Phosphor and manufacturing method therefore, and light source using the phosphor
View Patent ↗To provide a phosphor having a broad emission spectrum with a peak in the range from yellow color to red color (wavelength from 570 nm to 620 nm), having a flat excitation band with large area on the long wavelength side from near ultraviolet/ultraviolet to green color (wavelength from 250 nm to 550 nm), and excellent in emission intensity and luminance, and a method of manufacturing the same, and also a light source such as white LED using the phosphor. As raw materials, Ca 3 N 2 (2N), AlN(3N), Si 3 N 4 (3N), and Eu 2 O 3 (3N) are prepared, and out of each raw material, 0.950/3 mol of Ca 3 N 2 , 2 mol of AlN, 4/3 mol of Si 3 N 4 , and 0.050/2 mol of Eu 2 O 3 are weighed, and the raw materials thus weighed are mixed by using a mortar. The raw materials thus mixed are put in a BN crucible, and retained/fired for 3 hours at 1700° C. in a nitrogen atmosphere, and thereafter cooled from 1700° C. to 200° C., to thereby obtain the phosphor expressed by a composition formula Ca 0.950 Al 2 Si 4 O 0.075 N 7.917 :Eu 0.050 .
1. A phosphor which is given as a general composition formula expressed by MmAaBbOoNn:Z, (where element M is the element having bivalent valency, element A is the element having tervalent valency, element B is the element having tetravalent valency, O is oxygen, N is nitrogen, and element Z is the element acting as the activator), expressed by m=1, a+b<8, 0<o≦1.0, n=2/3m+a+4/3b−2/3o.
2. A phosphor which is given as a general composition formula expressed by MmAaBbOoNn: Z, (where element M is the element having bivalent valency, element A is the element having tervalent valency, element B is the element having tetravalent valency, O is oxygen, N is nitrogen, and element Z is the element acting as the activator), expressed by m=1, 1.8≦a/m≦5.0, a+b<8, o≦1.0, n=2/3m+a+4/3b−2/3o.
3. A phosphor which is given as a general composition formula expressed by MmAaBbOoNn:Z (where element M is the element having bivalent valency, element A is the element having tervalent valency, element B is the element having tetravalent valency, O is oxygen, N is nitrogen, and element Z is the element acting as the activator), expressed by m=1, 1.8≦a/m≦5.0, 3.0≦b/m≦6.2, a+b<8, o≦1.0, n=2/3m+a+4/3b−2/3o.
4. The phosphor according to claim 1 , which is given as the composition formula expressed by a=2, 4.0≦b/m≦5.5.
5. The phosphor according to claim 4 , which is given as the composition formula expressed by b/m=4.0.
6. The phosphor according to claim 1 , wherein the element M is one or more kind of element selected from a group consisting of Mg, Ca, Sr, Ba, Zn, and rare earth elements having bivalent valency, element A is one or more kind of element selected from a group consisting of B (boron), Al, Ga, In, Tl, Y, Sc, P, As, Sb, and Bi, element B is one or more kind of element selected from the group consisting of C, Si, Ge, Sn, Ti, Hf, Mo, W, Cr, Pb, Zr, and element Z is one or more kind of element selected from the group consisting of the rare earth elements and transition metal elements.
7. The phosphor according to claim 1 , wherein the element A is Al and the element B is Si.
8. The phosphor according to claim 1 , wherein the element M is one or more kind of element selected from the group consisting of Mg, Ca, Sr, Ba, and Zn.
9. The phosphor according to claim 1 , wherein the element Z is one or more kind of element selected from the group consisting of Eu, Mn, Ce, and Tb.
10. The phosphor according to claim 1 , wherein the element Z is Eu.
11. The phosphor according to claim 1 , wherein the element M is Ca, the element A is Al, and the element B is Si.
12. The phosphor according to claim 1 , wherein when the general formula is expressed by MmAaBbOoNn:Zz, the value of z/(m+z), which is a molar ratio of the element M to the element Z, is not less than 0.0001 and not more than 0.5.
13. The phosphor according to claim 2 , containing 8.4 to 13.5 wt % of Ca, 11.7 to 17.9 wt % of Al, 29.8 to 41.7 wt % of Si, 0 to 5.0 wt % of O, 30.5 to 37.0 wt % of N, and 0.01 to 5.0 wt % of Eu, wherein a peak wavelength in an emission spectrum is in a wavelength range from 570 to 620 nm, with chromaticity x of the emission in the range from 0.5 to 0.6, and y in the range from 0.4 to 0.5.
14. The phosphor according to claim 1 , wherein the phosphor is formed in hexagonal crystals.
15. The phosphor according to claim 1 , wherein the phosphor is a powdery form.
16. The phosphor according to claim 15 , wherein as average size of the phosphor is not less than 20 μm, and not more than 1.0 μm.
17. A method of manufacturing a phosphor according to claim 1 , wherein by using nitride of each element as a supply source of the element M, the element A, and the element B, the raw material is fired at 1000° C. or more in an atmosphere of inactive gas.
18. A light source, comprising the phosphor according to claim 1 and a light emitting part for emitting light of a first wavelength, wherein by using a part or the whole part of the light of the first wavelength as an excitation light, the phosphor is caused to emit light with a wavelength different from the first wavelength.
19. The light source according to claim 18 , wherein the first wavelength is the wavelength form 250 nm to 550 nm.
20. The light source according to claim 18 , wherein the light emitting part for emitting the light of the first wavelength is an LED.