# US 11,114,591 B2 · Core-shell materials with red-emitting phosphors

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- Number: US 11,114,591 B2
- Document ID: US11114591B2
- Status: Granted
- Kind: B2
- Application number: 15/238,989
- Filed: 2016-08-17
- Published: 2018-02-22
- Granted: 2021-09-07
- Earliest claimed: 2016-08-17
- Assignees: Current Lighting Solutions, LLC
- Applicants: Current Lighting Solutions, LLC
- Inventors: James Edward Murphy; William Winder Beers; William Erwin Cohen
- Web page: https://patentgrep.com/patent/US11114591B2

## CPC

- H10H 20/8513: {having two or more wavelength conversion materials}
- C09K 11/02: Use of particular materials as binders, particle coatings or suspension media therefor
- C09K 11/617: {Silicates}
- C09K 11/7774: {Aluminates}
- H10H 20/854: characterised by their material, e.g. epoxy or silicone resins
- H10H 20/0361: {of wavelength conversion means}
- H10H 20/0362: {of encapsulations}
- H10H 20/8512: {Wavelength conversion materials}
- H10H: INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
- C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE

## Abstract

A coated phosphors that include a shell comprising a first Mn4+ doped phosphor of formula I Ax[MFy]:Mn4+ I directly disposed on a core comprising a second phosphor. The second phosphor is a material other than a compound of formula I or formula II Ax[MFy] II wherein A is, independently at each occurrence, Li, Na, K, Rb, Cs, or a combination thereof; M is, independently at each occurrence, Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Hf, Y, La, Nb, Ta, Bi, Gd, or a combination thereof; x is the absolute value of the charge of the [MFy] ion; and y is 5, 6 or 7.

## Claims

### Claim 1

A process for preparing a coated phosphor, the process comprising contacting a suspension of a phosphor material in particulate form in a HF solution, with a source of Mn4+, A+, and M, to form a coated phosphor having a shell comprising a first phosphor of formula I,
Ax[MFy]:Mn4+ I
directly disposed on a core comprising a second phosphor; and
converting the coated phosphor to a color stable coated phosphor by contacting the already formed coated phosphor:
with a fluorine-containing oxidizing agent in gaseous form at an elevated temperature ranging from about 350 degrees Celsius to about 700 degrees Celsius,
and with a compound of formula II, Ax[MFy] in an aqueous hydrofluoric acid, wherein the second phosphor is a material other than a compound of formula I or formula II; and
Ax[MFy] II
wherein:
contact with the compound of formula II in the aqueous hydrofluoric acid is one of: 1, before, or 2, both before and after, the coated phosphor is contacted with the fluorine-containing oxidizing agent in gaseous form at the elevated temperature ranging from about 350 degrees Celsius to about 700 degrees Celsius,
A is, independently at each occurrence, Li, Na, K, Rb, Cs, or a combination thereof;
M is, independently at each occurrence, Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Hf, Y, La, Nb, Ta, Bi, Gd, or a combination thereof;
x is the absolute value of the charge of the [MFy] ion; and
y is 5, 6 or 7.

### Claim 2 (depends on 1)

The process of claim 1, wherein the second phosphor is a green phosphor.

### Claim 3 (depends on 1)

The process of claim 1, wherein the second phosphor is a Ce3+-doped garnet phosphor.

### Claim 4 (depends on 1)

The process of claim 1 wherein the second phosphor is (Y,Gd,Tb,La,Sm,Pr,Lu)3 (Al,Ga)5-αO12-3/2α:Ce3+ (wherein 0≤α≤0.5).

### Claim 5 (depends on 1)

The process of claim 1, wherein the second phosphor is a Eu2+-doped β-SiAION phosphor.

### Claim 6 (depends on 1)

The process of claim 1, wherein the second phosphor is CaAISiN3: Eu2+.

### Claim 7 (depends on 1)

The process of claim 1, wherein the second phosphor is a Eu2+-doped nitride phosphor.

### Claim 8 (depends on 1)

The process of claim 1, wherein the second phosphor is (Ba, Sr)2Si5N8:Eu2+, (Ca, Sr)AlSiN3:Eu2+′ Sr[LiAl3N4]:Eu2+′ Sr[Mg3SiN4]:Eu2+, (Sr, Ca)S:Eu2+, or a combination thereof.

### Claim 9 (depends on 1)

The process of claim 1, wherein M is Si, Ge, Sn, Ti, Zr, or a combination thereof.

### Claim 10 (depends on 1)

The process of claim 1, wherein A is Na, K, or a combination thereof.

### Claim 11 (depends on 1)

The process of claim 1, wherein
A is Na, K, Rb, Cs, or a combination thereof;
M is Si, Ge, Ti, or a combination thereof; and
Y is 6.

### Claim 12 (depends on 1)

The process of claim 1, wherein the first phosphor is K2SiF6:Mn4+.