Nanocrystal and preparation method thereof

Patent metadata

Field	Value
Publication number	US-9828395-B2
Application number	US-201615255369-A
Country	US
Kind code	B2
Filing date	Sep 2, 2016
Priority date	Mar 10, 2016
Publication date	Nov 28, 2017
Grant date	Nov 28, 2017

Abstract

A nanocrystal represented by the following Formula 1 and a preparation method thereof:

AMX 3 L  Formula 1
wherein A is cesium (Cs), rubidium (Rb), or an ammonium salt, M is germanium (Ge), tin (Sn), or lead (Pb), X is one or more selected from Cl, Br and I, and L is an organic functional group having one terminal selected from a phosphonic acid group, a carboxylic acid group, and an amino group.

First claim

What is claimed is:

1. A nanocrystal represented by Formula 1:
AMX 3 L  Formula 1

wherein A is selected from the group consisting of cesium (Cs), rubidium (Rb), and an ammonium salt,
M is selected from the group consisting of germanium (Ge), tin (Sn), and lead (Pb),
X is one or more selected from the group consisting of Cl, Br, and I, and
L is CH 3 (CH 2 ) 6 P(═O)(OH) 2 , CH 3 (CH 2 ) 7 P(═O)(OH) 2 , CH 3 (CH 2 ) 8 P(═O)(OH) 2 , CH 3 (CH 2 ) 9 P(═O)(OH) 2 , CH 3 (CH 2 ) 10 P(═O)(OH) 2 , CH 3 (CH 2 ) 11 P(═O)(OH) 2 , or CH 3 (CH 2 ) 12 P(═O)(OH) 2 .

2. The nanocrystal of claim 1 , wherein the nanocrystal represented by Formula 1 is a compound represented by Formula 2:
AMI x Br 3-x L  Formula 2

wherein A is selected from the group consisting of cesium (Cs), rubidium (Rb), and an ammonium salt,
M is selected from the group consisting of Ge, Sn, and Pb, and
0<x≦3.

3. The nanocrystal of claim 1 , wherein the nanocrystal is a compound represented by the following Formula 3:
CsPbI x Br 3-x L  Formula 3

wherein 0<x≦3.

4. The nanocrystal of claim 1 , wherein the nanocrystal is a compound represented by the following Formula 4:
CsPbI x Br 3-x L  Formula 4

wherein 0<x≦3.

5. The nanocrystal of claim 1 , wherein AMX 3 in the nanocrystal is CsPbI 3 , CsPbBr 1.92 I 1.08 , CsPbBr 1.8 I 1.2 , CsPbBr 1.7 I 1.3 , CsPbBr 1.6 I 1.4 , CsPbBr 1.1 I 1.9 , CsPbBr 1.2 I 1.8 , CsPbBr 0.9 I 2.1 , CsPbBr 0.7 I 2.3 , CsPbBr 0.5 I 2.5 , CsPbBr 0.3 I 2.7 , or CsPbBr 0.1 I 2.9 .

6. The nanocrystal of claim 4 , wherein the nanocrystal represented by Formula 4 is a nanocrystal of CsPbBr 1.92 I 1.08 .

7. The nanocrystal of claim 1 , wherein the nanocrystal is a colloidal perovskite quantum dot.

8. The nanocrystal of claim 1 , wherein an emission wavelength of the nanocrystal is 500 to 700 nm, and a difference in the emission wavelength after 1 week is less than 50 nm.

9. The nanocrystal of claim 1 , wherein a content of one or more selected from the group consisting of Cl, Br and I, when extracted from the nanocrystal to an aqueous layer, is 80 mg/l or less, and a content of one or more selected from the group consisting of cesium (Cs) and rubidium (Rb), when extracted from the nanocrystal to an aqueous layer, is 40 mg/l or less.

10. A method of preparing the nanocrystal of claim 1 , the method comprising:
mixing a metal halide comprising one or more selected from the group consisting of germanium (Ge), tin (Sn), and lead (Pb) with a solvent to form a mixture, and drying the mixture to form a dried mixture; and
adding, to the dried mixture, a surfactant, a compound comprising an organic functional group having one terminal as a phosphonic acid group, and an organic acid comprising one or more selected from the group consisting of cesium (Cs), rubidium (Rb), and an ammonium salt,
followed by mixing and heat-treatment.

11. The method of claim 10 , wherein the compound comprising an organic functional group having one terminal as a phosphonic acid group is added in an amount of 0.1 to 1 mole, based on 1 mole of the metal halide.

12. The method of claim 10 , wherein the organic acid is at least one selected from the group consisting of cesium oleate and rubidium oleate.

13. The method of claim 10 , wherein the heat treatment is performed at a temperature of from 100 to 200° C.

14. The method of claim 10 , wherein the compound comprising an organic functional group having one terminal as a phosphonic acid group is 1-tetradecyl phosphonic acid, n-hexyl phosphonic acid, or n-octadecyl phosphonic acid.

15. The method of claim 10 , wherein the metal halide is at least one selected from the group consisting of lead iodide (PbI 2 ), lead bromide (PbBr 2 ), germanium iodide (GeI 2 ), germanium bromide (GeBr 2 ), tin iodide (SnI 2 ), and tin bromide (SnBr 2 ).

16. The method of claim 10 , wherein the surfactant is at least one selected from the group consisting of C 1 -C 18 carboxylic acid, C 3 -C 18 alkyl amine, and C 1 -C 18 alcohol.

17. The method of claim 16 , wherein the C 1 -C 18 carboxylic acid is selected from the group consisting of oleic acid, octanoic acid, stearic acid, and decanoic acid,
the C 1 -C 18 alkylamine is selected from the group consisting of oleylamine, octylamine, hexadecylamine, octadecylamine, and tri-n-octylamine, and
the C 1 -C 18 alcohol is selected from the group consisting of oleyl alcohol, octanol, and butanol.

18. The method of claim 10 , wherein the solvent is one or more selected from the group consisting of 1-octadecene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-eicosene.

19. The method of claim 10 , wherein the drying is performed at a temperature of from 100 to 150° C.

Assignees

• Samsung Electronics Co Ltd

Inventors

• KOH Weonkyu
• Park Sungjun
• Yun Dongjin
• Lee Junho

Classifications

• C07F9/3808 Primary

  Acyclic saturated acids which can have further substituents on alkyl · CPC title

• B82Y40/00

  Manufacture or treatment of nanostructures · CPC title

• Y10S977/95

  Electromagnetic energy · CPC title

• B82Y20/00

  Nanooptics, e.g. quantum optics or photonic crystals · CPC title

• Y10S977/896

  Chemical synthesis, e.g. chemical bonding or breaking · CPC title