SILICATE PHOSPHOR, METHOD OF MANUFACTURING SILICATE PHOSPHOR, AND LIGHT-GENERATING DEVICE HAVING SILICATE PHOSPHOR

• US 20120223636A1
• Filed: 05/03/2012
• Published: 09/06/2012
• Est. Priority Date: 06/03/2011
• Status: Active Grant

• Current Assignee: PU-Kyong National University Industry-University Foundation, Samsung Display Company Limited (Samsung Group)
• Original Assignee: Samsung Display Company Limited (Samsung Group)
• Inventors: Shin, Myeong-Ju, Baek, Seung-Hwan, Kim, Young-Sic, Nam, Seok-Hyun, Yang, Byung-Choon, Lee, Yeong-Bae, Kim, Jong-Su, Park, Kwang-Won, Park, Yun-Hyoung, Yu, Ji-Su
• Granted Patent: US 9,096,797 B2
• Time in Patent Office: Days
• US Class Current: 313/512
• CPC Class Codes: C09K 11/77212 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

A silicate phosphor composition is provided having a γ-phase of an orthorhombic crystal structure whose space group is Pbnm 62, and whose composition is represented by the following chemical formula:

Ca_2-x-y-zMxSiO₄:yCe³⁺,zN(0≦x<0.5,0<y≦0.1,0≦z<0.15)

In the formula, M represents at least one member selected from the group consisting of Mg, Sr, Ba, Zn, Na, Al, Ga, Ge, P, As and Fe, and N represents at least one member selected from the group consisting of Eu²⁺, Mn²⁺, Tb³⁺, Yb²⁺ and Tm³⁺. The silicate phosphor has a maximum absorbance for a wavelength of about 450 nm to about 475 nm corresponding to a main part of a blue excitation light, and has a great stability at a high temperature. As such the silicate phosphor may be used in combination with a blue light source to produce a white light.

Claims

1. A silicate phosphor having a γ

-phase of an orthorhombic crystal structure of a Pbnm 62 space group, and being represented by the following Chemical Formula 1,

Ca_2-x-y-zMxSiO₄;

yCe³⁺,zN(0≦

x<

0.5,0<

y≦

0.1,0≦

z<

0.15) 

 

<

Chemical Formula 1>

wherein M represents at least one member selected from the group consisting of Mg, Sr, Ba, Zn, Na, Al, Ga, Ge, P, As and Fe, and N represents at least one member selected from the group consisting of Eu²⁺, Mn²⁺, Tb³⁺, Yb²⁺ and Tm³⁺.

2. The silicate phosphor of claim 1, wherein a content of Ca is about 1.25 mole to about 2 mole with respect to 1 mole of SiO₄.

3. The silicate phosphor of claim 1, wherein a powder diffraction pattern of the silicate phosphor coincides with JCPDS standard #76-0799, #77-0387, #86-0397, #87-1256, #87-1257 or #83-2457.

4. The silicate phosphor of claim 1, wherein a mole content of Ce³⁺ is about 0.01 mole to about 0.03 mole with respect to 1 mole of SiO₄.

5. A method of manufacturing a silicate phosphor, the method comprising:

preparing a raw-materials mixture including a Ca-containing compound, a Si-containing compound and a Ce-containing compound;

sintering the raw-material mixture; and

cooling the sintered raw-material mixture to obtain a solidified silicate phosphor having a γ

-phase of an orthorhombic crystal structure whose space group is Pbnm 62, and whose composition is represented by the following Chemical Formula 1,

Ca_2-x-y-zMxSiO₄;

yCe³⁺,zN(0≦

x<

0.5,0<

y≦

0.1,0≦

z<

0.15) 

 

<

Chemical Formula 1>

wherein M represents at least one member selected from the group consisting of Mg, Sr, Ba, Zn, Na, Al, Ga, Ge, P, As and Fe, and N represents at least one member selected from the group consisting of Eu²⁺, Mn²⁺, Tb³⁺, Yb²⁺ and Tm³⁺.

6. The method of claim 5, wherein the Ca-containing compound includes at least one selected member from the group consisting of CaO, CaCO₃, Ca(NO₃)₂, CaF₂ and CaCl₂, and the Si-containing compound includes at least one member selected from the group consisting of SiO₂, SiO and Si, and the Ce-containing compound includes at least one member selected from the group consisting of Ce₂O₃, CeO₂, Ce₂(SO₄)₃ and Ce(SO₄)₂.

7. The method of claim 5, wherein the raw-material mixture further includes at least one compound containing Mg, Sr, Ba, Zn, Na, Al, Ga, Ge, P, As or Fe, and further includes at least one compound containing Eu, Mn, Tb, Yb or Tm.

8. The method of claim 5, wherein the raw-material mixture further includes a flux including at least one member selected from the group consisting of MgF₂, MgCl₂, BaF₂, BaCl₂, SrF₂, SrCl₂, CaF₂, CaCl₂, NH₄F, NH₄Cl and LiF.

9. The method of claim 5, wherein the raw-material mixture is sintered at about 1,350°

C. to about 1,550°

C.

10. The method of claim 9, wherein the raw-material mixture is sintered in a reducing atmosphere including a hydrogen gas.

11. The method of claim 9, wherein the raw-material mixture is sintered under a pressure of about 0.05 atm to about 2.5 atm.

12. The method of claim 9, wherein the sintered raw-material mixture is cooled by a temperature ramp down speed of no less than about 15°

C./min.

13. The method of claim 12, wherein the sintered raw-material mixture is cooled during the temperature ramp down to have a temperature less than about 25°

C.

14. The method of claim 12, wherein the sintered raw-material mixture is cooled by a temperature ramp down speed of no less than about 45°

C./min.

15. The method of claim 5, further comprising crushing the solidified silicate phosphor.

16. A light-emitting device comprising:

a light source structured for generating at least an excitational light having a predetermined excitational wavelength; and

a silicate phosphor disposed to be excited by the excitational light to responsively emit a light having a wavelength longer than the predetermined excitational wavelength, the silicate phosphor having a γ

-phase of an orthorhombic crystal structure whose space group is Pbnm 62, and whose composition is represented by the following Chemical Formula 1,

Ca_2-x-y-zMxSiO₄;

yCe³⁺,zN(0≦

x<

0.5,0<

y≦

0.1,0≦

z<

0.15) 

 

<

Chemical Formula 1>

wherein M represents at least one member selected from the group consisting of Mg, Sr, Ba, Zn, Na, Al, Ga, Ge, P, As and Fe, and N represents at least member one selected from the group consisting of Eu²⁺, Mn²⁺, Tb³⁺, Yb²⁺ and Tm³⁺.

17. The light-emitting device of claim 16, wherein the light source includes an LED generating a blue light.

18. The light-emitting device of claim 17, wherein the silicate phosphor emits at least one light selected from the group consisting of a yellow light, a green light and a yellowish red light.

19. The light-emitting device of claim 16, wherein the light generated by the light source is combined with the light emitted by the silicate phosphor thereby forming a white light.

20. The light-emitting device of claim 16, further comprising a sealing member attached to or incorporating the silicate phosphor and covering the light source.