Dye-sensitized upconversion nanophosphor

Patent metadata

Field	Value
Publication number	US-11066598-B2
Application number	US-201916293960-A
Country	US
Kind code	B2
Filing date	Mar 6, 2019
Priority date	Sep 7, 2018
Publication date	Jul 20, 2021
Grant date	Jul 20, 2021

Abstract

Provided is a dye-sensitized upconversion nanophosphor including a core, a first shell surrounding at least part of the core, and an organic dye bonded to a surface of the nanophosphor which has an absorption band ranging from 650 nm to 850 nm and which is excited in a near-infrared region to emit visible light. The dye-sensitized upconversion nanophosphor may be included in a display apparatus, a fluorescent contrast agent, or an anti-counterfeiting code. The organic dye may be an IR-808 dye.

First claim

What is claimed is:

1. A dye-sensitized upconversion nanophosphor, comprising:
a core;
a first shell surrounding at least part of the core; and
an organic dye bonded to a surface of the nanophosphor which has an absorption band ranging from 650 nm to 850 nm and which is excited in a near-infrared region to emit visible light,
wherein the core is made of a fluoride-based material co-doped with Yb 3+ and Er 3+ and expressed by Chemical Formula 1 below,
LiGd x L 1-x-y-z F 4 :Yb 3+ y ,Er 3+ z ,  Chemical Formula 1

where x denotes a real number satisfying 0≤x≤0.6, y denotes a real number satisfying 0<y≤0.98, z denotes a real number satisfying 0<z≤0.2, 0<x+y+z≤1 is satisfied, and L denotes a rare-earth element selected from the group consisting of yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), terbium (Tb), dysprosium (Dy), holmium (Ho), thulium (Tm), and lutetium (Lu), and a combination thereof, and
wherein the first shell is made of a fluoride-based crystalline material co-doped with Nd 3+ and Yb 3+ and expressed by Chemical Formula 2 below,
LiY 1-p-q-r M r F 4 :Nd 3+ p ,Yb 3+ q ,  Chemical Formula 2

where p denotes a real number satisfying 0<p≤1, q denotes a real number satisfying 0<q≤0.5, r denotes a real number satisfying 0≤r≤1, 0<p+q+r≤1 is satisfied, and M denotes an element selected from the group consisting of La, gadolinium (Gd), Ce, Pr, Pm, Sm, Eu, Tb, Dy, Ho, erbium (Er), Tm, Lu, and a combination thereof.

2. The dye-sensitized upconversion nanophosphor of claim 1 , wherein the organic dye comprises C 45 H 51 N 2 NaO 8 S 3 which is an IR-808 dye.

3. A dye-sensitized upconversion nanophosphor, comprising:
a core;
a first shell surrounding at least part of the core; and
an organic dye bonded to a surface of the nanophosphor which has an absorption band ranging from 650 nm to 850 nm and which is excited in a near-infrared region to emit visible light,
wherein the core is made of a fluoride-based material co-doped with Yb 3+ and Tm 3+ and expressed by Chemical Formula 3 below,
LiGd x N 1-x-y-z F 4 :Yb 3+ y ,Tm 3+ z ,  Chemical Formula 3

where x denotes a real number satisfying 0≤x≤0.6, y denotes a real number satisfying 0<y≤0.98, z denotes a real number satisfying 0<z≤0.2, 0<x+y+z≤1 is satisfied, and N denotes an element selected from the group consisting of Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Tb, Dy, Ho, Er, Lu, and a combination thereof, and
wherein the first shell is made of a fluoride-based crystalline material co-doped with Nd 3+ and Yb 3+ and expressed by Chemical Formula 4 below,
LiY 1-p-q-r Q r F 4 :Nd 3+ p ,Yb 3+ q ,  Chemical Formula 4

where p denotes a real number satisfying 0<p≤1, q denotes a real number satisfying 0<q≤0.5, r denotes a real number satisfying 0≤r≤1, 0<p+q+r≤1 is satisfied, and Q denotes an element selected from the group consisting of La, Gd, Ce, Pr, Pm, Sm, Eu, Tb, Dy, Ho, Er, Tm, Lu, and a combination thereof.

4. The dye-sensitized upconversion nanophosphor of claim 3 , wherein the organic dye comprises C 45 H 51 N 2 NaO 8 S 3 , which is an IR-808 dye.

5. The dye-sensitized upconversion nanophosphor of claim 3 , wherein the organic dye consists of C 45 H 51 N 2 NaO 8 S 3 , which is an IR-808 dye.

6. A dye-sensitized upconversion nanophosphor, comprising:
a core;
a first shell surrounding at least part of the core; and
an organic dye bonded to a surface of the nanophosphor which has an absorption band ranging from 650 nm to 850 nm and which is excited in a near-infrared region to emit visible light,
wherein the core is made of a fluoride-based material co-doped with Yb 3+ , Ho 3+ , and Ce 3+ and expressed by Chemical Formula 5 below,
NaGd 1-a-b-c-d R d F 4 :Yb 3+ a ,Ho 3+ b ,Ce 3+ c ,  Chemical Formula 5

where “a” denotes a real number satisfying 0<a≤1, b denotes a real number satisfying 0<b≤0.2, c denotes a real number satisfying 0<c≤0.6, d denotes a real number satisfying 0≤d≤1, 0<a+b+c+d≤1 is satisfied, and R denotes an element selected from the group consisting of Y, La, Pr, Pm, Sm, Eu, Tb, Dy, Er, Tm, Lu, and a combination thereof, and
where the first shell is made of a fluoride-based crystalline material co-doped with Nd 3+ and Yb 3+ and expressed by Chemical Formula 6 below,
NaGd 1-p-q-r T r F 4 :Nd 3+ p ,Yb 3+ q ,  Chemical Formula 6

where p denotes a real number satisfying 0<p≤1, q denotes a real number satisfying 0<q≤0.5, r denotes a real number satisfying 0≤r≤1, 0<p+q+r≤1 is satisfied, and T denotes an element selected from the group consisting of Y, La, Ce, Pr, Pm, Sm, Eu, Tb, Dy, Ho, Er, Tm, Lu, and a combination thereof.

7. The dye-sensitized upconversion nanophosphor of claim 6 , further comprising a second shell surrounding at least part of the core and the first shell,
wherein the second shell is made of a fluoride-based material expressed by Chemical Formula 7 below,
NaGd 1-p-q X q F 4 :Nd 3+ p ,  Chemical Formula 7

where p denotes a real number satisfying 0≤p≤1, q denotes a real number satisfying 0≤q≤1, 0≤p+q≤1 is satisfied, and X denotes an element selected from the group consisting of Y, La, Ce, Pr, Pm, Sm, Eu, Tb, Dy, Ho, Yb, Er, Tm, Lu, and a combination thereof.

8. A display apparatus, comprising a dye-sensitized upconversion nanophosphor including:
a core;
a first shell surrounding at least part of the core; and
an organic dye bonded to a surface of the nanophosphor which has an absorption band ranging from 650 nm to 850 nm and which is excited in a near-infrared region to emit visible light.

9. A fluorescent contrast agent comprising the dye-sensitized upconversion nanophosphor of claim 1 .

10. An anti-counterfeiting code comprising the dye-sensitized upconversion nanophosphor of claim 1 .

11. A display apparatus, comprising the dye-sensitized upconversion nanophosphor of claim 1 .

12. A display apparatus comprising the dye-sensitized upconversion nanophosphor of claim 3 .

13. A fluorescent contrast agent comprising the dye-sensitized upconversion nanophosphor of claim 3 .

14. An anti-counterfeiting code comprising the dye-sensitized upconversion nanophosphor of claim 3 .

15. A display apparatus comprising the dye-sensitized upconversion nanophosphor of claim 6 .

16. A fluorescent contrast agent comprising the dye-sensitized upconversion nanophosphor of claim 6 .

17. An anti-counterfeiting code comprising the dye-sensitized upconversion nanophosphor of claim 6 .

Assignees

• Korea Inst Sci & Tech

Inventors

• Jang Ho Seong
• Han Joon Soo
• Hong A Ra
• Cho So Hye
• Lee Seung Yong
• Ko Hyung Duk

Classifications

• C09K11/025

  non-luminescent particle coatings or suspension media · CPC title

• A61K49/0019

  characterised by the fluorescent group, e.g. oligomeric, polymeric or dendritic molecules · CPC title

• A61K49/0093

  Nanoparticle, nanocapsule, nanobubble, nanosphere, nanobead, i.e. having a size or diameter smaller than 1 micrometer, e.g. polymeric nanoparticle · CPC title

• C09K11/7791

  with alkali or alkaline earth metals · CPC title

• C09K11/02 Primary

  Use of particular materials as binders, particle coatings or suspension media therefor · CPC title