Charge compensated nitride phosphors for use in lighting applications

• US 7,262,439 B2
• Filed: 11/22/2005
• Issued: 08/28/2007
• Est. Priority Date: 11/22/2005
• Status: Active Grant

• Current Assignee: Current Lighting Solutions, LLC (f/k/a GE Lighting Solutions, LLC) (American Industrial Partners)
• Original Assignee: Lumination LLC
• Inventors: Setlur, Anant Achyut, Radkov, Emil Vergilov
• Primary Examiner(s): TRAN, MINH LOAN
• Application Number:
  US11/285,024
• Publication Number:
  US 20070114548A1
• Time in Patent Office: 644 Days
• Field of Search: 257/98, 257/100, 257/E33.061, 313501-503, 313/486, 428/690, 252/301.4 R
• US Class Current: 257/98
• CPC Class Codes: C09K 11/0883 Arsenides; Nitrides; Phosphides
• CPC Class Codes: C09K 11/77218 Silicon Aluminium Nitrides or Silicon Aluminium Oxynitrides
• CPC Class Codes: C09K 11/77348 Silicon Aluminium Nitrides or Silicon Aluminium Oxynitrides
• CPC Class Codes: C09K 11/77928 Silicon Aluminium Nitrides or Silicon Aluminium Oxynitrides
• 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 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

Abstract

Disclosed are phosphor compositions having the formulas Ca_1−a−bCe_aEu_bAl_1+aSi_1−aN₃, where 0<a≦0.2, 0≦b≦0.2; Ca_1−c−dCe_cEu_dAl_1−c(Mg,Zn)_cSiN₃, where 0<c≦0.2, 0≦d≦0.2; Ca_1−2e−fCe_e(Li,Na)_eEu_fAlSiN₃, where 0≦e≦0.2, 0≦f≦0.2, g+h>0; and Ca_{1−g−h−i}Ce_g(Li,Na)_hEu_iAl_1+g−hSi_1−g+hN₃ where 0≦g≦0.2, 0<h≦0.4, 0≦i≦0.2,g+i>0. When combined with radiation from a blue or UV light source, these phosphors can provide light sources with good color quality having high CRI over a large color temperature range. Also disclosed are blends of the above phosphors and additional phosphors.

Claims

1. A lighting apparatus for emitting white light comprising:

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

a phosphor material radiationally coupled to the light source, the phosphor material comprising at least one of Ca<sub>1−

a−

b</sub>Ce_aEu_bAl_1+aSi<sub>1−

a</sub>N₃, where 0<

a≦

0.2, 0≦

b≦

0.2;

Ca<sub>1−

c−

d</sub>Ce_cEu_dAl<sub>1−

c</sub>(Mg,Zn)_cSiN₃, where 0<

c≦

0.2, 0≦

d≦

0.2;

Ca<sub>1−

2e−

f</sub>Ce_e(Li,Na)_eEu_fAlSiN₃, where 0<

e≦

0.2, 0≦

f≦

0.2, e+f>

0;

or Ca<sub>1−

g−

h−

i</sub>Ce_g(Li,Na)_hEu_jAl<sub>1+g−

h</sub>Si<sub>1−

g+h</sub>N₃ where 0≦

g≦

0.2, 0<

h≦

0.4, 0≦

i≦

0.2, g+i>

0.

2. The lighting apparatus of claim 1, wherein the light source is a semiconductor light emitting diode (LED) emitting radiation having a peak wavelength in the range of from about 350 to about 500 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 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 further comprises one or more additional phosphor.

10. The lighting apparatus of claim 9, wherein said one or more additional phosphors are selected from the group including:

(Ba,Sr,Ca)₅(PO₄)₃(Cl,F,Br,OH);

Eu²⁺,Mn²⁺;

(Ba,Sr,Ca)BPO₅;

Eu²⁺,Mn²⁺;

(Sr,Ca)₁₀(PO₄)₆*ν

B₂O₃;

Eu²⁺ (wherein 0<

ν

≦

1);

Sr₂Si₃O₈*2SrCl₂;

Eu²⁺;

(Ca,Sr,Ba)₃MgSi₂O₈;

Eu²⁺,Mn²⁺;

BaAl₈O₁₃;

Eu²⁺;

2SrO*0.84P₂O₅*0.16B₂O₃;

Eu²⁺;

(Ba,Sr,Ca)MgAl₁₀O₁₇;

Eu²⁺, Mn²⁺;

(Ba,Sr,Ca)Al₂O₄;

Eu²⁺;

(Y,Gd,Lu,Sc,La)BO₃;

Ce³⁺,Tb³⁺;

(Ba,Sr,Ca)₂Si<sub>1−

ξ</sub>

O<sub>4−

2ξ</sub>

;

Eu²⁺ (wherein 0≦

ξ

≦

0.2);

(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)<sub>5−

λ</sub>

O<sub>12−

3/2λ</sub>

;

Ce³⁺ (wherein 0≦

λ

≦

0.5);

(Lu,Y,SC)<sub>2−

ρ</sub>

(Ca,Mg)_1+ρ

Li_σ

Mg<sub>2−

σ</sub>

(Si,Ge)<sub>3−

σ</sub>

P_σ

O<sub>12−

ρ</sub>

;

Ce³⁺ (wherein 0≦

ρ

≦

0.5, 0≦

σ

0.5);

(Ca,Sr)₈(Mg,Zn)(SiO₄)₄Cl₂;

Eu²⁺, Mn²⁺;

Na₂Gd₂B₂O₇;

Ce³⁺,Tb³⁺;

(Sr,Ca,Ba,Mg,Zn)₂P₂O₇;

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⁺;

(Ca,Sr)S;

Eu²⁺,Ce³⁺;

SrY₂S₄;

Eu²⁺;

CaLa₂S₄;

Ce³⁺;

(Ba,Sr,Ca)MgP₂O₇;

Eu²⁺,Mn²⁺;

(Y,Lu)₂WO₆;

Eu³⁺,Mo⁶⁺;

(Ba,Sr,Ca)_β

Si_γ

N_μ

;

Eu²⁺ (wherein 2β

+4γ

=3μ

);

Ca₃(SiO₄)Cl₂;

Eu²⁺;

(Y,Lu,Gd)<sub>2−

φ</sub>

Ca_φ

Si₄N_6+φ

C<sub>1−

φ</sub>

;

Ce³⁺ (wherein 0≦

φ

≦

0.5);

(Lu,Ca,Li,Mg,Y)α

-SiAlON doped with Eu²⁺ and/or Ce³⁺; and

3.5MgO*0.5MgF₂*GeO₂;

Mn⁴⁺.

11. The lighting apparatus of claim 1, wherein the light emitted by said apparatus has a general CRI (Ra) of at least 80.

12. The lighting apparatus of claim 11, wherein the light emitted by said apparatus has a general CRI (Ra) of at least 90.

13. A phosphor material comprising at least one of Ca₁₋

a−

bCe_aEu_bAl_1+aSi<sub>1−

a</sub>N₃, where 0<

a≦

0.2, 0≦

b≦

0.2;

Ca<sub>1−

c−

d</sub>Ce_cEu_dAl<sub>1−

c</sub>(Mg,Zn)_cSiN₃, where 0<

c≦

0.2, 0≦

d0.2;

Ca<sub>1−

2e−

f</sub>Ce_e(Li,Na)_eEu_fAlSiN₃, where 0<

e≦

0.2, 0≦

f≦

0.2,e+f>

0;

or Ca<sub>1−

g−

h−

i</sub>Ce_g(Li,Na)_hEu_iAl<sub>1+g−

h</sub>Si<sub>1−

g+h</sub>N₃, where 0≦

g≦

0.2, 0<

h≦

0.4, 0≦

i≦

0.2, g+i>

0.

14. A phosphor material according to claim 13, comprising at least one of (Ca_0.97Eu_0.01Ce_0.02)(Al_0.98Mg_0.02)SiN₃;

(Ca_0.99Ce_0.01)(Al_0.99Mg_0.01) SiN₃;

(Ca_0.95Eu_0.02Li_0.03)Al_0.97Si_1.03N₃;

or (Ca_0.90Eu_0.02Li_0.08)Al_0.92Si_1.08N₃.

15. A phosphor blend including at least one of Ca₁₋

a−

bCe_aEu_bAl_1+aSi<sub>1−

a</sub>N₃, where 0<

a≦

0.2, 0≦

b≦

0.2;

Ca<sub>1−

c−

d</sub>Ce_cEu_dAl<sub>1−

c</sub>(Mg,Zn)_cSiN₃, where 0<

c≦

0.2, 0≦

d≦

0.2;

Ca<sub>1−

2e−

f</sub>Ce_e(Li,Na)_eEu_fAlSiN₃, where 0<

e≦

0.2, 0≦

f≦

0.2, e+f<

0;

or Ca<sub>1−

g−

h−

i</sub>Ce_g(Li,Na)_hEu_iAl<sub>1+g−

h</sub>Si<sub>1−

g+h</sub>N₃, where 0≦

g≦

0.2, 0<

h≦

0.4, 0≦

i≦

0.2, g+i>

0; and

at least one additional phosphor, wherein the phosphor blend is capable of emitting light suitable for use in general illumination either alone or in combination with radiation emitted by a light source radiationally coupled to the phosphor.

16. The phosphor blend of claim 15, wherein said one or more additional phosphors are selected from the group including:

(Ba,Sr,Ca)₅(PO₄)₃(Cl,F,Br,OH);

Eu²⁺,Mn²⁺;

(Ba,Sr,Ca)BPO₅;

Eu²⁺,Mn²⁺;

(Sr,Ca)₁₀(PO₄)₆*ν

B₂O₃;

Eu²⁺ (wherein 0<

ν

≦

1);

Sr₂Si₃O₈*2SrCl₂;

Eu²⁺;

(Ca,Sr,Ba)₃MgSi₂O₈;

Eu²⁺,Mn²⁺;

BaAl₈O₁₃;

Eu²⁺;

2SrO*0.84P₂O₅*0.16B₂O₃;

Eu²⁺;

(Ba,Sr,Ca)MgAl_10O17;

Eu²⁺,Mn²⁺;

(Ba,Sr,Ca)Al₂O₄;

Eu²⁺;

(Y,Gd,Lu,Sc,La)BO₃;

Ce³⁺,Tb³⁺;

(Ba,Sr,Ca)₂Si<sub>1−

ξ</sub>

O<sub>4−

2ξ</sub>

;

Eu²⁺ (wherein 0≦

ξ

≦

0.2);

(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)<sub>5−

λ</sub>

O<sub>12−

3/2λ</sub>

;

Ce³⁺ (wherein 0≦

λ

≦

0.5);

(Lu,Y,SC)<sub>2−

ρ</sub>

(Ca,Mg)_1+ρ

Li_σ

Mg<sub>2−

σ</sub>

(Si,Ge)<sub>3−

σ</sub>

P_σ

O<sub>12−

ρ</sub>

;

Ce₃₊ (wherein 0≦

ρ

≦

0.5, 0≦

σ

≦

0.5);

(Ca,Sr)₈(Mg,Zn)(SiO₄)₄Cl₂;

Eu²⁺, Mn²⁺;

Na₂Gd₂B₂O₇;

Ce³⁺,Tb³⁺;

(Sr,Ca,Ba,Mg,Zn)₂P₂O₇;

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⁺;

(Ca,Sr)S;

Eu²⁺, Ce³⁺;

SrY₂S₄;

Eu²⁺;

CaLa₂S₄;

Ce³⁺;

(Ba,Sr,Ca)MgP₂O₇;

Eu²⁺, Mn²⁺;

(Y,Lu)₂WO₆;

Eu³⁺,Mo⁶⁺;

(Ba,Sr,Ca)_β

Si_γ

N_μ

;

Eu²⁺ (wherein 2β

+4γ

=3μ

);

Ca₃(SiO₄)Cl₂;

Eu²⁺;

(Y,Lu,Gd)<sub>2−

φ</sub>

Ca_φ

Si₄N_6+φ

C<sub>1−

φ</sub>

;

Ce³⁺ (wherein 0≦

φ

≦

0.5);

(Lu,Ca,Li,Mg,Y)α

-SiAlON doped with Eu²⁺ and/or Ce³⁺; and

3.5MgO*0.5MgF2*GeO2;

Mn⁴⁺.

17. The phosphor blend of claim 15, wherein the light emitted by the blend alone or in combination with radiation emitted by a light source radiationally coupled to the phosphor is white.

18. The phosphor blend of claim 17, wherein the light emitted by the blend alone or in combination with radiation emitted by a light source radiationally coupled to the phosphor has a general CRI (Ra) of at least 80.

19. The phosphor blend of claim 18, wherein the light emitted by the blend alone or in combination with radiation emitted by a light source radiationally coupled to the phosphor has a general CRI (Ra) of at least 90.