Phosphor and production method of the same, method of shifting emission wavelength of phosphor, and light source and LED

• US RE44,996 E1
• Filed: 03/07/2012
• Issued: 07/08/2014
• Est. Priority Date: 06/25/2004
• Status: Active Grant

• Current Assignee: Citizen Electronics Company Limited, Nichia Corporation
• Original Assignee: Dowa Electronics Materials Co. Ltd. (DOWA Holdings Company Limited), Nichia Corporation
• Inventors: Nagatomi, Akira, Gotoh, Masahiro, Sakane, Kenji, Yamashita, Shuji
• Primary Examiner(s): Koslow, Carol M
• Application Number:
  US13/414,704
• Time in Patent Office: 853 Days
• Field of Search: None
• US Class Current: 252/301.4F
• CPC Class Codes: C04B 2235/3208 Calcium oxide or oxide-forming salts thereof, e.g. lime
• CPC Class Codes: C04B 2235/3224 Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
• CPC Class Codes: C04B 2235/3852 Nitrides, e.g. oxynitrides, carbonitrides, oxycarbonitrides, lithium nitride, magnesium nitride
• CPC Class Codes: C04B 2235/3865 Aluminium nitrides
• CPC Class Codes: C04B 2235/3869 Aluminium oxynitrides, e.g. AlON, sialon
• CPC Class Codes: C04B 2235/3873 Silicon nitrides, e.g. silicon carbonitride, silicon oxynitride
• CPC Class Codes: C04B 2235/3895 Non-oxides with a defined oxygen content, e.g. SiOC, TiON
• CPC Class Codes: C04B 2235/5436 micrometer sized, i.e. from 1 to 100 micron
• CPC Class Codes: C04B 35/597 based on silicon oxynitride, e.g. SIALONS
• CPC Class Codes: C09K 11/7734 Aluminates

Abstract

A phosphor including a main production phase of a phosphor expressed by a composition formula of MmAaBbOoNn:Zz (where an element M is one or more bivalent elements, an element A is one or more trivalent elements, an element B is one or more tetravalent elements, O is oxygen, N is nitrogen, an element Z is an activator, n=2/3m+a+4/3b−2/3o, m/(a+b)≧1/2, (o+n)/(a+b)>4/3, wherein m=a=b=1 and o and n is not 0). A phosphor including 24 wt % to 30 wt % of Ca (calcium), 17 wt % to 21 wt % of Al (aluminum), 18 wt % to 22 wt % of Si (silicon), 1 wt % to 15 wt % of oxygen, 15 wt % to 33 wt % of nitrogen and 0.01 wt % to 10 wt % of Eu (europium), wherein an emission maximum in an emission spectrum is in a range of 600 nm to 660 nm; and wherein color chromaticity x of light emission is in a range of 0.5 to 0.7, and color chromaticity y of the light emission is in a range of 0.3 to 0.5.

Claims

1. A phosphor comprising a main production phase of a phosphor expressed by a composition formula of MmAaBbOoNn:

Zz (where an element M is one or more bivalent elements, an element A is one or more trivalent elements, an element B is one or more tetravalent elements, O is oxygen, N is nitrogen, an element Z is an activator, n=2/3m+a+4/3b−

2/3o, wherein m=a=b=1 and o and n is not

     0).

2. The phosphor according to claim 1, wherein 0<

o≦

m, and 0.0001≦

z/(m+z)≦

0.5.

3. The phosphor according to claim 1, wherein the element M is one or more elements selected from Mg (magnesium), Ca (calcium), Sr (strontium), Ba (barium) and Zn (zinc), the element A is one or more elements selected from B (boron), Al (aluminum) and Ga (gallium), the element B is Si (silicon) and/or Ge (germanium), and the element Z is one or more elements selected from rare earth or transition metals.

4. The phosphor according to claim 1, wherein the element A is Al (aluminum), and the element B is Si (silicon).

5. The phosphor according to claim 1, wherein the element Z is at least one or more elements selected from Eu (europium), Mn (manganese), Sm (samarium) and Ce (cerium).

6. The phosphor according to claim 1, wherein the element Z is Eu (europium).

7. The phosphor according to claim 1, claim 16, wherein said phosphor is in a powder form.

8. The phosphor according to claim 7, wherein an average particle size of the phosphor in the powder form is from 0.1 μ

m to 20 μ

m inclusive.

17. A manufacturing method of the phosphor according to claim 1, claim 16, comprising:

as a raw material of at least one element selected from the element M, element A and element B, group consisting of Ca, Al, and Si, preparing a compound having the element and oxygen, and a compound having the element and nitrogen;

mixing the compound thus prepared and baking a mixture thereof; and

controlling an oxygen concentration included in the main production phase of said phosphor by compounding of the compound having the element and oxygen and the compound having the element and nitrogen.

18. A method of shifting an emission wavelength of the phosphor according to claim 1, claim 16, comprising:

in a manufacturing step of mixing raw materials and baking a mixture thereof, as a raw material of at least one element selected from the element M, element A and element B, group consisting of Ca, Al, and Si, preparing a compound having the element and oxygen, and a compound having the element and nitrogen; and

controlling an oxygen concentration included in the main production phase of said phosphor by compounding of the compound having the element and oxygen and the compound having the element and nitrogen, and thereby shifting the emission wavelength.

19. A method of shifting an emission wavelength of the phosphor according to claim 1, claim 16, comprising:

in a manufacturing step of mixing raw materials and baking a mixture thereof, controlling a compounding amount of the element Z, Eu and thereby shifting the emission wavelength.

20. A method of shifting an emission wavelength of the phosphor according to claim 1, claim 16, comprising:

in a manufacturing step of mixing raw materials and baking a mixture thereof, as a raw material of at least one element selected from the element M, element A and element B, group consisting of Ca, Al, and Si, preparing a compound having the element and oxygen, and a compound having the element and nitrogen;

controlling an oxygen concentration included in the main production phase of the phosphor by compounding of the compound having the element and oxygen and the compound having the element and nitrogen, and thereby shifting the emission wavelength; and

controlling a compounding amount of the element Z, Eu and thereby sifting shifting the emission wavelength.

21. A light source comprising the phosphor according to claim 1, claim 16, and a light emitting portion emitting light of a predetermined wavelength, wherein a part of the light of the predetermined wavelength is set to be an excitation source, and said phosphor is made to emit light of a different wavelength from the predetermined wavelength.

22. The light source according to claim 21, the predetermined wavelength is a wavelength of any one of 250 nm to 600 nm.

23. An LED comprising the phosphor according to claim 1, claim 16, and a light emitting portion emitting light of a predetermined wavelength, wherein a part of the light of the predetermined wavelength is set to be an excitation source, and said phosphor is made to emit light of a different wavelength from the predetermined wavelength.

24. The LED according to claim 23, wherein the predetermined wavelength is a wavelength of any one of 250 nm to 600 nm.

25. A manufacturing method of the phosphor according to claim 7, comprising:

as a raw material of at least one element selected from the element M, element A and element B, preparing a compound having the element and oxygen, and a compound having the element and nitrogen;

mixing the compound thus prepared and baking a mixture thereof; and

controlling an oxygen concentration included in the main production phase of said phosphor by compounding of the compound having the element and oxygen and the compound having the element and nitrogen.

26. A method of shifting an emission wavelength of the phosphor according to claim 7, comprising:

in a manufacturing step of mixing raw materials and baking a mixture thereof, as a raw material of at least one element selected from the element M, element A and element B, preparing a compound having the element and oxygen, and a compound having the element and nitrogen; and

controlling an oxygen concentration included in the main production phase of said phosphor by compounding of the compound having the element and oxygen and the compound having the element and nitrogen, and thereby shifting the emission wavelength.

27. A method of shifting an emission wavelength of the phosphor according to claim 7, comprising:

in a manufacturing step of mixing raw materials and baking a mixture thereof controlling a compounding amount of the element Z, and thereby shifting the emission wavelength.

28. A method of shifting an emission wavelength of the phosphor according to claim 7, comprising:

in a manufacturing step of mixing raw materials and baking a mixture thereof as a raw material of at least one element selected from the element M, element A and element B, preparing a compound having the element and oxygen, and a compound having the element and nitrogen; and

controlling an oxygen concentration included in the main production phase of said phosphor by compounding of the compound having the element and oxygen and the compound having the element and nitrogen, and thereby shifting the emission wavelength, and

controlling a compounding amount of the element Z, and thereby shifting the emission wavelength.

29. A light source, comprising the phosphor according to claim 7, and a light emitting portion emitting light of a predetermined wavelength, wherein a part of the light of the predetermined wavelength is set to be an excitation source, and said phosphor is made to emit light of a different wavelength from the predetermined wavelength.

30. The light source according to claim 29, wherein the predetermined wavelength is a wavelength of any one of 250 nm to 600 nm.

31. An LED comprising the phosphor according to claim 7, and a light emitting portion emitting light of a predetermined wavelength, wherein a part of the light of the predetermined wavelength is set to be an excitation source, and said phosphor is made to emit light of a different wavelength from the predetermined wavelength.

32. The LED according to claim 31, wherein the predetermined wavelength is a wavelength of any one of 250 mm to 600 nm.

9. A phosphor comprising the main production phase of the phosphor expressed by the composition formula of MmAaBbOoNn:

Zz (where an element M is one or more bivalent elements, an element A is one or more trivalent elements, an element B is one or more tetravalent elements, O is oxygen, N is nitrogen, an element Z is an activator, n=2/3m+a+4/3b−

2/3o, m/(a+b)≧

1/2,(o+n)/(a+b)>

4/3, and none of m, a, b, o, n is equal to

     0),

said phosphor including said oxygen by 3 wt % or less with respect to a mass of the main production phase of the phosphor.

10. The phosphor according to claim 9, satisfying m−

a−

b−

1.

11. The phosphor according to claim 9, satisfying 0<

o≦

m, and 0.0001≦

z/(m+z)≦

0.5.

12. The phosphor according to claim 9, wherein the element M is one or more elements selected form Mg (magnesium), Ca (calcium), Sr (strontium), Ba (barium), and Zn (zinc), the element A is one or more elements selected from B (boron), Al (aluminum) and Ga (gallium), the element B is Si (silicon) and/or Ge (germanium), and the element Z is one or more elements selected from rare earth and transition metals.

13. The phosphor according to claim 9, wherein the element A is Al (aluminum), and the element B is Si (silicon).

14. The phosphor according to claim 9, wherein the element Z is at least one or more elements selected from Eu (europium), Mn (manganese), Sm (samarium), and Ce (cerium).

15. The phosphor according to claim 9, wherein the element Z is Eu (europium).

16. A phosphor comprising 24 wt % to 30 wt % of Ca (calcium), 17 wt % to 21 wt % of Al (aluminum), 18 wt % to 22 wt % of Si (silicon), 1 wt % to 15 wt % of oxygen, 15 wt % to 33 wt % of nitrogen and 0.01 wt % to 10 wt % of Eu (europium), wherein an emission maximum in an emission spectrum is in a range of 600 nm to 660 nm;

and wherein color chromaticity x of light emission is in a range of 0.5 to 0.7, and color chromaticity y of the light emission is in a range of 0.3 to 0.5, and wherein part of said 1 wt % to 15 wt % of oxygen is separate from a production phase of said phosphor.