Garnet phosphor materials having enhanced spectral characteristics

• US 7,252,787 B2
• Filed: 08/04/2004
• Issued: 08/07/2007
• 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: Hancu, Dan, Srivastava, Alok Mani, Comanzo, Holly Ann, Setlur, Anant Achyut, Chandran, Gopi, Briel, Linda, Venugopal, Shankar
• Primary Examiner(s): KOSLOW, CAROL M
• Application Number:
  US10/910,991
• Publication Number:
  US 20050093431A1
• Time in Patent Office: 1,098 Days
• Field of Search: 313/503, 257/98, 252/301.4 R, 252/301.4 F, 252/301.6 F, 252/301.4 H, 252/301.4 P, 252/301.6 P, 252/301.4 S, 252/301.5
• US Class Current: 252/301.40R
• CPC Class Codes: C09K 11/77744 Aluminosilicates
• 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 2924/181 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
• CPC Class Codes: Y02B 20/00 Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps

Abstract

Phosphor compositions having the formula (Y_1-x-y-zTb_xGd_yCe_z)₃(M₁M₂)_t(Al_1-r-sGa_rIn_s)_A-2tO_12+D, where M₁ is Mg or Zn, M₂ is Si or Ge, 0<x+y<1, 0.01<z<0.1, 0.1<t<1.5, 0<r, s<0.5, 4.5<A<5.0, and −1<D<1. Also disclosed are light emitting devices including a light source and at least one phosphor having the above formula. Such phosphors exhibit a deeper red emission when compared to conventional TAG phosphors, allowing the production of white light sources having improved properties.

Claims

1. A lighting apparatus for emitting white light comprising:

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

a phosphor composition radiationally coupled to the light source, the phosphor composition comprising (Y_1-x-y-zTb_xGd_yCe_z)₃(M₁M₂)_t(Al_1-r-sGa_rIn_s)_A-2tO_12+D, where M₁ is Mg or Zn, M₂ is Si or Ge, 0<

x+y<

1, 0.01<

z<

0.1, 0.1<

t<

1.5, 0<

r, s<

0.5, 4.5<

A<

5.0, and −

1<

D<

1.

2. The lighting apparatus of claim 1, wherein the light source is a semiconductor light emitting diode (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 the 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 6, 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 (Y_0.49Gd_0.48Ce_0.03)₃(MgSi)_1.5Al₂O₁₂.

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

11. The lighting apparatus of claim 10, 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⁺;

Sr₄A₁₄O₂₅;

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⁺; and

(Sr,Ca,Ba)₃MgSi₂O₈;

Eu²⁺,Mn²⁺.

12. The lighting apparatus of claim 1, further including a pigment, filter or other absorber capable of absorbing radiation generated between 250 nm and 450 nm.

13. The lighting apparatus of claim 1, wherein said lighting apparatus has a CCT value from about 2500 to 10,000.

14. The lighting apparatus of claim 1, wherein said lighting apparatus has a CRI value of from about 70 to 95.

15. A phosphor composition comprising (Y_1-x-y-zTb_xGd_yCe_z)₃(M₁M₂)_t(Al_1-r-sGa_rIn_s)_A-2tO_12+D, where M₁ is Mg or Zn, M₂ is Si or Ge, 0<

x+y<

1, 0.01<

z<

0.1, 0.1<

t<

1.5, 0<

r, s<

0.5, 4.5<

A<

5.0, and −

1<

D<

1.

16. The phosphor composition according to claim 15 comprising (Y_0.49Gd_0.48Ce_0.03)₃(MgSi)_1.5Al₂O₁₂.

17. The phosphor composition according to claim 15, wherein said phosphor composition is capable of absorbing the radiation emitted by a light source emitting from 350-500 nm and emitting radiation that, when combined with said radiation from said light source, produces white light.

19. The phosphor blend according to claim 17, comprising (Y_0.49Gd_0.48Ce_0.03)₃(MgSi)_1.5Al₂O₁₂.

20. The phosphor blend according to claim 17, further comprising one or more additional phosphors.

21. The phosphor blend according to claim 20, 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⁺,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⁺;

CaLa₂S₄Ce³⁺;

3.5MgO*0.5MgF₂*GeO₂;

Mn⁴⁺;

(Ba,Sr,Ca)MgP₂O₇;

Eu²⁺,Mn²⁺;

(Y,Lu)₂WO₆;

Eu³⁺,Mo⁶⁺;

(Ba,Sr,Ca)_xSi_yN_z;

Eu²⁺; and

(Sr,Ca,Ba)₃MgSi₂O₈;

Eu²⁺,Mn²⁺.

18. A phosphor blend including a first phosphor having the formula (Y_1-x-y-zTb_xGd_yCe_z)₃(M₁M₂)_t(Al_1-r-sGa_rIn_s)_A-2tO_12+D, where M₁ is Mg or Zn, M₂ is Si or Ge, 0<

x+y<

1, 0.01<

z<

0.1, 0.1<

t<

1.5, 0<

r, s<

0.5, 4.5<

A<

5.0, and −

1<

D<

1, and a TAG;

Ce phosphor.