts of Mg and Zn in M 6 , and a proportion of the total amounts of Si and Ge in M 7 is each 95 mol % or greater.
20. The light emitting device according to claim 18 , wherein M 5 represents at least one metal element selected from Ba, Sr and Ca, M 6 represents at least one metal element selected from Mg and Zn and M 7 represents at least one metal element selected from Si and Ge.
21. The light emitting device according to claim 18 , wherein M 5 represents at least one metal element selected from Ba and Sr, M 6 represents Mg, and M 7 represents Si.
22. The light emitting device according to claim 18 , wherein k stands for a number satisfying 0.001≦k≦1.
23. The light emitting device according to claim 18 , wherein a molar ratio of Ba to Sr in M 5 is 0.05 or greater.
24. The light emitting device according to claim 18 , wherein j stands for a number satisfying 2.7≦j≦3.3.
25. The light emitting device according to claim 1 , wherein the phosphor has formula [4].
26. The light emitting device according to claim 25 , wherein o stands for a number satisfying 0.015≦o≦2.1.
27. The light emitting device according to claim 25 , wherein a proportion, in M 8 , of Ca to the total amount of Ca and Mg is 40 mol % or greater.
28. The light emitting device according to claim 25 , wherein q stands for a number satisfying 1.6≦q≦2.
29. The light emitting device according to claim 25 , wherein M 8 has least one element selected from the group consisting of Ca and Mg and comprises 40 mol % or greater of Ca.
30. The light emitting device according to claim 25 , wherein q is 2.
31. The light emitting device according to claim 1 , wherein the first light emitter is a laser diode or light emitting diode.
32. The light emitting device according to claim 31 , wherein the first light emitter is a laser diode.
33. The light emitting device according to claim 31 , wherein the first light emitter uses a GaN compound semiconductor.
34. The light emitting device according to claim 31 , wherein the first light emitter is a vertical cavity surface emitting GaN laser diode.
35. The light emitting device according to claim 1 , wherein the second light emitter is in the film form.
36. The light emitting device according to claim 35 , wherein the visible light is emitted directly while bringing a film surface of the second light emitter into direct contact with a light emitting surface of the first light emitter.
37. The light emitting device according to claim 1 , wherein the second light emitter is obtainable by dispersing the phosphor in the powder form in a resin.
38. The light emitting device according to claim 1 , wherein the light coming out from the light emitting device is a mixture of the light from the first light emitter and the light from the second light emitter and is white in color.
39. An illuminator having a light emitting device according to claim 1 .