Red garnet phosphors for use in LEDs

US 7,442,326 B2
Filed: 11/23/2005
Issued: 10/28/2008
Est. Priority Date: 10/29/2003
Status: Active Grant

First Claim

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1. A lighting apparatus for emitting light comprising:

a light source emitting radiation having a peak emission from about 200 nm to about 500 nm; and

a phosphor material radiationally coupled to the light source, the phosphor material comprising L_lM_mA_aG_gP_pQ_qN_nZ_z;

Ce³⁺, where L is at least one of Li, Na, K, Rb, and/or Cs;

M is at least one of Be, Mg, Ca, Sr, Ba, Mn, Sn, Pb, and/or Zn;

A is at least one of Bi, Sb, In, Sc, Y, and/or any of the rare earth elements;

G is Si and/or Ge;

Q is at least one of O, S, and/or Se;

Z is at least one of F, Cl, Br, and/or I; and

wherein 0≦

l≦

1, 2.5≦

m≦

5, 1.5≦

a≦

2.5, 2≦

g≦

2.5, 0≦

p≦

1, 0≦

n≦

1, 0≦

z≦

1, and l+2m+3a+4g+5p=2q+3n+z.

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Abstract

Phosphor compositions having the formula L_lM_mA_aG_gP_pQ_qN_nZ_z:Ce³⁺, where L is at least one of Li, Na, K, Rb, and/or Cs; M is at least one of Be, Mg, Ca, Sr, Ba, Mn, Sn, Pb, and/or Zn; A is at least one of Bi, Sb, In, Sc, Y, and/or any of the rare earth elements; G is Si and/or Ge; Q is at least one of O, S, and/or Se; Z is at least one of F, Cl, Br, and/or I; and wherein 0≦l≦1, 2.5≦m≦5, 1.5≦a≦2.5, 2≦g≦2.5, 0≦p≦1, 0≦n≦1, 0≦z≦1, and l+2m+3a+4g+5p=2q+3n+z; and light emitting devices including a light source and the above phosphor. Also disclosed are blends of L_lM_mA_aG_gP_pQ_qN_nZ_z:Ce³⁺ and one or more additional phosphors and light emitting devices incorporating the same.

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22 Claims

1. A lighting apparatus for emitting light comprising:
- a light source emitting radiation having a peak emission from about 200 nm to about 500 nm; and
  
  a phosphor material radiationally coupled to the light source, the phosphor material comprising L_lM_mA_aG_gP_pQ_qN_nZ_z;
  
  Ce³⁺, where L is at least one of Li, Na, K, Rb, and/or Cs;
  
  M is at least one of Be, Mg, Ca, Sr, Ba, Mn, Sn, Pb, and/or Zn;
  
  A is at least one of Bi, Sb, In, Sc, Y, and/or any of the rare earth elements;
  
  G is Si and/or Ge;
  
  Q is at least one of O, S, and/or Se;
  
  Z is at least one of F, Cl, Br, and/or I; and
  
  wherein 0≦
  
  l≦
  
  1, 2.5≦
  
  m≦
  
  5, 1.5≦
  
  a≦
  
  2.5, 2≦
  
  g≦
  
  2.5, 0≦
  
  p≦
  
  1, 0≦
  
  n≦
  
  1, 0≦
  
  z≦
  
  1, and l+2m+3a+4g+5p=2q+3n+z.
- View Dependent Claims (2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16)
- - 2. The lighting apparatus according to claim 1, wherein the light source is an LED.
  - 3. The lighting apparatus according to 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 according to claim 1, wherein the amount of Ce³⁺ doping is from 0.0001 to 10 mole percent.
  - 5. The lighting apparatus according to claim 1, wherein the light source is an organic emissive structure.
  - 6. The lighting apparatus according to claim 1, wherein the phosphor material is coated on a surface of the light source.
  - 7. The lighting apparatus according to claim 1, further comprising an encapsulant surrounding the light source and the phosphor material.
  - 8. The lighting apparatus according to claim 1, wherein the phosphor material is dispersed in the encapsulant.
  - 9. The lighting apparatus according to claim 1, further comprising a reflector cup.
  - 10. The lighting apparatus according to claim 1, wherein the lighting apparatus comprises a discharge lamp and wherein said phosphor material is coated on a surface of a glass envelope.
  - 11. The lighting apparatus according to claim 1, wherein said phosphor material further comprises one or more additional phosphors.
  - 12. The lighting apparatus according to claim 11, 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_1−
      
      ξO_4−
      
      2ξ;
      
      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)_5−
      
      αO_12−
      
      3/2α;
      
      Ce³⁺ (wherein 0≦
      
      α
      
      ≦
      
      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⁺,Ce³⁺;
      
      SrY₂S₄;
      
      Eu²⁺;
      
      CaLa₂S₄;
      
      Ce³⁺;
      
      (Ba,Sr,Ca)MgP₂O₇;
      
      Eu²⁺,Mn²⁺;
      
      (Y,Lu)₂WO₆;
      
      Eu³⁺,Mo⁶⁺;
      
      (Ba,Sr,Ca)_βSi_γN_μ;
      
      Eu²⁺ (wherein 2β
      
      +4γ
      
      =3μ
      
      );
      
      Ca₃(SiO₄)Cl₂;
      
      Eu²⁺;
      
      (Y,Lu,Gd)_2−
      
      φCa_φSi₄N_6+φC_1−
      
      φ;
      
      Ce³⁺, (wherein 0≦
      
      φ
      
      ≦
      
      0.5);
      
      (Lu,Ca,Li,Mg,Y)alpha-SiAlON doped with Eu²⁺ and/or Ce³⁺;
      
      3.5MgO*0.5MgF₂*GeO₂;
      
      Mn⁴⁺;
      
      Ca_{1−
      
      c−
      
      f}Ce_cEu_fAl_1+cSi_1−
      
      cN₃, (where 0≦
      
      c≦
      
      0.2, 0≦
      
      f≦
      
      0.2);
      
      Ca_{1−
      
      h−
      
      r}Ce_hEu_rAl_1−
      
      h(Mg,Zn)_hSiN₃, (where 0<
      
      h≦
      
      0.2, 0≦
      
      r≦
      
      0.2);
      
      Ca_{1−
      
      2s−
      
      t}Ce_s(Li,Na)_sEu_tAlSiN₃, (where 0≦
      
      s≦
      
      0.2, 0≦
      
      f≦
      
      0.2, s+t>
      
      0); and
      
      Ca_{1−
      
      σ
      
      −
      
      χ
      
      −
      
      i}Ce_σ(Li,Na)_χEu_φAl_{1+σ
      
      −
      
      χ}Si_{1−
      
      σ
      
      +χ}N₃, (where 0≦
      
      σ
      
      ≦
      
      0.2, 0≦
      
      χ
      
      ≦
      
      0.4, 0≦
      
      φ
      
      ≦
      
      0.2).
  - 13. The lighting apparatus according to claim 11, wherein said phosphor material is capable of absorbing the radiation emitted by a light source having a peak emission from 200-500 nm and emitting radiation that, when combined with said radiation from said light source, produces white light.
  - 14. The lighting apparatus according to claim 13, wherein said apparatus has a color temperature of <
    - 4500 K.
  - 15. The lighting apparatus according to claim 13, wherein said apparatus has a general CRI (R_a) of 90 or greater.
  - 16. The lighting apparatus of claim 1, wherein said phosphor material comprises (Lu,Sc,Y,Tb)₂₋
    - d−
      
      eCe_eCa_1+dMg₂Si₃O_12−
      
      d/2where −
      
      0.5≦
      
      d≦
      
      1 and 0<
      
      e≦
      
      0.1.

17. A phosphor blend comprising a first phosphor composition comprising L_lM_mA_aG_gP_pQ_qN_nZ_z:
- Ce³⁺, where L is at least one of Li, Na, K, Rb, and/or Cs;
  
  M is at least one of Be, Mg, Ca, Sr, Ba, Mn, Sn, Pb, and/or Zn;
  
  A is at least one of Bi, Sb, In, Sc, Y, and/or any of the rare earth elements;
  
  G is Si and/or Ge;
  
  Q is at least one of O, S, and/or Se;
  
  Z is at least one of F, Cl, Br, and/or I; and
  
  wherein 0≦
  
  l≦
  
  1, 2.5≦
  
  m≦
  
  5, 1.5≦
  
  a≦
  
  2.5, 2≦
  
  g≦
  
  2.5, 0≦
  
  p≦
  
  1, 0≦
  
  n≦
  
  1, 0≦
  
  z≦
  
  1, and l+2m+3a+4g+5p=2q+3n+z; and
  
  at least one additional phosphor composition.
- View Dependent Claims (18)
- - 18. The phosphor blend according to claim 17, wherein said phosphor blend comprises one or more of 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_1−
      
      ξO_4−
      
      2ξ;
      
      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)_5−
      
      αO_12−
      
      3/2α;
      
      Ce³⁺ (wherein 0≦
      
      α
      
      ≦
      
      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⁺,Ce³⁺;
      
      SrY₂S₄;
      
      Eu²⁺;
      
      CaLa₂S₄;
      
      Ce³⁺;
      
      (Ba,Sr,Ca)MgP₂O₇;
      
      Eu²⁺,Mn²⁺;
      
      (Y,Lu)₂WO₆;
      
      Eu³⁺,Mo⁶⁺;
      
      (Ba,Sr,Ca)_βSi_γN_μ;
      
      Eu²⁺ (wherein 2β
      
      +4γ
      
      =3μ
      
      );
      
      Ca₃(SiO₄)Cl₂;
      
      Eu²⁺;
      
      (Y,Lu,Gd)_2−
      
      φCa_φSi₄N_6+φC_1−
      
      φ;
      
      Ce³⁺, (wherein 0≦
      
      φ
      
      ≦
      
      0.5);
      
      (Lu,Ca,Li,Mg,Y)alpha-Si doped with Eu²⁺ and/or Ce³⁺;
      
      3.5MgO*0.5MgF₂*GeO₂;
      
      Mn⁴⁺;
      
      Ca_{1−
      
      c−
      
      f}Ce_cEu_fAl_1+cSi_1−
      
      cN₃, (where 0<
      
      c≦
      
      0.2, 0≦
      
      f≦
      
      0.2);
      
      Ca_{1−
      
      h−
      
      r}Ce_hEu_rAl_1−
      
      h(Mg,Zn)_hSiN₃, (where 0<
      
      h≦
      
      0.2, 0≦
      
      r≦
      
      0.2);
      
      Ca_{1−
      
      2s−
      
      t}Ce_s(Li,Na)_sEu_tAlSiN₃, (where 0≦
      
      s≦
      
      0.2, 0≦
      
      f≦
      
      0.2, s+t>
      
      0); and
      
      Ca_{1−
      
      σ
      
      −
      
      χ
      
      −
      
      i}Ce_σ(Li,Na)_χEu_φAl_{1+σ
      
      −
      
      χ}Si_{1−
      
      σ
      
      +χ}N₃, (where 0≦
      
      σ
      
      ≦
      
      0.2, 0≦
      
      χ
      
      ≦
      
      0.4, 0≦
      
      φ
      
      ≦
      
      0.2).

19. A phosphor material comprising L_lM_mA_aG_gP_pQ_qN_nZ_z:
- Ce³⁺, where L is at least one of Li, Na, K, Rb, and/or Cs;
  
  M is at least one of Be, Mg, Ca, Sr, Ba, Mn, Sn, Pb, and/or Zn;
  
  A is at least one of Bi, Sb, In, Y, and/or any of the rare earth elements;
  
  G is Si and/or Ge;
  
  Q is at least one of O, S, and/or Se;
  
  Z is at least one of F, Cl, Br, and/or I; and
  
  wherein 0≦
  
  l≦
  
  1, 2.5≦
  
  m≦
  
  5, 1.5≦
  
  a≦
  
  2.5, 2≦
  
  g≦
  
  2.5, 0≦
  
  p≦
  
  1, 0≦
  
  n≦
  
  1, 0≦
  
  z≦
  
  1, and l+2m+3a+4g+5p=2q+3n+z and the amount of Ce³⁺ doping is from 0.0001 to 10 mole percent.
- View Dependent Claims (20)
- - 20. The phosphor material of claim 19, wherein said phosphor material comprises (Lu,Sc,Y,Tb)₂₋
    - d−
      
      eCe_eCa_1+dMg₂Si₃O_12−
      
      e/2where −
      
      0.5≦
      
      d≦
      
      1 and 0<
      
      e≦
      
      0.1.

21. A phosphor material comprising L_lM_mA_aG_gP_pQ_qN_nZ_zCe³⁺, where L is at least one of Li, Na, K, Rb, and/or Cs;
- M is at least one of Be, Mg, Ca, Sr, Ba, Mn, Sn, Pb, and/or Zn;
  
  A is at least one of Bi, Sb, In, Sc, Y, and/or any of the rare earth elements;
  
  G is Si;
  
  Q is at least one of O, S, and/or Se;
  
  Z is at least one of F, Cl, Br, and/or I; and
  
  wherein 0≦
  
  l≦
  
  1, 2.5≦
  
  m≦
  
  5, 1.5≦
  
  a≦
  
  2.5, 2≦
  
  g≦
  
  2.5, 0≦
  
  p≦
  
  1, 0≦
  
  n≦
  
  1, 0≦
  
  z≦
  
  1, and l+2m+3a+4g+5p=2q+3n+z and the amount of Ce³⁺ doping is from 0.0001 to 10 mole percent.

22. A phosphor material comprising L_lM_mA_aG_gP_pQ_qN_nZ_zCe³⁺, where L is at least one of Li, Na, K, Rb, and/or Cs;
- M is at least one of Be, Mg, Ca, Sr, Ba, Mn, Sn, Pb, and/or Zn;
  
  A is at least one of Bi, Sb, In, Y, and/or any of the rare earth elements;
  
  G is Si;
  
  Q is at least one of O, S, and/or Se;
  
  Z is at least one of F, Cl, Br, and/or I; and
  
  wherein 0≦
  
  l≦
  
  1, 2.5≦
  
  m≦
  
  5, 1.5≦
  
  a≦
  
  2.5, 2≦
  
  g≦
  
  2.5, 0≦
  
  p≦
  
  1, 0≦
  
  n≦
  
  1, 0≦
  
  z≦
  
  1, and l+2m+3a+4g+5p=2q+3n+z and the amount of Ce³⁺ doping is from 0.0001 to 10 mole percent.

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Litigation Campaign Assessment

Current Assignee
Current Lighting Solutions, LLC (f/k/a GE Lighting Solutions, LLC) (American Industrial Partners)
Original Assignee
Lumination LLC
Inventors
Srivastava, Alok Mani, Gao, Yan, Comanzo, Holly Ann, Setlur, Anant Achyut, Radkov, Emil Vergilov
Primary Examiner(s)
Koslow; C. Melissa

Application Number

US11/285,685
Publication Number

US 20060284196A1
Time in Patent Office

1,070 Days
Field of Search

313/503, 313/485, 313/487, 257/98, 252/301.4 R, 252/301.6 R, 252/301.4 F, 252/301.6 F, 252/301.4 P, 252/301.6 P, 252/301.4 H, 252/301.4 S, 252/301.6 S
US Class Current

252/301.40F
CPC Class Codes

C09K 11/77742   Silicates

H01L 2224/48091   Arched

H01L 2224/48247   connecting the wire to a bo...

H01L 2924/00012   Relevant to the scope of th...

H01L 2924/181   Encapsulation

H01L 33/502   Wavelength conversion mater...

H01L 33/507   the elements being in intim...

H10K 50/125   specially adapted for multi...

Red garnet phosphors for use in LEDs

First Claim

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Red garnet phosphors for use in LEDs

First Claim

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