Garnet phosphor materials having enhanced spectral characteristics

• US 7,094,362 B2
• Filed: 10/29/2003
• Issued: 08/22/2006
• Est. Priority Date: 10/29/2003
• Status: Active Grant

• Current Assignee: Current Lighting Solutions, LLC (f/k/a GE Lighting Solutions, LLC) (American Industrial Partners)
• Original Assignee: General Electric Company
• Inventors: Venugopal, Shankar, Radkov, Emil, Srivastava, Alok Mani, Comanzo, Holly Ann, Setlur, Anant Achyut, Chandran, Gopi
• Primary Examiner(s): KOSLOW, CAROL M
• Application Number:
  US10/696,637
• Publication Number:
  US 20050093442A1
• Time in Patent Office: 1,028 Days
• Field of Search: None
• US Class Current: 252/301.40F
• CPC Class Codes: C09K 11/7774 Aluminates
• CPC Class Codes: C09K 11/77742 Silicates
• CPC Class Codes: H01L 2224/48091 Arched
• CPC Class Codes: H01L 2224/48247 connecting the wire to a bond pad of the item
• CPC Class Codes: H01L 2224/48257 connecting the wire to a die pad of the item
• CPC Class Codes: H01L 2924/00012 Relevant to the scope of the group, the symbol of which is combined with the symbol of this group
• CPC Class Codes: H01L 2924/00014 the subject-matter covered by the group, the symbol of which is combined with the symbol of this group, being disclosed without further technical details
• CPC Class Codes: H01L 2924/181 Encapsulation
• CPC Class Codes: H01L 33/502 Wavelength conversion materials
• CPC Class Codes: H01L 33/507 the elements being in intimate contact with parts other than the semiconductor body or integrated with parts other than the semiconductor body
• CPC Class Codes: H10K 50/125 specially adapted for multicolour light emission, e.g. for emitting white light

Abstract

Phosphor compositions having the formulas (Tb_{1−x−y−z−w}Y_xGd_yLu_zCe_w)₃M_rAl_s−rO_12+δ, where M is selected from Sc, In, Ga, Zn, or Mg, and where 0<w≦0.3, 0≦x<1, 0≦y≦0.4, 0≦z<1, 0≦r≦4.5, 4.5≦s≦6, and −1.5≦δ≦1.5; (RE_1−x−ySc_xCe_y)₂A_3−pB_pSi_z−qGe_qO_12+δ, where RE is selected from a lanthanide ion or Y³⁺, A is selected from Mg, Ca, Sr, or Ba, B is selected from Mg and Zn, and where 0≦p≦3, 0≦q≦3, 2.5≦z≦3.5, 0≦x≦1, 0≦y≦0.3, −1.5≦δ≦1.5; and (Ca_{1−x−y−z}Sr_xBa_yCe_z)₃(Sc_1−a−cLu_aD_c)₂Si_n−wGe_wO_12+δ, where D is either Mg or Zn, 0≦x<1, 0≦y<1, 0<z≦0.3, 0≦a<1, 0≦c≦1, 0≦w≦3, 2.5≦n≦3.5, and −1.5≦δ≦1.5. Also disclosed are light emitting devices including a light source and at least one of the above phosphor compositions.

Claims

1. A lighting apparatus for emitting white light comprising:

a light source emitting radiation at from about 250 to about 550 nm; and

a phosphor composition radiationally coupled to the light source, the phosphor composition comprising (RE<sub>1−

x−

y</sub>Sc_xCe_y)₂A<sub>3−

p</sub>B_pSi<sub>z−

q</sub>Ge_qO_12+δ

, where RE is selected from a lanthanide ion or Y³⁺, A is selected from Mg, Ca, Sr, or Ba, B is selected from Mg and Zn, and where 0≦

p≦

3, 0≦

q≦

3, 2.5≦

z≦

3.5, 0≦

x<

1, 0<

y≦

0.3, −

1.5≦

δ

≦

1.5.

2. The lighting apparatus of claim 1, wherein the light source is a semiconductor LED emitting radiation having a wavelength in the range of from about 350 to about 550 nm.

3. The lighting apparatus of claim 2, wherein the LED comprises a nitride compound semiconductor represented by the formula In_iGa_jAl_kN, where 0≦

i;

0≦

j, 0≦

K, and i+j+k=1.

4. The lighting apparatus of claim 1, wherein said light source is an organic emissive structure.

5. The lighting apparatus of claim 1, wherein the phosphor composition is coated on the surface of the light source.

6. The lighting apparatus of claim 1, further comprising an encapsulant surrounding the light source and the phosphor composition.

7. The lighting apparatus of claim 1, wherein the phosphor composition is dispersed in the encapsulant.

8. The lighting apparatus of claim 1, further comprising a reflector cup.

9. The lighting apparatus of claim 1, wherein said phosphor composition comprises (Lu_0.955Ce_0.045)₂CaMg₂Si₃O₁₂.

10. The lighting apparatus of claim 1, wherein said phosphor composition comprises two or more distinct phosphors having the formula (RE₁₋

x−

ySc_xCe_y)₂A<sub>3−

p</sub>B_pSi<sub>z−

q</sub>Ge_qO_12+δ

, where RE is selected from a lanthanide ion or Y³⁺, A is selected from Mg, Ca, Sr, or Ba, B is selected from Mg and Zn, and where 0≦

p≦

3, 0≦

q≦

3, 2.5≦

z≦

3.5, 0≦

x<

1, 0<

y≦

0.3, −

1.5≦

δ

≦

1.5, wherein each of said distinct phosphors has a different emission spectrum.

11. The lighting apparatus of claim 1, wherein said phosphor composition further comprises one or more additional phosphors.

12. The lighting apparatus of claim 11, wherein said one or more additional phosphors are selected from the group consisting of (Ba,Sr,Ca)₅(PO₄)₃(Cl,F,Br,OH):

Eu²⁺, Mn²⁺, Sb³⁺;

(Ba,Sr,Ca)MgAl₁₀O₁₇;

Eu²⁺,Mn²⁺;

(Ba,Sr,Ca)BPO₅;

Eu²⁺,Mn²⁺;

(Sr,Ca)₁₀(PO₄)₆*nB₂O₃;

Eu²⁺;

2SrO*0.84P₂O₅*0.16B₂O₃;

Eu²⁺;

Sr₂Si₃O₈*2SrCl₂;

Eu²⁺;

Ba₃MgSi₂O₈;

Eu²⁺;

Sr₄Al₁₄O₂₅;

Eu²⁺;

BaAl₈O₁₃;

Eu²⁺;

(Ba,Sr,Ca)Al₂O₄;

Eu²⁺;

(Y,Gd,Lu,Sc,La)BO₃;

Ce³⁺,Tb³⁺;

Ca₈Mg(SiO₄)₄Cl₂;

Eu²⁺,Mn²⁺;

(Ba,Sr,Ca)₂SiO₄;

Eu²⁺;

(Ba,Sr,Ca)₂(Mg,Zn)Si₂O₇;

Eu²⁺;

(Sr,Ca,Ba)(Al,Ga,In)₂S₄;

Eu²⁺;

(Y,Gd,Tb,La,Sm,Pr,Lu)₃(Al,Ga)₅O₁₂;

Ce³⁺;

(Ca,Sr)₈(Mg,Zn)(SiO₄)₄Cl₂;

Eu²⁺,Mn<sup>2+;

Na</sup>₂Gd₂B₂O₇;

Ce³⁺,Tb³⁺;

(Ba, Sr)₂(Ca,Mg,Zn)B₂O₆;

K,Ce,Tb;

(Sr,Ca,Ba,Mg,Zn)₂P₂O₇;

Eu²⁺,Mn²⁺;

(Ca,Sr,Ba,Mg)₁₀(PO₄)₆(F,Cl,Br,OH);

Eu²⁺,Mn²⁺;

(Gd,Y,Lu,La)₂O₃;

Eu³⁺, Bi³⁺;

(Gd,Y,Lu,La)₂O₂S;

Eu³⁺,Bi³⁺;

(Gd,Y,Lu,La)VO₄;

Eu³⁺,Bi³⁺;

(Ca,Sr)S;

Eu²⁺;

SrY₂S₄;

Eu²⁺;

CaLa₂S₄;

Ce³⁺;

3.5MgO*0.5MgF₂*GeO₂;

Mn⁴⁺;

(Ba,Sr,Ca)MgP₂O₇;

Eu²⁺,Mn²⁺;

(Y,Lu)₂WO₆;

Eu³+,Mo⁶⁺;

(Ba,Sr,Ca)_xSi_yN_z;

Eu²⁺.

13. The lighting apparatus of claim 1, further comprising a (Tb,Y)₃Al_4.9O₁₂₋

δ

;

Ce³⁺ phosphor wherein −

1≦

δ

≦

1.

14. The lighting apparatus of claim 1, wherein 2.9≦

z≦

3.1.

15. The lighting apparatus of claim 1, wherein 0≦

q/(z−

q)≦

0.5.

16. The lighting apparatus of claim 1, wherein A is Ca.

17. The lighting apparatus of claim 1, wherein A is Mg.

18. The lighting apparatus of claim 1, wherein B is Mg.

19. The lighting apparatus of claim 1, wherein y≦

0.05.

20. The lighting apparatus of claim 1, wherein said lighting apparatus has a CCT value from about 2500 to 8000.

21. The lighting apparatus of claim 1, wherein said lighting apparatus has a CRI value of greater than 60.

22. A phosphor composition comprising (RE₁₋

x−

ySc_xCe_y)₂A<sub>3−

p</sub>B_pSi<sub>z−

q</sub>Ge_qO_12+δ

, where RE is selected from a lanthanide ion or Y³⁺, A is selected from Mg, Ca, Sr, or Ba, B is selected from Mg and Zn, and where 0≦

p≦

3, 0≦

q≦

3, 2.5≦

z≦

3.5, 0≦

x<

1, 0<

y≦

0.3, −

1.5≦

δ

≦

1.5.

23. The phosphor composition according to claim 22, wherein 2.9≦

z≦

3.1.

24. The phosphor composition according to claim 22, wherein 0≦

q/(z−

q)≦

0.5.

25. The phosphor composition according to claim 22, wherein A is Ca.

26. The phosphor composition according to claim 22, wherein A is Mg.

27. The phosphor composition according to claim 22, wherein B is Mg.

28. The phosphor composition according to claim 22, wherein y≦

0.05.

29. The phosphor composition according to claim 22 comprising (Lu_0.955Ce_0.045)₂CaMg₂Si₃O₁₂.

30. The phosphor composition according to claim 22, wherein said phosphor composition is capable of absorbing the radiation emitted by a light source emitting from 400–

500 nm and emitting radiation that, when combined with said radiation from said light source, produces white light.

31. A phosphor blend including a first phosphor selected from the group consisting of (Tb,Y)₃Al_4.9O₁₂₋

δ

;

Ce³⁺ wherein −

1≦

δ

≦

1 and (Tb<sub>1−

x−

y−

z−

w</sub>Y_xGd_yLu_zCe_w)₃M_rAl<sub>s−

r</sub>O_12+δ

, where M is selected from Sc, In, Ga, Zn, or Mg, and where 0<

w≦

0.3, 0≦

x<

1, 0≦

y≦

0.4, 0≦

z<

1, 0≦

r≦

4.5, 4.5≦

s≦

6, and −

1.5≦

δ

≦

1.5, and a second phosphor having the formula (RE<sub>1−

x−

y</sub>Sc_xCe_y)₂A<sub>3−

p</sub>B_pSi<sub>z−

q</sub>Ge_qO_12+δ

, where RE is selected from a lanthanide ion or Y³⁺, A is selected from Mg, Ca, Sr, or Ba, B is selected from Mg and Zn, and where 0≦

p≦

3, 0≦

q≦

3, 2.5≦

z≦

3.5, 0≦

x<

1, 0<

y≦

0.3, −

1.5≦

δ

≦

1.5.

32. A phosphor composition comprising (Ca₁₋

x−

y−

zSr_xBa_yCe_z)₃(Sc<sub>1−

a−

c</sub>Lu_aD_c)₂Si<sub>n−

w</sub>Ge_wO_12+δ

, where D is either Mg or Zn, 0≦

x<

1, 0≦

y<

1, 0<

z≦

0.3, 0≦

a<

1, 0≦

c≦

1, 0≦

w≦

1, 2.5≦

n≦

3.5, and −

1.5≦

δ

≦

1.5.

33. The phosphor composition according to claim 32, comprising (Ca₁₋

zCe_z)₃Sc₂Si<sub>n−

w</sub>Ge_wO₁₂.

34. The phosphor composition according to claim 33, comprising (Ca₁₋

zCe_z)₃Sc₂Si₃O₁₂.

35. The phosphor composition according to claim 33, comprising (Ca_0.99Ce_0.01)₃Sc₂Si₃O₁₂.

36. The phosphor composition according to claim 32, wherein said phosphor composition is capable of absorbing radiation having a wavelength of from about 250 to about 490 nm and emitting radiation with an emission maximum at about 505 nm.

37. The phosphor composition according to claim 32, wherein 2.9≦

n≦

3.1.

38. The phosphor composition according to claim 32, wherein x≦

0.1.

39. The phosphor composition according to claim 32, wherein y≦

0.1.

40. The phosphor composition according to claim 32, wherein z≦

0.05.

41. The phosphor composition according to claim 32, wherein a≦

0.10.

42. The phosphor composition according to claim 32, further comprising (Tb₁₋

x−

y−

z−

wY_xGd_yLu_zCe_w)₃M_rAl<sub>s−

r</sub>O_12+δ

, where M is selected from Sc, In, Ga, Zn, or Mg, and where 0<

w≦

0.3, 0≦

x<

1, 0≦

y≦

0.4, 0≦

z<

1, 0≦

r≦

4.5, 4.5≦

s≦

6, and −

1.5≦

δ

≦

1.5; and

(RE<sub>1−

x−

y</sub>Sc_xCe_y)₂A<sub>3−

p</sub>B_pSi<sub>z−

q</sub>Ge_qO_12+δ

, where RE is selected from a lanthanide ion or Y³⁺, A is selected from Mg, Ca, Sr, or Ba, B is selected from Mg and Zn, and where 0≦

p≦

3, 0≦

q≦

3, 2.5≦

z≦

3.5, 0≦

x<

1, 0≦

y≦

0.3, −

1.5≦

δ

≦

1.5.

43. A lighting apparatus comprising a light source emitting radiation having an emission wavelength of from about 250 to about 500 nm and a phosphor composition comprising (Ca₁₋

x−

y−

zSr_xBa_yCe_z)₃(Sc<sub>1−

a−

c</sub>Lu_aD_c)₂Si<sub>n−

w</sub>Ge_wO_12+δ

, where D is either Mg or Zn, 0≦

x<

1, 0≦

y<

1, 0<

z≦

0.3, 0≦

a≦

1, 0≦

c<

1, 0≦

w≦

3, 2.5≦

n≦

3.5, and −

1.5≦

δ

≦

1.5.

44. The lighting apparatus of claim 43, wherein said lighting apparatus is a white light emitting device.

45. The lighting apparatus of claim 43, further comprising one or more additional phosphors.

46. The lighting apparatus of claim 45, wherein said one or more additional phosphors are selected from the group consisting of (Ba,Sr,Ca)₅(PO₄)₃(Cl,F,Br,OH):

Eu²⁺,Mn²⁺,Sb³⁺;

(Ba,Sr,Ca)MgAl₁₀O₁₇;

Eu²⁺,Mn²⁺;

(Ba,Sr,Ca)BPO₅;

Eu²⁺,Mn²⁺;

(Sr,Ca)₁₀(PO₄)₆*nB₂O₃;

Eu²⁺;

2SrO*0.84P₂O₅*0.16B₂O₃;

E²⁺;

Sr₂Si₃O₈*2SrCl₂;

Eu²⁺;

Ba₃MgSi₂O₈;

Eu²⁺;

Sr₄Al₁₄O₂₅;

Eu²⁺;

BaAl₈O₁₃;

Eu²⁺;

(Ba,Sr,Ca)Al₂O₄;

Eu²⁺;

(Y,Gd,Lu,Sc,La)BO₃;

Ce³⁺, Tb³⁺;

Ca₈Mg(SiO₄)₄Cl₂;

Eu²⁺, Mn²⁺;

(Ba,Sr,Ca)₂SiO₄;

Eu²⁺;

(Ba,Sr,Ca)₂(Mg,Zn)Si₂O₇;

Eu²⁺;

(Sr,Ca,Ba)(Al,Ga,In)₂S₄;

Eu²⁺;

(Y,Gd,Tb,La,Sm,Pr,Lu)₃(Al,Ga)₅O₁₂;

Ce³⁺;

(Ca,Sr)₈(Mg,Zn)(SiO₄)₄Cl₂;

Eu²⁺,Mn²⁺;

Na₂Gd₂B₂O₇;

Ce³⁺, Tb³⁺;

(Ba,Sr)₂(Ca,Mg,Zn)B₂O₆;

K,Ce,Tb;

(Sr,Ca,Ba,Mg,Zn)₂P₂O₇;

Eu²⁺, Mn²⁺;

(Ca,Sr,Ba,Mg)₁₀(PO₄)₆(F,Cl,Br,OH);

Eu²⁺,Mn²⁺;

(Gd,Y,Lu,La)₂O₃;

Eu³⁺,Bi³⁺;

(Gd,Y,Lu,La)₂O₂S;

Eu³⁺,Bi³⁺;

(Gd,Y,Lu,La)VO₄;

Eu³⁺,Bi³⁺;

(Ca,Sr)S;

Eu²⁺;

SrY₂S₄;

Eu²⁺;

CaLa₂S₄;

Ce³⁺;

3.5MgO*0.5MgF₂*GeO₂;

Mn⁴+;

(Ba,Sr,Ca)MgP₂O₇;

Eu²⁺,Mn²⁺;

(Y,Lu)₂WO₆;

Eu³+,Mo⁶⁺;

(Ba,Sr,Ca)_xSi_yN_z;

Eu²⁺.

47. The lighting apparatus of claim 43, further comprising at least one phosphor selected from the group consisting of (Tb₁₋

x−

y−

z−

wY_xGd_yLu_zCe_w)₃M_rAl<sub>s−

r</sub>O_12+δ

, where M is selected from Sc, In, Ga, Zn, or Mg, and where 0<

w≦

0.3, 0≦

x<

1, 0≦

y≦

0.4, 0≦

z<

1, 0≦

r≦

4.5, 4.5≦

s≦

6, and −

1.5≦

δ

≦

1.5; and

further wherein at least one of y or z is >

0;

(RE<sub>1−

x−

y</sub>Sc_xCe_y)₂A<sub>3−

p</sub>B_pSi<sub>z−

q</sub>Ge_qO_12+δ

, where RE is selected from a lanthanide ion or Y³⁺, A is selected from Mg, Ca, Sr, or Ba, B is selected from Mg and Zn, and where 0≦

p≦

3, 0≦

q≦

3, 2.5≦

z≦

3.5, 0≦

x<

1, 0<

y≦

0.3, −

1.5≦

δ

≦

1.5; and

(Tb,Y)₃Al_4.9O<sub>12−

δ</sub>

;

Ce³⁺ wherein −

1≦

δ

≦

1.

48. The lighting apparatus of claim 43, wherein the light source is a semiconductor light emitting diode.

49. The lighting apparatus of claim 43, wherein said lighting apparatus has a CRI value of greater than 60.

50. The lighting apparatus of claim 43, wherein said phosphor comprises Ca₃Sc₂(Si_xGe₁₋

x)₃O₁₂;

Ce³⁺, wherein x is from 0.67 to 1.0.

51. The lighting apparatus of claim 43, wherein said phosphor comprises Ca₃Sc₂Si₃O₁₂:

Ce³⁺.

52. The lighting apparatus of claim 43, wherein said phosphor comprises (Ca_0.99Ce_0.01)₃Sc₂Si₃O₁₂.