IP Library › Granted Patent US 7,094,362
Granted Patent B2
US 7,094,362 · App. 10/696,637 · Granted Aug 22, 2006

Garnet phosphor materials having enhanced spectral characteristics

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Quick Facts
Patent No.
US 7,094,362
App. No.
10/696,637
Granted
Aug 22, 2006
Kind
B2
Abstract

Phosphor compositions having the formulas (Tb 1−x−y−z−w Y x Gd y Lu z Ce w ) 3 M r Al s−r 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; (RE 1−x−y Sc x Ce y ) 2 A 3−p B p Si z−q Ge q O 12+δ , where RE is selected from a lanthanide ion or Y 3+ , 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 x Ba y Ce z ) 3 (Sc 1−a−c Lu a D c ) 2 Si n−w Ge w O 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 (54)

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 1−x−y Sc x Ce y ) 2 A 3−p B p Si z−q Ge q O 12+δ , where RE is selected from a lanthanide ion or Y 3+ , 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 i Ga j Al k N, 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 0.955 Ce 0.045 ) 2 CaMg 2 Si 3 O 12 .

10. The lighting apparatus of claim 1 , wherein said phosphor composition comprises two or more distinct phosphors having the formula (RE 1−x−y Sc x Ce y ) 2 A 3−p B p Si z−q Ge q O 12+δ , where RE is selected from a lanthanide ion or Y 3+ , 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 (PO 4 ) 3 (Cl,F,Br,OH):Eu 2+ , Mn 2+ , Sb 3+ ; (Ba,Sr,Ca)MgAl 10 O 17 :Eu 2+ ,Mn 2+ ; (Ba,Sr,Ca)BPO 5 :Eu 2+ ,Mn 2+ ; (Sr,Ca) 10 (PO 4 ) 6 *nB 2 O 3 :Eu 2+ ; 2SrO*0.84P 2 O 5 *0.16B 2 O 3 :Eu 2+ ; Sr 2 Si 3 O 8 *2SrCl 2 :Eu 2+ ; Ba 3 MgSi 2 O 8 :Eu 2+ ; Sr 4 Al 14 O 25 :Eu 2+ ; BaAl 8 O 13 :Eu 2+ ; (Ba,Sr,Ca)Al 2 O 4 :Eu 2+ ; (Y,Gd,Lu,Sc,La)BO 3 :Ce 3+ ,Tb 3+ ; Ca 8 Mg(SiO 4 ) 4 Cl 2 :Eu 2+ ,Mn 2+ ; (Ba,Sr,Ca) 2 SiO 4 :Eu 2+ ; (Ba,Sr,Ca) 2 (Mg,Zn)Si 2 O 7 :Eu 2+ ; (Sr,Ca,Ba)(Al,Ga,In) 2 S 4 :Eu 2+ ; (Y,Gd,Tb,La,Sm,Pr,Lu) 3 (Al,Ga) 5 O 12 :Ce 3+ ; (Ca,Sr) 8 (Mg,Zn)(SiO 4 ) 4 Cl 2 :Eu 2+ ,Mn 2+; Na 2 Gd 2 B 2 O 7 :Ce 3+ ,Tb 3+ ; (Ba, Sr) 2 (Ca,Mg,Zn)B 2 O 6 :K,Ce,Tb; (Sr,Ca,Ba,Mg,Zn) 2 P 2 O 7 :Eu 2+ ,Mn 2+ ; (Ca,Sr,Ba,Mg) 10 (PO 4 ) 6 (F,Cl,Br,OH):Eu 2+ ,Mn 2+ ; (Gd,Y,Lu,La) 2 O 3 :Eu 3+ , Bi 3+ ; (Gd,Y,Lu,La) 2 O 2 S:Eu 3+ ,Bi 3+ ; (Gd,Y,Lu,La)VO 4 :Eu 3+ ,Bi 3+ ; (Ca,Sr)S:Eu 2+ ; SrY 2 S 4 :Eu 2+ ; CaLa 2 S 4 :Ce 3+ ; 3.5MgO*0.5MgF 2 *GeO 2 :Mn 4+ ; (Ba,Sr,Ca)MgP 2 O 7 :Eu 2+ ,Mn 2+ ; (Y,Lu) 2 WO 6 :Eu 3 +,Mo 6+ ; (Ba,Sr,Ca) x Si y N z :Eu 2+ .

13. The lighting apparatus of claim 1 , further comprising a (Tb,Y) 3 Al 4.9 O 12−δ :Ce 3+ 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 (RE 1−x−y Sc x Ce y ) 2 A 3−p B p Si z−q Ge q O 12+δ , where RE is selected from a lanthanide ion or Y 3+ , 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 0.955 Ce 0.045 ) 2 CaMg 2 Si 3 O 12 .

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) 3 Al 4.9 O 12−δ :Ce 3+ wherein −1≦δ≦1 and (Tb 1−x−y−z−w Y x Gd y Lu z Ce w ) 3 M r Al s−r 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 1−x−y Sc x Ce y ) 2 A 3−p B p Si z−q Ge q O 12+δ , where RE is selected from a lanthanide ion or Y 3+ , 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 (Ca 1−x−y−z Sr x Ba y Ce z ) 3 (Sc 1−a−c Lu a D c ) 2 Si n−w Ge w O 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 (Ca 1−z Ce z ) 3 Sc 2 Si n−w Ge w O 12 .

34. The phosphor composition according to claim 33 , comprising (Ca 1−z Ce z ) 3 Sc 2 Si 3 O 12 .

35. The phosphor composition according to claim 33 , comprising (Ca 0.99 Ce 0.01 ) 3 Sc 2 Si 3 O 12 .

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 (Tb 1−x−y−z−w Y x Gd y Lu z Ce w ) 3 M r Al s−r 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 1−x−y Sc x Ce y ) 2 A 3−p B p Si z−q Ge q O 12+δ , where RE is selected from a lanthanide ion or Y 3+ , 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 (Ca 1−x−y−z Sr x Ba y Ce z ) 3 (Sc 1−a−c Lu a D c ) 2 Si n−w Ge w O 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 (PO 4 ) 3 (Cl,F,Br,OH):Eu 2+ ,Mn 2+ ,Sb 3+ ; (Ba,Sr,Ca)MgAl 10 O 17 :Eu 2+ ,Mn 2+ ; (Ba,Sr,Ca)BPO 5 :Eu 2+ ,Mn 2+ ; (Sr,Ca) 10 (PO 4 ) 6 *nB 2 O 3 :Eu 2+ ; 2SrO*0.84P 2 O 5 *0.16B 2 O 3 :E 2+ ; Sr 2 Si 3 O 8 *2SrCl 2 :Eu 2+ ; Ba 3 MgSi 2 O 8 :Eu 2+ ; Sr 4 Al 14 O 25 :Eu 2+ ; BaAl 8 O 13 :Eu 2+ ; (Ba,Sr,Ca)Al 2 O 4 :Eu 2+ ; (Y,Gd,Lu,Sc,La)BO 3 :Ce 3+ , Tb 3+ ; Ca 8 Mg(SiO 4 ) 4 Cl 2 :Eu 2+ , Mn 2+ ; (Ba,Sr,Ca) 2 SiO 4 :Eu 2+ ; (Ba,Sr,Ca) 2 (Mg,Zn)Si 2 O 7 :Eu 2+ ; (Sr,Ca,Ba)(Al,Ga,In) 2 S 4 :Eu 2+ ; (Y,Gd,Tb,La,Sm,Pr,Lu) 3 (Al,Ga) 5 O 12 :Ce 3+ ; (Ca,Sr) 8 (Mg,Zn)(SiO 4 ) 4 Cl 2 :Eu 2+ ,Mn 2+ ; Na 2 Gd 2 B 2 O 7 :Ce 3+ , Tb 3+ ; (Ba,Sr) 2 (Ca,Mg,Zn)B 2 O 6 :K,Ce,Tb; (Sr,Ca,Ba,Mg,Zn) 2 P 2 O 7 :Eu 2+ , Mn 2+ ; (Ca,Sr,Ba,Mg) 10 (PO 4 ) 6 (F,Cl,Br,OH):Eu 2+ ,Mn 2+ ; (Gd,Y,Lu,La) 2 O 3 :Eu 3+ ,Bi 3+ ; (Gd,Y,Lu,La) 2 O 2 S:Eu 3+ ,Bi 3+ ; (Gd,Y,Lu,La)VO 4 :Eu 3+ ,Bi 3+ ; (Ca,Sr)S:Eu 2+ ; SrY 2 S 4 :Eu 2+ ; CaLa 2 S 4 :Ce 3+ ; 3.5MgO*0.5MgF 2 *GeO 2 :Mn 4 +; (Ba,Sr,Ca)MgP 2 O 7 :Eu 2+ ,Mn 2+ ; (Y,Lu) 2 WO 6 :Eu 3 +,Mo 6+ ; (Ba,Sr,Ca) x Si y N z :Eu 2+ .

47. The lighting apparatus of claim 43 , further comprising at least one phosphor selected from the group consisting of (Tb 1−x−y−z−w Y x Gd y Lu z Ce w ) 3 M r Al s−r 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 1−x−y Sc x Ce y ) 2 A 3−p B p Si z−q Ge q O 12+δ , where RE is selected from a lanthanide ion or Y 3+ , 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) 3 Al 4.9 O 12−δ :Ce 3+ 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 Ca 3 Sc 2 (Si x Ge 1−x ) 3 O 12 :Ce 3+ , wherein x is from 0.67 to 1.0.

51. The lighting apparatus of claim 43 , wherein said phosphor comprises Ca 3 Sc 2 Si 3 O 12 :Ce 3+ .

52. The lighting apparatus of claim 43 , wherein said phosphor comprises (Ca 0.99 Ce 0.01 ) 3 Sc 2 Si 3 O 12 .

Assignments (10)
CORRECTIVE ASSIGNMENT TO CORRECT THE PATENT NUMBER PREVIOUSLY RECORDED AT REEL: 059034 FRAME: 0469. ASSIGNOR(S) HEREBY CONFIRMS THE SECURITY INTEREST. Recorded Jan 25, 2024
From: HUBBELL LIGHTING, INC.; LITECONTROL CORPORATION; CURRENT LIGHTING SOLUTIONS, LLC; DAINTREE NETWORKS INC.; FORUM, INC.
To: ATLANTIC PARK STRATEGIC CAPITAL FUND, L.P., AS COLLATERAL AGENT
Reel/Frame 066372/0590 →
CORRECTIVE ASSIGNMENT TO CORRECT THE PATENT NUMBER 10841994 TO PATENT NUMBER 11570872 PREVIOUSLY RECORDED ON REEL 058982 FRAME 0844. ASSIGNOR(S) HEREBY CONFIRMS THE SECURITY AGREEMENT. Recorded Jan 19, 2024
From: HUBBELL LIGHTING, INC.; LITECONTROL CORPORATION; CURRENT LIGHTING SOLUTIONS, LLC; DAINTREE NETWORKS INC.; FORUM, INC.
To: ALLY BANK, AS COLLATERAL AGENT
Reel/Frame 066355/0455 →
RELEASE OF SECURITY INTEREST Recorded Mar 17, 2022
From: ALLY BANK
To: CURRENT LIGHTING SOLUTIONS, LLC; FORUM, INC.
Reel/Frame 059432/0592 →
RELEASE OF SECURITY INTEREST Recorded Mar 17, 2022
From: ALLY BANK
To: CURRENT LIGHTING SOLUTIONS, LLC; FORUM, INC.
Reel/Frame 059392/0079 →
SECURITY INTEREST Recorded Feb 11, 2022
From: HUBBELL LIGHTING, INC.; LITECONTROL CORPORATION; CURRENT LIGHTING SOLUTIONS, LLC; DAINTREE NETWORKS INC.; FORUM, INC.
To: ATLANTIC PARK STRATEGIC CAPITAL FUND, L.P., AS COLLATERAL AGENT
Reel/Frame 059034/0469 →
SECURITY AGREEMENT Recorded Feb 2, 2022
From: HUBBELL LIGHTING, INC.; LITECONTROL CORPORATION; CURRENT LIGHTING SOLUTIONS, LLC; DAINTREE NEETWORKS INC.; FORUM, INC.
To: ALLY BANK, AS COLLATERAL AGENT
Reel/Frame 058982/0844 →
SECURITY AGREEMENT Recorded May 27, 2020
From: CURRENT LIGHTING SOLUTIONS, LLC
To: ALLY BANK, AS COLLATERAL AGENT
Reel/Frame 052763/0643 →
SECURITY AGREEMENT Recorded Jun 28, 2019
From: CURRENT LIGHTING SOLUTIONS, LLC
To: ALLY BANK, AS COLLATERAL AGENT
Reel/Frame 049672/0294 →
SECURITY AGREEMENT Recorded Jun 28, 2019
From: CURRENT LIGHTING SOLUTIONS, LLC
To: ALLY BANK, AS COLLATERAL AGENT
Reel/Frame 051047/0210 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Apr 3, 2019
From: GENERAL ELECTRIC COMPANY
To: CURRENT LIGHTING SOLUTIONS, LLC F/K/A GE LIGHTING SOLUTIONS, LLC
Reel/Frame 048791/0001 →