# US 10,479,937 B2 · Narrow band red phosphor

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- Number: US 10,479,937 B2
- Document ID: US10479937B2
- Status: Granted
- Kind: B2
- Application number: 15/282,551
- Filed: 2016-09-30
- Published: 2017-05-25
- Granted: 2019-11-19
- Earliest claimed: 2015-10-09
- Assignees: Intematix Corporation
- Applicants: Intematix Corporation
- Inventors: Haoguo Zhu; Yi-Qun Li
- Web page: https://patentgrep.com/patent/US10479937B2

## CPC

- C09K 11/885: {with alkaline earth metals}
- C09K 11/025: {non-luminescent particle coatings or suspension media}
- C09K 11/88: containing selenium, tellurium or unspecified chalcogen elements
- G02B 6/005: {provided by one optical element, or plurality thereof, placed on the light output side of the light guide}
- G02F 1/133514: {Colour filters}
- G02F 1/133603: {with LEDs}
- H10H 20/825: containing nitrogen, e.g. GaN
- H10H 20/8506: {Containers}
- H10H 20/8513: {having two or more wavelength conversion materials}
- H10H 20/854: characterised by their material, e.g. epoxy or silicone resins
- H10H 20/856: Reflecting means
- H10H 20/857: Interconnections, e.g. lead-frames, bond wires or solder balls
- H10H 20/8581: {characterised by their material}
- H10W 90/00: Package configurations
- G02F 1/133614: {using photoluminescence, e.g. phosphors illuminated by UV or blue light}
- H10W 72/07554: {changes in dispositions}
- H10W 72/547: {Dispositions of multiple bond wires}
- H10W 72/884: {Die-attach connectors and bond wires}
- H10W 90/756: {between a chip and a stacked lead frame, conducting package substrate or heat sink}
- Y02B 20/00: Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
- C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- G02B: OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02F: OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- H10H: INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
- H10W: GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
- Y02B: CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS

## Abstract

A narrow band red phosphor may have a general composition MSxSeyAz:Eu, wherein M is at least one of Mg, Ca, Sr and Ba, A is at least one of C, N, B, P and a monovalent combining group NCN (cyanamide), and may in some embodiments further include one or more of O, F, Cl, Br and I. In embodiments 0.8<x+y<1.25 and 0<z≤0.05, and in some embodiments x, y and z are determined strictly by charge balancing. A white light emitting device may comprise: a blue and/or UV excitation source; a narrow band red phosphor of the present invention; and phosphors with peak emission at shorter wavelengths, such as yellow, green, yellow/green and/or blue.

## Claims

### Claim 1

A red-emitting phosphor, comprising:
phosphor particles with a composition represented by the chemical formula MSxSeyAz:Eu, wherein
M is at least one of Mg, Ca, Sr and Ba;
A comprises one or more of carbon, nitrogen, boron, phosphorous and a monovalent combining group NCN (cyanamide);
x≥0;
y≥0.1;
0<z≤0.05; and
0.8<x+y<1.25.

### Claim 2 (depends on 1)

The red-emitting phosphor of claim 1, wherein x+y is not equal to 1.

### Claim 3 (depends on 1)

The red-emitting phosphor of claim 1, wherein 1.0<x+y<1.25.

### Claim 4 (depends on 1)

The red-emitting phosphor of claim 1, wherein x, y and z have values which provide a charge balanced chemical formula.

### Claim 5 (depends on 1)

The red-emitting phosphor of claim 1, further comprising one or more of oxygen, fluorine, chlorine, bromine and iodine.

### Claim 6 (depends on 1)

The red-emitting phosphor of claim 1, wherein M is calcium.

### Claim 7 (depends on 1)

The red-emitting phosphor of claim 1, wherein M is strontium.

### Claim 8 (depends on 1)

The red-emitting phosphor of claim 1, wherein A is carbon.

### Claim 9 (depends on 1)

The red-emitting phosphor of claim 1, wherein A is boron.

### Claim 10 (depends on 1)

The red-emitting phosphor of claim 1, wherein 0<z<0.03.

### Claim 11 (depends on 1)

The red-emitting phosphor of claim 1, further comprising a coating on individual ones of said phosphor particles, said coating comprising one or more materials chosen from the group consisting of aluminum oxide, silicon oxide, titanium oxide, zinc oxide, magnesium oxide, zirconium oxide, boron oxide, chromium oxide, calcium fluoride, magnesium fluoride, zinc fluoride, aluminum fluoride and titanium fluoride.

### Claim 12 (depends on 1)

The red-emitting phosphor of claim 1, wherein said coating comprises aluminum oxide.

### Claim 13 (depends on 1)

The red-emitting phosphor of claim 1, wherein said phosphor particles have a particle size distribution defined by diameter, D50, being in the range of 3 to 45 microns.

### Claim 14 (depends on 1)

The red-emitting phosphor of claim 1, wherein said phosphor particles have a particle size distribution defined by diameter, D50, being in the range of 5 to 25 microns.

### Claim 15 (depends on 1)

A white light emitting device, comprising:
at least one of a blue and UV excitation source;
a red-emitting phosphor as in claim 1; and
a green or yellow-emitting phosphor having a peak emission wavelength in the range from about 515 nm to about 570 nm.

### Claim 16 (depends on 15)

The white light source of claim 15, wherein said excitation source has a peak emission wavelength within a range from 200 nm to 480 nm.

### Claim 17 (depends on 15)

The white light source of claim 15, wherein said excitation source has a peak emission wavelength within a range from 400 nm to 480 nm.

### Claim 18 (depends on 15)

The white light source of claim 15, wherein said excitation source has a peak emission wavelength within a range from 450 nm to 480 nm.

### Claim 19 (depends on 15)

The white light source of claim 15, wherein said red-emitting phosphor particles absorb radiation at a wavelength of 450 nm and emit light with a photoluminescence peak emission wavelength between about 600 nm and about 630 nm.

### Claim 20 (depends on 15)

The white light source of claim 15, wherein said red-emitting phosphor has an emission peak full width half maximum of less than 55 nm.

### Claim 21 (depends on 1)

A display backlight, comprising:
an excitation source with peak emission in the blue part of the visible spectrum;
a red-emitting phosphor as in claim 1; and
a green-emitting phosphor having a peak emission in the green part of the visible spectrum.

### Claim 22 (depends on 21)

The display backlight of claim 21, wherein the white light illumination emitted by the display backlight covers an area including greater than 90% of NTSC 1953 color gamut specification as mapped on CIE 1931 xy chromaticity diagram.

### Claim 23 (depends on 21)

A liquid crystal color display comprising:
a display panel comprising a plurality of red, green and blue pixel areas;
a display backlight as in claim 21; and
a color filter plate located on a side of the display panel that is distal to the white light illumination system, wherein the color filter plate comprises at least one of:
first filter areas corresponding to red pixel areas of the display that are operable to allow the passage of red light;
second filter areas corresponding to green pixel areas of the display that are operable to allow the passage of green light; and
third filter areas corresponding to blue pixel areas of the display that are operable to allow the passage of blue light.

### Claim 24 (depends on 1)

A photoluminescence color display comprising:
a display panel comprising a plurality of red, green and blue pixel areas;
an excitation source operable to generate excitation radiation for operating the display;
a photoluminescence color-elements plate comprising at least one of:
a first photoluminescence material corresponding to red pixel areas of the display that is operable to emit red light in response to said excitation radiation, said first photoluminescence material comprising a red-emitting phosphor as in claim 1;
a second photoluminescence material corresponding to green pixel areas of the display that is operable to emit green light in response to said excitation radiation; and
a third photoluminescence material corresponding to blue pixel areas of the display that is operable to emit blue light in response to said excitation radiation; and
a color filter plate located on a side of the display panel that is distal to the excitation source, wherein the color filter plate comprises at least one of:
first filter areas corresponding to red pixel areas of the display that are operable to allow the passage of red light;
second filter areas corresponding to green pixel areas of the display that are operable to allow the passage of green light; and
third filter areas corresponding to blue pixel areas of the display that are operable to allow the passage of blue light.

### Claim 25

A method of making a phosphor, comprising:
combining in a crucible MSeO4:Eu crystals, powdered sulphur and powdered material comprising A; and
sintering the combined materials;
grinding the sintered material; and
washing the ground material;
wherein M is at least one of Mg, Ca, Sr and Ba;
wherein A comprises one or more of carbon, nitrogen, boron, phosphorous and the monovalent combining group NCN(cyanamide);
wherein the amount of S is chosen to provide a desired stoichiometric ratio of Se to S; wherein the amount of A is between 2.0 and 5.5 wt. %; and
wherein said phosphor has a composition represented by the chemical formula MSxSeyAz:Eu, wherein 0<z≤0.5, x≥0, y≥0.1, and 0.8<x+y<1.25.

### Claim 26 (depends on 25)

The method as in claim 25, further comprising adding a flux material in said combining, wherein said flux material is chosen from the group consisting of LiF, NH4Cl, CaCl2) and NH4Br.

### Claim 27 (depends on 25)

The method as in claim 25, wherein said material comprising A is carbon.

### Claim 28 (depends on 25)

The method as in claim 25, wherein said material comprising A is boric acid.

### Claim 29 (depends on 25)

The method as in claim 25, wherein A is between 3.0 and 4.5 wt. %.

### Claim 30 (depends on 25)

The method as in claim 25, wherein A is between 3.3 and 4.3 wt. %.