Silicate phosphors

Patent metadata

Field	Value
Publication number	US-10689570-B2
Application number	US-201615569438-A
Country	US
Kind code	B2
Filing date	Mar 30, 2016
Priority date	Apr 27, 2015
Publication date	Jun 23, 2020
Grant date	Jun 23, 2020

Abstract

The invention relates to pyrosilicate phosphors comprising a coating of aluminum oxide, to a process for the preparation of these compounds, and to the use thereof as conversion phosphors or in lamps.

First claim

The invention claimed is:

1. A compound of formula (1),
(Ba 2−a−b−c−d M a A b RE c D d )(Mg 1−e−f−g−j M′ e A′ f RE′ g C′ j )(Si 2−h−i B′ h C″ i )(O 7+m−k−l X k N l )  Formula (1)

where the following applies to the symbols and indices used:
M is Ca, Sr, Zn or a mixture of these elements;
A is Na, K, Rb or a mixture of these elements;
RE is La, Y, Gd or a mixture of these elements;
D is Eu 2+ , Mn 2+ , Yb 2+ , Sm 2+ or a mixture of these elements;
M′ is Zr, Hf or a mixture of these elements;
A′ is Li, Na or a mixture of these elements;
RE′ is Sc, Lu or a mixture of these elements;
C′ is B, Al, Ga, In or a mixture of these elements;
B′ is Ge, Sn or a mixture of these elements;
C″ is B, Al, Ga, In or a mixture of these elements;
X is F, Cl or a mixture of these elements;
N is nitrogen;
0≤a≤1.0;
0≤b≤0.6;
0≤c≤0.6;
0<d≤2;
0≤e≤0.3;
0≤f≤0.3;
0≤g≤0.3;
0≤j≤0.6;
0≤h≤1.0;
0≤i≤0.6;
0≤k≤2.1;
0≤l≤2.1;
−2.0≤m≤2.0;

wherein at least one and a maximum of three of the indices b, c, e, f, g, h, i, j, k, and l is ≠0; and
wherein the compound contains a coating of aluminum oxide which has been deposited by an ALD process.

2. The compound according to claim 1 , wherein the following applies for the indices used:
0≤a≤0.4;
0≤b≤0.2;
0≤c≤0.2;
0.01≤d≤0.2,
0≤e≤0.1;
0≤f≤0.1;
0≤g≤0.1;
0≤j≤0.2;
0≤h≤0.4;
0≤i≤0.2;
0≤k≤0.7;
0≤l≤0.7;
−0.5≤m≤0.5.

3. The compound according to claim 1 , wherein said compound is selected from compounds of formula (2),
(Ba 2−a−b−c−d M a K b La c Eu d )(Mg 1−e−f−g−j Zr c Li f Sc g C′ j )(Si 2−h−i Ge h C′ j )(O 7+m−k−l X k N l )  Formula (2)

where the following applies for the symbols and indices used:
M is Ca, Sr or a mixture of these elements;
C′ is Al, Ga or a mixture of these elements;
C″ is Al, Ga or a mixture of these elements;
X is F, Cl or a mixture of these elements;
N is nitrogen;
0≤a≤0.4;
0≤b≤0.2;
0≤c≤0.2;
0≤d≤0.4,
0≤e≤0.1;
0≤f≤0.1;
0≤g≤0.1;
0≤j≤0.2;
0≤h≤0.4;
0≤i≤0.2;
0≤k≤0.7;
0≤l≤0.7;
−0.5≤m≤0.5.

4. The compound according to claim 3 , wherein the index d satisfies the following equation: 0.01≤d≤0.2.

5. The compound according to claim 1 , wherein said compound is selected from compounds of the following formulae:
(Ba 2−b−d A b D d )Mg Si 2 (O 7−b X b )  (3)

(Ba 2−b−d A b D d )(Mg 1−b RE′ b )Si 2 O 7   (4)

(Ba 2−b−d A b D d )Mg Si 2 O 7−0.5b   (5)

(Ba 2−c−d RE c D d )Mg Si 2 (O 7−c N c )  (6)

(Ba 2−d D d )(Mg 1−g RE′ g )Si 2 (O 7−g N g )  (7)

(Ba 2−d D d )(Mg 1−e M′ e )Si 2 O 7+e   (8)

(Ba 2−d−0.5e D d )(Mg 1−e M′ e )Si 2 O 7+0.5e   (9)

(Ba 2−d D d )(Mg 1−f A′ f )Si 2 (O 7−f X f )  (10)

(Ba 2−d D d )(Mg 1-2f A′ f C′ f )Si 2 O 7   (11)

(Ba 2−d D d )(Mg 1−f A′ f )(Si 2−f C″ f )O 7   (12)

(Ba 2−d D d )(Mg 1−2e M′ e RE′ e )Si 2 (O 7−e N e )  (13)

(Ba 2−a−d M a D d )Mg Si 2 O 7   (15)

(Ba 2−d D d )Mg(Si 2−h B′ b )O 7   (16)

(Ba 2−d D d )(Mg 1−j C′ j )(Si 2−j C″ j )O 7   (17)

where the symbols and indices have the meanings given above and furthermore:
b≠0 in formula (3), (4) and (5),
c≠0 in formula (6),
g≠0 in formula (7),
e≠0 in formula (8) and (9),
f≠0 in formula (10), (11) and (12), and
e≠0 in formula (13).

6. The compound according to claim 1 , selected from the compounds of the following formulae:
(Ba 2−b−d K b Eu d )Mg Si 2 (O 7−b F b )  (3a)

(Ba 2−b−d K b Eu d )Mg Si 2 (O 7−b Cl b )  (3b)

(Ba 2−b−d K b Eu d )(Mg 1−b Sc b )Si 2 O 7   (4a)

(Ba 2−b−d K b Eu d )Mg Si 2 O 7−0.5b   (5a)

(Ba 2−c−d La c Eu d )Mg Si 2 (O 7−c N c )  (6a)

(Ba 2−d Eu d )(Mg 1−g Sc g )Si 2 (O 7−g N g )  (7a)

(Ba 2−d Eu d )(Mg 1−e Zr e )Si 2 O 7+e   (8a)

(Ba 2−d−0.5e Eu d )(Mg 1−e Zr′ e )Si 2 O 7+0.5e   (9a)

(Ba 2−d Eu d )(Mg 1−f Li f )Si 2 (O 7−f F f )  (10a)

(Ba 2−d Eu d )(Mg 1−f Li f )Si 2 (O 7−f Cl f )  (10b)

(Ba 2−d Eu d )(Mg 1−2f Li f Al f )Si 2 O 7   (11a)

(Ba 2−d Eu d )(Mg 1−2f Li f Ga f )Si 2 O 7   (11b)

(Ba 2−d Eu d )(Mg 1−f Li f )(Si 2−f Al f )O 7   (12a)

(Ba 2−d Eu d )(Mg 1−f Li f )(Si 2−f Ga f )O 7   (12b)

(Ba 2−d Eu d )(Mg 1−2e Zr e Sc e )Si 2 (O 7−e N e )  (13a)

(Ba 1−a−d Sr a Eu d ) 2 Mg Si 2 O 7   (15a)

(Ba 1−a−d Ca a Eu d ) 2 Mg Si 2 O 7   (15b)

(Ba 1−d Eu d ) 2 Mg(Si 1−h Ge h ) 2 O 7   (16a)

(Ba 2−d Eu d )(Mg 1−j Al j )(Si 2−j Al j )O 7   (17a)

where the symbols and indices have the meanings given above and furthermore:
b≠0 in formula (3a), (3b), (4a) and (5a),
c≠0 in formula (6a),
g≠0 in formula (7a),
e≠0 in formula (8a) and (9a),
f≠0 in formula (10a), (10b), (11a), (11 b), (12a) and (12b), and
e≠0 in formula (13a).

7. The compound according to claim 1 , wherein said compound is selected from the following compounds:
Ba 1.85 K 0.05 Eu 0.10 MgSi 2 O 6.95 Cl 0.05 ,
Ba 1.85 K 0.05 Eu 0.10 MgSi 2 O 6.95 F 0.05 ,
Ba 1.90 Eu 0.10 Mg 0.95 Li 0.05 Si 2 O 6.95 Cl 0.05 ,
Ba 1.90 Eu 0.10 Mg 0.95 Li 0.05 Si 2 O 6.95 F 0.05 ,
Ba 1.90 Eu 0.10 Mg 0.80 Li 0.1 Al 0.1 Si 2 O 7 ,
Ba 1.90 Eu 0.10 Mg 0.95 Zr 0.05 Si 2 O 7.05 ,
Ba 1.90 Eu 0.10 Mg 0.95 Sc 0.05 Si 2 O 7.025 , and
Ba 1.86 Eu 0.10 La 0.04 MgSi 2 O 7.02 .

8. The compound according to claim 1 , wherein a maximum of two of the indices b, c, e, f, g, h, i, j, k, and l is ≠0.

9. The compound Previously Presented according to claim 1 , wherein the coating has a thickness between 0.5 and 150 nm.

10. The compound according to claim 9 , wherein the coating has a thickness between 2 and 75 nm.

11. The compound according to claim 10 , wherein the coating has a thickness between 3 and 50 nm.

12. A method for preparation of a phosphor according to claim 1 , comprising:
a) providing a compound of formula (1); and
b) forming a layer of aluminum oxide on the surface of the compound via an atomic layer deposition process.

13. The method according to claim 12 , wherein the formation of the layer of aluminum oxide comprises:
b1) introducing a purge/fluidizing gas;
b2) introducing a mixture of carrier gas and first reagent;
b3) introducing a purge/fluidizing gas and/or pulling a vacuum to remove excess quantities of the first reagent and reaction by-products;
b4) introducing a mixture of carrier gas and second reagent;
b5) introducing a purge/fluidizing gas and/or pulling a vacuum to remove excess quantities of the second reagent and reaction by-products; and
b6) repeating b2) to b5) until desired coating thickness is obtained.

14. The method according to claim 13 , wherein argon, nitrogen, other inert gas, or a mixture of inert gases is used as the purge/fluidizing gas and argon, nitrogen, other inert gas, or a mixture of inert gases is used as carrier gas.

15. The method according to claim 13 , wherein trialkyl aluminum or an aluminum trihalide are used as the first reagent and an oxidizer is used as the second reagent.

16. The method according to claim 13 , wherein trimethyl aluminum, triethyl aluminum, or aluminum trichloride are used as the first reagent and an oxidizer selected from water, oxygen plasma species, ozone or alcohols is used as the second reagent.

17. A method comprising partial or complete conversion of near-UV emission or violet emission of a light-emitting diode into light having a longer wavelength by a conversion phosphor comprising a compound according to claim 1 .

18. A light source comprising at least one primary light source and at least one compound according to claim 1 .

19. The light source according to claim 18 , wherein the primary light source is a luminescent

Assignees

• Merck Patent Gmbh

Inventors

• Zych Aleksander
• Petry Ralf
• Rapphahn Mathias
• Koehler Ingo
• Tews Stefan

Classifications

• C09K11/77922

  Silicates · CPC title

• C09K11/77344

  Aluminosilicates · CPC title

• C09K11/77342 Primary

  Silicates · CPC title

• C09K11/025 Primary

  non-luminescent particle coatings or suspension media · CPC title

• C09K11/7792

  Aluminates · CPC title