Silicate-based yellow-green phosphors

• US 7,311,858 B2
• Filed: 09/22/2004
• Issued: 12/25/2007
• Est. Priority Date: 08/04/2004
• Status: Active Grant

• Current Assignee: Intematix Corporation
• Original Assignee: Intematix Corporation
• Inventors: Dong, Yi, Cheng, Shifan, Li, Yi-Qun, Wang, Ning
• Primary Examiner(s): KOSLOW, CAROL M
• Application Number:
  US10/948,764
• Publication Number:
  US 20060028122A1
• Time in Patent Office: 1,189 Days
• Field of Search: 252/301.4 F, 252/301.6 F, 252/301.4 S, 252/301.4 H, 252/301.4 R, 313/503, 257/98
• US Class Current: 252/301.40F
• CPC Class Codes: C09K 11/0883 Arsenides; Nitrides; Phosphides
• CPC Class Codes: C09K 11/7734 Aluminates
• CPC Class Codes: C09K 11/77342 Silicates
• CPC Class Codes: H01L 33/502 Wavelength conversion materials
• CPC Class Codes: Y02B 20/00 Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps

Abstract

Novel phosphor systems are disclosed having the formula A₂SiO₄:Eu²⁺D, where A is at least one of a divalent metal selected from the group consisting of Sr, Ca, Ba, Mg, Zn, and Cd; and D is a dopant selected from the group consisting of F, Cl, Br, I, P, S and N. In one embodiment, the novel phosphor has the formula (Sr_1-x-yBa_xM_y)₂ SiO₄:Eu²⁺F (where M is one of Ca, Mg, Zn, or Cd in an amount ranging from 0<y<0.5). The phosphor is configured to absorb visible light from a blue LED, and luminescent light from the phosphor plus light from the blue LED may be combined to form white light. The novel phosphors can emit light at intensities greater than either conventionally known YAG compounds, or silicate-based phosphors that do not contain the inventive dopant ion.

Claims

1. A silicate-based yellow-green phosphor having the formula A₂SiO₄:

Eu²⁺D, wherein;

A is at least one of a divalent metal selected from the group consisting of Sr, Ca, Ba, Mg, Zn, and Cd; and

D is a dopant selected from the group consisting of F, Cl, Br, I, P, S and N, wherein D is present in the phosphor in an amount ranging from about 0.01 to 20 mole percent, and wherein at least some of the D dopant substitutes for oxygen anions to become incorporated into the crystal lattice of the silicate-based yellow-green phosphor.

2. The silicate-based phosphor of claim 1, wherein the phosphor is configured to absorb radiation in a wavelength ranging from about 280 nm to 490 nm.

3. The silicate-based phosphor of claim 1, wherein the phosphor emits visible light having a wavelength ranging from about 460 nm to 590 mm.

4. The silicate-based phosphor of claim 1, wherein the phosphor has the formula (Sr_1-x-yBa_xM_y)₂ SiO₄:

Eu²⁺D, where M is at least one of an element selected from the group consisting of Ca, Mg, Zn, and Cd, and where

0≦

x≦

1;

0≦

y≦

1 when M is Ca;

0≦

y≦

1 when M is Mg; and

0≦

y≦

1 when M is selected from the group consisting of Zn and Cd.

5. The silicate-based phosphor of claim 1, wherein D is F.

6. The silicate-based phosphor of claim 1, wherein the phosphor has the formula (Sr_1-x-yBa_xM_y)₂ SiO₄:

Eu²⁺F, where M is at least one of an element selected from the group consisting Ca, Mg, Zn, Cd, and where

0≦

x≦

0.3;

0≦

y≦

0.5 when M is Ca;

0≦

y≦

0.1 when M is Mg; and

0≦

y≦

0.5 when M is selected from the group consisting of Zn and Cd.

7. The silicate-based phosphor of claim 6, wherein the phosphor emits light in the yellow region of the electromagnetic spectrum, and has a peak emission wavelength ranging from about 540 to 590 nm.

8. The silicate-based phosphor of claim 1, wherein the phosphor has the formula (Sr_1-x-yBa_xM_y)₂ SiO₄:

Eu²⁺F, where M is at least one of an element selected from the group consisting of Ca, Mg, Zn, and Cd, and where

0.3≦

x≦

1;

0≦

y≦

0.5 when M is Ca;

0≦

y≦

0.1 when M is Mg; and

0≦

y≦

0.5 when M is selected from the group consisting of Zn and Cd.

9. The silicate-based phosphor of claim 8, wherein the phosphor emits light in the green region of the electromagnetic spectrum, and has a peak emission wavelenth ranging from about 500 to 530 nm.

10. A white LED comprising:

a radiation source configured to emit radiation having a wavelength ranging from about 410 to 500 nm;

a yellow phosphor according to claim 7, the yellow phosphor configured to absorb at least a portion of the radiation from the radiation source and emit light with a peak intensity in a wavelength ranging from about 530 to 590 nm.

11. A white LED comprising:

a radiation source configured to emit radiation having a wavelength ranging from about 410 to 500 nm;

a yellow phosphor according to claim 7, the yellow phosphor configured to absorb at least a portion of the radiation from the radiation source and emit light with peak intensity in a wavelength ranging from about 530 to 590 nm; and

a green phosphor according to claim 9, the green phosphor configured to absorb at least a portion of the radiation from the radiation source and emit light with peak intensity in a wavelength ranging from about 500 to 540 nm.

12. A white LED comprising:

a radiation source configured to emit radiation having a wavelength ranging from about 410 to 500 nm;

a green phosphor according to claim 9, the green phosphor configured to absorb at least a portion of the radiation from the radiation source and emit light with peak intensity in a wavelength ranging from about 500 to 540 nm;

a red phosphor selected from the group consisting of CaS;

Eu²⁺, SrS;

Eu²⁺, MgO*MgF*GeO;

Mn⁴⁺, and M_xSi_yN_z;

Eu⁺² where M is selected from the group consisting of Ca, Sr, Ba, and Zn;

Z=2/3x+4/3y, wherein the red phosphor is configured to absorb at least a portion of the radiation from the radiation source and emit light with peak intensity in a wavelength ranging from about 590 to 690 nm.

13. A white LED comprising:

a radiation source configured to emit radiation having a wavelength ranging from about 410 to 500 nm;

a yellow phosphor according to claim 7, the yellow phosphor configured to absorb at least a portion of the radiation from the radiation source and emit light with a peak intensity in a wavelength ranging from about 540 to 590 nm;

a red phosphor selected from the group consisting of CaS;

Eu²⁺, SrS;

Eu²⁺, MgO*MgF*GeO;

Mn⁴⁺, and M_xSi_yN_z;

Eu⁺², where M is selected from the group consisting of Ca, Sr, Ba, and Zn; and

Z=2/3x+4/3y, wherein the red phosphor is configured to absorb at least a portion of the radiation from the radiation source and emit light with peak intensity in a wavelength ranging from about 590 to 690 nm.

14. A composition comprising:

a silicate-based yellow phosphor having the formula A₂SiO₄;

Eu²⁺D, wherein A is at least one divalent metal selected from the group consisting of Sr, Ca, Ba, Mg, Zn, and Cd; and

D is a negatively changed halogen ion that is present in the yellow phosphor in an amount ranging from about 0.01 to 20 mole percent;

wherein at least some of the negativety charged halogen ions D sudstitute for oxygen anions to become incorporate into the crystal lattice of the silicate-base yellow phosphor, and

a blue phosphor;

wherein the yellow phosphor is configured to emit visible light with a peak intensity in a wavelength ranging from about 540 nm to 590 nm; and

the blue phosphor is configured to emit visible light with a peak intensity in a wavelength ranging from about 480 to 510 nm.

15. The composition of claim 14, wherein the blue phosphor is selected from the group consisting of silicate-based phosphors and aluminate-based phosphors.

16. The composition of claim 15, wherein the silicate-based blue phosphor has the formula Sr_1-x-yMg_xBa_ySiO₄:

Eu²⁺F; and

where

0.5≦

x≦

1.0; and

0≦

y≦

0.5.

17. The composition of claim 15, wherein the aluminate-based blue phosphor has the formula Sr_1-xMgEu_xAl₁₀O₁₇;

and where 0.01<

x≦

1.0.

18. A composition comprising:

a silicate-based green phosphor having the formula A₂SiO₄;

Eu²⁺D, wherein A is at least one of a divalent metal selected from the group consisting of Sr, Ca, Ba, Mg, Zn, and Cd; and

D is a negatively charged halogen ion that is present in the yellow phosphor in an amount ranging from about 0.01 to 20 mole percent, wherein at least some of the negativety charged halogen ion D substituted for oxygen anions and thus are incorporated into the crystal lattice of the silicate-based green phosphor;

a blue phosphor; and

a red phosphor;

wherein the green phosphor is configured to emit visible light with a peak intensity in a wavelength ranging from about 500 nm to 540 nm;

the blue phosphor is configured to emit visible light with a peak intensity in a wavelength ranging from about 480 to 510 nm; and

the red phosphor is configured to emit visible light with a peak intensity in a wavelength ranging from about 575 to 620 nm.

19. A method of preparing a silicate-based yellow phosphor having the formula A₂SiO₄:

Eu²⁺D, wherein A is at least one of a divalent metal selected from the group consisting of Sr, Ca, Ba, Mg, Zn, and Cd; and

D is a dopant selected from the group consisting of F, Cl, Br,and I, wherein D is present in the phosphor in an amount ranging from about 0.01 to 20 mole percent, the method comprising using a wet mixing step to incorporate at least some of the D dopant into the crystal lattice of the silicate-based yellow phosphor.

20. The method of claim 19, wherein the method comprises:

a) dissolving a desired amount of an alkaline earth nitrate selected from the group consisting of Mg, Ca, Sr, and Ba-containing nitrates with Eu₂O₃ and BaF₂ or other alkaline metal halides, in an acid ,to prepered first solution;

b) dissolving a corresponding amount of a silica gel in de-ionized water to prepare a second solution;

c) stirring together the solutions produced in steps a) and b), and then adding ammonia to generate a gel from the mixture solution;

d) adjusting the pH of the solution produced in step c) to a value of about 9, and then stirring the solution continuously at about 60°

C. for about 3 hours;

e) drying the gelled solution of step d) by evaporation, and then decomposing the resulting dried gel at 500 to 700°

C. for about 60 minutes to decompose and acquire product oxides;

f) cooling and grinding the gelled solution of step e) with NH₄F or other ammonia halides when alkaline earth metal halides are not used in step a) to produce a powder;

g) calcining/sintering the powder of step f) in a reduced atmosphere for about 6 to 10 hours, the sintering temperature ranging from about 1200 to 1400°

C.

21. The method of claim 19, wherein the mixing method comprises:

a) wet mixing desired amounts of alkaline earth oxides or carbonates (Mg, Ca, Sr, Ba), dopants of Eu₂O₃ and BaF₂ or other alkaline earth metal halides, corresponding SiO₂ and NH₄F or other ammonia halides with a ball mill; and

b) after drying and grinding, calcining and/or sintering the resulting powder in a reduced atmosphere for about 6 to 10 hours, at a calcining/sintering temperature ranging from about 1200 to 1400°

C.