Borate phosphor materials for use in lighting applications

• US 7,274,045 B2
• Filed: 03/17/2005
• Issued: 09/25/2007
• Est. Priority Date: 03/17/2005
• Status: Expired due to Fees

• Current Assignee: Gelcore (General Electric Company)
• Original Assignee: Lumination LLC
• Inventors: Seshadri, Hari Nadathur, Chandran, Ramachandran Gopi, Shankar, Madras Venugopal, Sivaramakrishan, Venkatraman
• Primary Examiner(s): NGUYEN, CUONG QUANG
• Application Number:
  US11/082,425
• Publication Number:
  US 20060208270A1
• Time in Patent Office: 922 Days
• Field of Search: 257 79-103
• US Class Current: 257/100
• CPC Class Codes: C09K 11/0883 Arsenides; Nitrides; Phosphides
• CPC Class Codes: C09K 11/774 Borates
• 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: H05B 33/14 characterised by the chemical or physical composition or the arrangement of the electroluminescent material , or by the simultaneous addition of the electroluminescent material in or onto the light source

Abstract

Boron containing phosphor compositions having the formulas (1) M₃Ln₂(BO₃)₄ doped with at least one activator selected from the group of Eu²⁺, Mn²⁺, Pb²⁺, Ce³⁺, Eu³⁺, Tb³⁺, and Bi³⁺ where M is at least one of Mg, Ca, Sr, Ba, or Zn, and Ln is at least one of Sc, Y, La, Gd, or Lu; (2) M_2−xM′_x(Al, Ga)_2−y(Si, Ge)_yB₂O_7−zN_z:Eu²⁺, Mn²⁺, Pb²⁺ where M′ is one or more of alkali metals Na and/or K, M″ is one or more of alkaline earth Mg, Ca, Sr, Ba or Zn, 0≦x≦2, 0≦y≦2, 0≦z≦4; and z=x+y; (3) M′_2−x+y′M″_x−y′(Al, Ga)_2−y(Si, Ge)_yB₂O_7−z−y′N_zX_y:Eu²⁺, Mn²⁺, Pb²⁺, where M′ is one or more of alkali metals Na and/or K, M″ is one or more of alkaline earth metals Mg, Ca, Sr, Ba and/or Zn, 0≦x≦2, 0≦y≦2, 0≦z≦4; z=x+y, X═F and/or Cl, and 0≦y′≦2; (4) M′_2−xM″_xAl_2−y+y′Si_y−y′B₂O_7−z−y′N_zX_y:Eu²⁺, Mn²⁺, Pb²⁺, where M′ and M″ are defined above, 0≦x≦2, 0≦y≦2, 0≦z≦4; z=x+y, X═F and/or Cl, and 0≦y′≦2; (5) M′_2−x+x′M″_x−x″Al_2−y+y′Si_y−y′B₂O_{7−z−x′−y′}N_zX_(x′+y′):Eu²⁺, Mn²⁺, Pb²⁺, where M′ and M″ are defined above, 0≦x≦2, 0≦y≦2, 0≦z≦4; z=x+y, X═F and/or Cl, and 0≦y′≦2; (6) MAl₂B₂O₇:Eu²⁺, Mn²⁺, Pb²⁺; where M═Mg, Ca, Sr, Ba or Zn; (7) MAl_2−xSi_xB₂O_7−xN_x:Eu²⁺, Mn²⁺, Pb²⁺, where M═Mg, Ca, Sr, Ba and/or Zn, and 0≦x≦2; and (8) MAl₂B_2−xSi_xO_7−xN_x:Eu²⁺, Mn²⁺, Pb²⁺, where M═Mg, Ca, Sr, Ba and/or Zn, and 0≦x≦2. Also disclosed are light emitting devices including a light source and at least one of the above phosphor compositions.

Claims

1. A lighting apparatus for emitting white light comprising:

a semiconductor light source; and

a phosphor composition radiationally coupled to the light source, the phosphor composition comprising a phosphor composition including at least one of;

(A) M₃Ln₂(BO₃)₄ doped with at least one activator selected from the group of Eu²⁺, Mn²⁺, Pb²⁺, Ce³⁺, Eu³⁺, Tb³⁺, and Bi³⁺ where M is at least one of Mg, Ca, Sr, Ba, or Zn, and Ln is at least one of Sc, Y, La, Gd, or Lu;

(B) M′

<sub>2−

x</sub>M′

_x(Al, Ga)<sub>2−

y</sub>(Si, Ge)_yB₂O<sub>7−

z</sub>N_z;

Eu²⁺, Mn²⁺, Pb²⁺ where M′

is one or more of alkali metals Na and/or K, M″

is one or more of alkaline earth Mg, Ca, Sr, Ba or Zn, 0≦

x≦

2, 0≦

y≦

2, 0≦

z≦

4; and

z=x+y;

(C) M′

<sub>2−

x+y′</sub>

M″

<sub>x−

y′</sub>

(Al, Ga)<sub>2−

y</sub>(Si, Ge)_yB₂O<sub>7−

z−

y′</sub>

N_zX_y;

Eu²⁺, Mn²⁺, Pb²⁺, where M′

is one or more of alkali metals Na and/or K, M″

is one or more of alkaline earth metals Mg, Ca, Sr, Ba and/or Zn, 0≦

x≦

2, 0≦

y≦

2, 0≦

z≦

4;

z=x+y, X═

F and/or Cl, and 0≦

y′

≦

2;

(D) M′

<sub>2−

x</sub>M″

_xAl<sub>2−

y+y′</sub>

Si<sub>y−

y′</sub>

B₂O<sub>7−

z−

y′</sub>

N_zX_y;

Eu²⁺, Mn²⁺, Pb²⁺, where M′ and

M″

are defined above, 0≦

x≦

2, 0≦

y≦

2, 0≦

z≦

4;

z=x+y, X═

F and/or Cl, and 0≦

y′

≦

2;

(E) M′

<sub>2−

x+x′</sub>

M″

<sub>x−

x″</sub>

Al<sub>2−

y+y′</sub>

Si<sub>y−

y′</sub>

B₂O<sub>7−

z−

x′

−

y′</sub>

N_zX<sub>(x′

+y′

)</sub>;

Eu²⁺, Mn²⁺, Pb²⁺, where M′ and

M″

are defined above, 0≦

x≦

2, 0≦

y≦

2, 0≦

z≦

4;

z=x+y, X═

F and/or Cl, and 0≦

y′

≦

2;

(F) MAl₂B₂O₇;

Eu²⁺, Mn²⁺, Pb²⁺ where M═

Mg, Ca, Sr, Ba and/or Zn;

(G) MAl<sub>2−

x</sub>Si_xB₂O<sub>7−

x</sub>N_x;

Eu²⁺, Mn²⁺, Pb²⁺, where M═

Mg, Ca, Sr, Ba and/or Zn, and 0≦

x≦

2;

or

(H), MAl₂B<sub>2−

x</sub>Si_xO<sub>7−

x</sub>N_x;

Eu²⁺, Mn²⁺, Pb²⁺, where M═

Mg, Ca, Sr, Ba and/or Zn, and 0≦

x≦

2.

2. The lighting apparatus of claim 1, wherein the light source is a semiconductor light emitting diode (LED) emitting radiation having a wavelength in the range of from about 370 to about 405 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 consisting of (Ba, Sr, Ca)₅(PO₄)₃(Cl, F, Br, OH):

Eu²⁺, Mn²⁺, Sb³⁺;

(Ba, Sr, Ca)MgAl₁₀O₁₇;

Eu²⁺, Mn²⁺;

(Ba, Sr, Ca)BPO₅;

Eu²⁺, Mn²⁺;

(Sr, Ca)₁₀(PO₄)₆*nB₂O₃;

Eu²⁺;

2SrO*0.84P₂O₅*0.16B₂O₃;

Eu²⁺;

Sr₂Si₃O_8*2SrCl₂;

Eu²⁺;

Ba₃MgSi₂O₈;

Eu²⁺;

Sr₄Al₁₄O₂₅;

Eu²⁺;

BaAl₈O₁₃;

Eu²⁺;

Sr₄Al₁₄O₂₅;

Eu²⁺;

BaAl₈O₁₃;

Eu²⁺;

2SrO-0.84P₂O<sub>5−

0.16</sub>B₂O₃;

Eu²⁺;

(Ba, Sr, Ca)MgAl₁₀O₁₇;

Eu²⁺, Mn²⁺;

(Ba, Sr, Ca)₅(PO₄)₃(Cl, F, OH);

Eu²⁺, Mn²⁺, Sb³⁺;

(Ba, Sr, Ca)MgAl₁₀O₁₇;

Eu²⁺, Mn²⁺;

(Ba, Sr, Ca)Al₂O₄;

Eu²⁺;

(Y, Gd, Lu, Sc, La)BO₃;

Ce³⁺, Tb³⁺;

Ca₈Mg(SiO₄)₄Cl₂;

Eu²⁺, Mn²⁺;

(Ba, Sr, Ca)₂SiO₄;

Eu²⁺;

(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)₅O₁₂;

Ce³⁺;

(Ca, Sr)₈(Mg, Zn)(SiO₄)₄Cl₂;

Eu²⁺, Mn²⁺ (CASI);

Na₂Gd₂B₂O₇;

Ce³⁺, Tb³⁺;

(Ba, Sr)₂(Ca, Mg, Zn)B₂O₆;

K, Ce, Tb;

(Sr, Ca, Ba, Mg, Zn)₂P₂O₇;

Eu²⁺, Mn²⁺ (SPP);

(Ca, Sr, Ba, Mg)₁₀(PO₄)₆(F, Cl, Br, OH);

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⁺;

SrY₂S₄;

Eu²⁺;

CaLa₂S₄;

Ce³⁺;

(Ca, Sr)S;

Eu²⁺;

3.5 MgO*0.5 MgF₂*GeO₂;

Mn⁴⁺;

(Ba, Sr, Ca)MgP₂O₇;

Eu²⁺, Mn²⁺;

(Y, Lu)₂WO₆;

Eu³⁺, Mo⁶⁺;

(Ba, Sr, Ca)_xSi_yN_z;

Eu²⁺.

11. The lighting apparatus of claim 1, wherein said phosphor is selected from the group consisting of (Sr_0.95Eu_0.05)₃Y₂(BO₃)₄;

Sr₃(Y_0.95Ce_0.05)₂(BO₃)₄;

Sr₃Y_1.9Eu_0.1(BO₃)₄;

(Sr_0.95Eu_0.05)₃Sc₂(BO₃)₄;

Sr₃(Y_0.45Sc_0.5Ce_0.05)₂(BO₃)₄;

Sr₃Sc_1.9Eu_0.1(BO₃)₄; and

(Ca_0.95Mn_0.05)₃Y₂(BO₃)₄.

12. The lighting apparatus of claim 1, wherein said phosphor is selected from the group consisting of Ca_0.9NaAlSiB₂O₅N₂:

Mn²⁺;

Sr_0.9NaAlSiB₂O₅N₂;

Eu²⁺;

Ca_0.9Si₂B₂O₅N₂;

Mn²⁺;

Sr_0.9Si₂B₂O₅N₂;

Eu²⁺; and

Na₂Si₂B₂O₅N₂;

Eu²⁺.

13. A phosphor having the formula M₃Ln₂(BO₃)₄ doped with at least one activator selected from the group of Eu²⁺, Mn²⁺, Pb²⁺, Ce³⁺, Eu³⁺, Tb³⁺, and Bi³⁺ where M is at least one of Mg, Ca, Sr, Ba, or Zn, and Ln is at least one of Sc, Y, La, Gd, or Lu.

14. The phosphor of claim 13, comprising at least one of (Sr_0.95Eu_0.05)₃Y₂(BO₃)₄;

Sr₃(Y_0.95Ce_0.05)₂(BO₃)₄;

Sr₃Y_1.9Eu_0.1(BO₃)₄;

(Sr_0.95Eu_0.05)₃Sc₂(BO₃)₄;

Sr₃(Y_0.45Sc_0.5Ce_0.05)₂(BO₃)₄;

Sr₃Sc_1.9Eu_0.1(BO₃)₄; and

(Ca_0.95Mn_0.05)₃Y₂(BO₃)₄.

15. A phosphor having the formula M′

<sub>2−

x</sub>M′

_x(Al, Ga)<sub>2−

y</sub>(Si, Ge)_yB₂O<sub>7−

z</sub>N_z;

Eu²⁺, Mn²⁺, Pb²⁺ where M′

is one or more of alkali metals Na and/or K, M″

is one or more of alkaline earth Mg, Ca, Sr, Ba or Zn, 0≦

x≦

2, 0≦

y≦

2, 0≦

z≦

4; and

z=x+y.

16. The phosphor of claim 15 comprising at least one of Ca_0.9NaAlSiB₂O₅N₂:

Mn²⁺;

Sr_0.9NaAlSiB₂O₅N₂;

Eu²⁺;

Ca_0.9Si₂B₂O₅N₂;

Mn²⁺;

Sr_0.9Si₂B₂O₅N₂;

Eu²⁺; and

Na₂Si₂B₂O₅N₂.

17. A phosphor blend comprising:

(A) a first phosphor selected from the group consisting of (1) M₃Ln₂(BO₃)₄ doped with at least one activator selected from the group of Eu²⁺, Mn²⁺, Pb²⁺, Ce³⁺, Eu³⁺, Tb³⁺, and Bi³⁺ where M is at least one of Mg, Ca, Sr, Ba, or Zn, and Ln is at least one of Sc, Y, La, Gd, or Lu;

(2) M<sub>2−

x</sub>M′

_x(Al, Ga)<sub>2−

y</sub>(Si, Ge)_yB₂O<sub>7−

z</sub>N_z;

Eu²⁺, Mn²⁺, Pb²⁺ where M′

is one or more of alkali metals Na and/or K, M″

is one or more of alkaline earth Mg, Ca, Sr, Ba or Zn, 0≦

x≦

2, 0≦

y≦

2, 0≦

z≦

4; and

z=x+y;

(3) M′

<sub>2−

x+y′</sub>

M″

<sub>x−

y′</sub>

(Al, Ga)<sub>2−

y</sub>(Si, Ge)_yB₂O<sub>7−

z−

y′</sub>

N_zX_y;

Eu²⁺, Mn²⁺, Pb²⁺, where M′

is one or more of alkali metals Na and/or K, M″

is one or more of alkaline earth metals Mg, Ca, Sr, Ba and/or Zn, 0≦

x≦

2, 0≦

y≦

2, 0≦

z≦

4;

z=x+y, X═

F and/or Cl, and 0≦

y′

≦

2;

(4) M′

<sub>2−

x</sub>M″

_xAl<sub>2−

y+y′</sub>

Si<sub>y−

y′</sub>

B₂O<sub>7−

z−

y′</sub>

N_zX_y;

Eu²⁺, Mn²⁺, Pb²⁺, where M′ and

M″

are defined above, 0≦

x≦

2, 0≦

y≦

2, 0≦

z≦

4;

z=x+y, X═

F and/or Cl, and 0≦

y′

≦

2;

(5) M′

<sub>2−

x+x′</sub>

M″

<sub>x−

x″</sub>

Al<sub>2−

y+y</sub>Si<sub>y−

y′</sub>

B₂O<sub>7−

z−

x′

−

y′</sub>

N_zX<sub>(x′

+y′

)</sub>;

Eu²⁺, Mn²⁺, Pb²⁺, where M′ and

M″

are defined above, 0≦

x≦

2, 0≦

y≦

2, 0≦

z≦

4;

z=x+y, X═

F and/or Cl, and 0≦

y′

≦

2;

(6) MAl₂B₂O₇;

Eu²⁺, Mn²⁺, Pb²⁺;

where M═

Mg, Ca, Sr, Ba or Zn;

(7) MAl<sub>2−

x</sub>Si_xB₂O<sub>7−

x</sub>N_x;

Eu²⁺, Mn²⁺, Pb²⁺ where M═

Mg, Ca, Sr, Ba and/or Zn, and 0≦

x≦

2; and

(8), MAl₂B<sub>2−

x</sub>Si_xO<sub>7−

x</sub>N_x;

Eu²⁺, Mn²⁺, Pb²⁺ where M═

Mg, Ca, Sr, Ba and/or Zn, and 0≦

x≦

2;

(B) and at least one additional phosphor.

18. A phosphor blend according to claim 17, wherein said at least one additional phosphor is selected from the group consisting of (Ba, Sr, Ca)₅(PO₄)₃(Cl, F, Br, OH):

Eu²⁺, Mn²⁺, Sb³⁺;

(Ba, Sr, Ca)MgAl₁₀O₁₇;

Eu²⁺, Mn²⁺;

(Ba, Sr, Ca)BPO₅;

Eu²⁺, Mn²⁺;

(Sr, Ca)₁₀(PO₄)₆*nB₂O₃;

Eu²⁺;

2SrO*0.84P₂O₅*0.16B₂O₃;

Eu²⁺;

Sr₂Si₃O_8*2SrCl₂;

Eu²⁺;

Ba₃MgSi₂O₈;

Eu²⁺;

Sr₄Al₁₄O₂₅;

Eu²⁺;

BaAl₈O₁₃;

Eu²⁺;

Sr₄Al₁₄O₂₅;

Eu²⁺;

BaAl₈O₁₃;

Eu²⁺;

2SrO-0.84P₂O<sub>5−

0.16</sub>B₂O₃;

Eu²⁺;

(Ba, Sr, Ca)MgAl₁₀O₁₇;

Eu²⁺, Mn²⁺;

(Ba, Sr, Ca)₅(PO₄)₃(Cl, F, OH);

Eu²⁺, Mn²⁺, Sb³⁺;

(Ba, Sr, Ca)MgAl₁₀O₁₇;

Eu²⁺, Mn²⁺;

(Ba, Sr, Ca)Al₂O₄;

Eu²⁺;

(Y, Gd, Lu, Sc, La)BO₃;

Ce³⁺, Tb³⁺;

Ca₈Mg(SiO₄)₄Cl₂;

Eu²⁺, Mn²⁺;

(Ba, Sr, Ca)₂SiO₄;

Eu²⁺;

(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)₅O₁₂;

Ce³⁺;

(Ca, Sr)₈(Mg, Zn)(SiO₄)₄Cl₂;

Eu²⁺, Mn²⁺ (CASI);

Na₂Gd₂B₂O₇;

Ce³⁺, Tb³⁺;

(Ba, Sr)₂(Ca, Mg, Zn)B₂O₆;

K, Ce, Tb;

(Sr, Ca, Ba, Mg, Zn)₂P₂O₇;

Eu²⁺, Mn²⁺ (SPP);

(Ca, Sr, Ba, Mg)₁₀(PO₄)₆(F, Cl, Br, OH);

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⁺;

SrY₂S₄;

Eu²⁺;

CaLa₂S₄;

Ce³⁺;

(Ca, Sr)S;

Eu²⁺;

3.5 MgO*0.5 MgF₂*GeO₂;

Mn⁴⁺;

(Ba, Sr, Ca)MgP₂O₇;

Eu²⁺, Mn²⁺;

(Y, Lu)₂WO₆;

Eu³⁺, Mo⁶⁺;

(Ba, Sr, Ca)_xSi_yN_z;

Eu²⁺; and

blends thereof.

19. An arc discharge lamp having an improved color rendering index for a given color coordinated temperature, the lamp comprising:

a lamp envelope enclosing a discharge space and having an inner surface;

an ionizable medium within said lamp envelope comprising mercury and an inert gas;

first and second electrodes; and

a phosphor layer disposed on an inner surface of the lamp envelope comprising a phosphor composition including at least one of;

(A) M₃Ln₂(BO₃)₄ doped with at least one activator selected from the group of Eu²⁺, Mn²⁺, Pb²⁺, Ce³⁺, Eu³⁺, Tb³⁺, and Bi³⁺ where M is at least one of Mg, Ca, Sr, Ba, or Zn, and Ln is at least one of Sc, Y, La, Gd, or Lu;

(B) M′

<sub>2−

x</sub>M″

_x(Al, Ga)<sub>2−

y</sub>(Si, Ge)_yB₂O<sub>7−

z</sub>N_z;

Eu²⁺, Mn²⁺, Pb²⁺ where M′

is one or more of alkali metals Na and/or K, M″

is one or more of alkaline earth Mg, Ca, Sr, Ba or Zn, 0≦

x≦

2, 0≦

y≦

2, 0≦

z≦

4; and

z=x+y;

(C) M′

<sub>2−

x+y′</sub>

M″

<sub>x−

y′</sub>

(Al, Ga)<sub>2−

y</sub>(Si, Ge)_yB₂O<sub>7−

z−

y′</sub>

N_zX_y;

Eu²⁺, Mn²⁺, Pb²⁺, where M′

is one or more of alkali metals Na and/or K, M″

is one or more of alkaline earth metals Mg, Ca, Sr, Ba and/or Zn, 0≦

x≦

2, 0≦

y≦

2, 0≦

z≦

4;

z=x+y, X═

F and/or Cl, and 0≦

y′

≦

2;

(D) M′

<sub>2−

x</sub>M″

_xAl<sub>2−

y+y′</sub>

Si<sub>y−

y′</sub>

B₂O<sub>7−

z−

y′</sub>

N_zX_y;

Eu²⁺, Mn²⁺, Pb²⁺, where M′ and

M″

are defined above, 0≦

x≦

2, 0≦

y≦

2, 0≦

z≦

4;

z=x+y, X═

F and/or Cl, and 0≦

y′

≦

2;

(E) M′

<sub>2−

x+x′</sub>

M″

<sub>x−

x′</sub>

Al<sub>2−

y+y</sub>Si<sub>y−

y′</sub>

B₂O<sub>7−

z−

x′

−

y′</sub>

N_zX<sub>(x′

+y′

)</sub>;

Eu²⁺, Mn²⁺, Pb²⁺, where M′ and

M″

are defined above, 0≦

x≦

2, 0≦

y≦

2, 0≦

z≦

4;

z=x+y, X═

F and/or Cl, and 0≦

y′

≦

2;

(F) MAl₂B₂O₇;

Eu²⁺, Mn²⁺, Pb²⁺ where M═

Mg, Ca, Sr, Ba and/or Zn;

(G) MAl<sub>2−

x</sub>Si_xB₂O<sub>7−

x</sub>N_x;

Eu²⁺, Mn²⁺, Pb²⁺, where M═

Mg, Ca, Sr, Ba and/or Zn, and 0≦

x≦

2;

or

(H) MAl₂B<sub>2−

x</sub>S_xO<sub>7−

x</sub>N_x;

Eu²⁺, Mn²⁺, Pb²⁺, where M═

Mg, Ca, Sr, Ba and/or Zn, and 0≦

x≦

2.