# US 8,771,547 B2 · Oxycarbonitride phosphors and light emitting devices using the same

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- Number: US 8,771,547 B2
- Document ID: US8771547B2
- Status: Granted
- Kind: B2
- Application number: 13/950,354
- Filed: 2013-07-25
- Published: 2014-06-12
- Granted: 2014-07-08
- Earliest claimed: 2010-05-14
- Assignees: Lightscape Materials, Inc.
- Applicants: Rohm and Haas Electronic Materials LLC
- Inventors: Yuanqiang Li; Michael Dennis Romanelli; Yongchi Tian
- Web page: https://patentgrep.com/patent/US8771547B2

## CPC

- C09K 11/7728: {containing europium}
- C09K 11/0883: {Arsenides; Nitrides; Phosphides}
- C09K 11/7705: {with alkali or alkaline earth metals}
- C09K 11/7731: {with alkaline earth metals}
- C09K 11/7733: {with alkali or alkaline earth metals}
- C09K 11/77347: {Silicon Nitrides or Silicon Oxynitrides}
- C09K 11/77348: {Silicon Aluminium Nitrides or Silicon Aluminium Oxynitrides}
- F21K 9/64: using wavelength conversion means distinct or spaced from the light-generating element, e.g. a remote phosphor layer
- H01J 1/63: characterised by the luminescent material
- H01J 29/20: characterised by the luminescent material
- H10H 20/8512: {Wavelength conversion materials}
- Y02B 20/00: Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
- C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- F21K: NON-ELECTRIC LIGHT SOURCES USING LUMINESCENCE; LIGHT SOURCES USING ELECTROCHEMILUMINESCENCE; LIGHT SOURCES USING CHARGES OF COMBUSTIBLE MATERIAL; LIGHT SOURCES USING SEMICONDUCTOR DEVICES AS LIGHT-GENERATING ELEMENTS; LIGHT SOURCES NOT OTHERWISE PROVIDED FOR
- H01J: ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS (spark-gaps H01T; electric arc lamps H05B31/00; particle accelerators H05H)
- H10H: INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
- Y02B: CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS

## Abstract

Disclosed herein is a novel family of oxycarbonitride phosphor compositions and light emitting devices incorporating the same. Within the sextant system of M—Al—Si—O—N—C—Ln and quintuplet system of M—Si—O—N—C—Ln (M=alkaline earth element, Ln=rare earth element), the phosphors are composed of either one single crystalline phase or two crystalline phases with high chemical and thermal stability. In certain embodiments, the disclosed phosphor of silicon oxycarbonitrides emits green light at wavelength between 530-550 nm. In further embodiments, the disclosed phosphor compositions emit blue-green to yellow light in a wavelength range of 450-650 nm under near-UV and blue light excitation.

## Claims

### Claim 1

A composition comprising a phosphor having a formula selected from the group consisting of:
M(II)7−yM(I)yM(III)12−x−y−zSix+y+zO25−x±δ/2Nx±δ−zCz:A, wherein 0<x<12, 0≦y<x, 0<z<x, 0<x+y+z≦12, z<x+δ, and 0<δ≦3; (a)
M(II)7−yM(I)yM(III)12−x−y−zSix+y+zO25−x±δ/2Nx±δ−zC25δ/2:A, wherein 0<x<12, 0≦y<x, 0<z<x, 0<x+y+z≦12, z<x+δ, and 0<δ≦3; (b)
M(II)7−yM(I)yM(III)12−x−y−zSix+y+zO25−x−y/2±3δ/2Nx±δ−zCzDv:A, wherein 0<x<12, 0≦y<1, 0<z<x, z<x+δ, 0<δ≦3, 0≦v<1, and 0<x+y+z≦12; (c) and
M(II)7−yM(I)yM(III)12−x−y−zSix+y+zO25−x−v/2±δ/2Nx±δ−zCz±δ/2Dv:A, wherein 0<x<12, 0≦y<1, 0<z<x, z<x+δ, 0<δ≦3, 0≦v<1, and 0<x+y+z≦12; (d)
wherein:
M(II) comprises at least one divalent cation;
M(I) comprises at least one monovalent cation;
M(III) comprises at least one trivalent cation;
D comprises at least one monovalent anion; and
A comprises a luminescence activator doped in the crystal structure.

### Claim 2 (depends on 1)

The composition of claim 1, wherein
M(II) comprises at least one divalent cation selected from the group consisting of Be, Mg, Ca, Sr, Ba, Cu, Co, Ni, Pd, Zn, and Cd;
M(I) comprises at least one monovalent cation selected from the group consisting of Li, Na, K, Rb, Cu, Ag and Au;
M(III) comprises at least one trivalent cation selected from the group consisting of B, Al, Ga, In, Sc, Y, La and Gd;
D comprises at least one anion selected from the group consisting of F, Cl, Br and I; and
A comprises at least one luminescence activator selected from the group consisting of Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Mn, Bi, and Sb.

### Claim 3

A light emitting device comprising:
a light source emitting a first luminescence spectrum;
a phosphor composition, which, when irradiated with light from the light source, emits light having a second luminescence spectrum;
wherein a phosphor composition comprises at least one phosphor selected from the group consisting of:
M(II)7Al12−x−ySix+yO25−xNx−yCy:A, wherein 0<x≦12, 0<y<x, and 0<x+y≦12; (a)
M(II)7M(III)12−x−ySix+yO25−xNx−yCy:A, wherein 0<x≦12, 0<x+y≦12, and 0<y<x; (b)
M(II)7M(III)12−x−ySix+yO25−x±3δ/2Nx±δ−yCy:A, wherein 0<x<12, 0≦y<x, 0<x+y≦12, 0<δ≦3, and δ<x+y; (c)
M(II)7M(III)12−x−ySix+yO25−x±δ/2Nx±δ−yCy±δ/2:A, wherein 0≦x<12, 0≦y<x, 0<x+y≦12, 0<δ≦3, and δ<x+y; (d)
M(II)7−yM(I)yM(III)12−x−y−zSix+y+zO25−x±3δ/2Nx±δ−zCz:A, wherein 0<x<12, 0≦y<x, 0<z<x, 0<x+y+z±12, z<x+δ, and 0<δ≦3; (e)
M(II)7−yM(I)yM(III)12−x−y−zSix+y+zO25−x±δ/2Nx±δ−zCz±δ/2:A, wherein 0<x<12, 0≦y<x, 0<z<x, 0<x+y+z≦12, z<x+δ, and 0<δ≦3; (f)
M(II)7−yM(I)yM(III)12−x−y−zSix+y+zO25−x−v/2±3δ/2Nx±δ−zCzDv:A, wherein 0<x<12, 0≦y<1, 0<z<x, z<x+δ, 0<δ≦3, 0≦v<1, and 0<x+y+z≦12; (g) and
M(II)7−yM(I)yM(III)12−x−y−zSix+y+zO25−x−v/2±δ/2Nx±δ/2Dv:A, wherein 0<x<12, 0≦y<1, 0<z<x, z<x+δ, 0<δ≦3, 0≦v<1, and 0<x+y+z≦12; (h)
wherein:
M(II) comprises at least one divalent cation selected from the group consisting of Be, Mg, Ca, Sr, Ba, Cu, Co, Ni, Pd, Zn, and Cd;
M(I) comprises at least one monovalent cation selected from the group consisting of Li, Na, K, Rb, Cu, Ag and Au;
M(III) comprises at least one trivalent cation selected from the group consisting of B, Al, Ga, In, Sc, Y, La and Gd;
D comprises at least one monovalent anion selected from the group consisting of F, Cl, Br and I; and
A comprises a luminescence activator doped in the crystal structure, wherein the luminescence activator is selected from the group consisting of Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Mn, Bi, and Sb.

### Claim 4 (depends on 3)

The light emitting device of claim 3, further comprising a second phosphor having a formula selected from the group consisting of:
Ca1−xAlx−xySi1−x+xyN2−x−xyCxy:A; (a)
Ca1−x−zNazM(III)x−xy−zSi1−x+xy+zN22−x−xyCxy:A; (b)
M(II)1−x−zM(I)zM(III)x−xy−zSi1−x+xy+zN2−x−xyCxy:A; (c)
M(II)1−x−zM(I)zM(III)x−xy−zSi1−x+xy+zN2−x−xy−2w/3CxyO2−v/2Dv:A; (d) and
M(II)1−x−zM(I)zM(III)x−xy−zSi1−x+xy+zN2−x−xy−2w/3−v/3CxyOwDv:A; (e)
wherein:
0<x<1, 0<y<1, 0≦z<1, 0<w<1, x+z<1, x>xy+z, v/2≦w, x−xy−2w/3−v/3<2, and 0<x−xy−z<1;
M(II) is at least one divalent cation;
M(I) is at least one monovalent cation;
M(II) is at least one trivalent cation;
D is at least one monovalent anion; and
A is a luminescence activator.

### Claim 5 (depends on 3)

The light emitting device of claim 3, further comprising at least two additional phosphors.

### Claim 6 (depends on 3)

The light emitting device of claim 3, wherein the device emits white light.

### Claim 7 (depends on 3)

The light emitting device of claim 3, further comprising at least one phosphor selected from the group consisting of Ca1−xSrxS:Eu2+(0≦x≦1), 3.5 MgO.0.5 MgF2.GeO2:Mn4+, Y2O2S:Eu3+, M2Si5N8:Eu2+(M=Ca, Sr, Ba), MAlSiN3:Eu2+(M=Ca, Sr), Y2Si4N6C:Eu2+, CaSiN2:Eu2+, Ca1−xSrxGa2S4:Eu2+(0≦x≦1), Ca1−x−y−zMgxSryBazSiO4:Eu2+(0≦x≦1, 0≦y≦1, 0≦z≦1, x+y+z≦1), BaMgAl10O17:Eu2+, Mn2+, MYSi4N7:Eu2+(M=Ca, Sr, Ba), β-sialon:Eu2+, MSi2O2N2:Eu2+(M=Ca, Sr, Ba), Ba3Si6O12N2:Eu2+, M2Si5N8:Ce3+(M=Ca, Sr, Ba), Y2Si4N6C:Ce3+, α-sialon:Yb2+, (MSiO3)m.(SiO2)n:Eu2+, X(M=Mg, Ca, Sr, Ba; X=F, Cl, Br, I; m is 0 or 0, and either (i) n>3 if M=1 or (ii) n=1 if m=0), MAl2O4:Eu2+(M=Mg, Ca, Sr), BaMgAl10O17:Eu2+, Y3Al5O12:Ce3+ (cerium-doped garnet type phosphor), and α-sialon:Eu2+.