Nanocrystal particles and processes for synthesizing the same

Patent metadata

Field	Value
Publication number	US-9834724-B2
Application number	US-201414494673-A
Country	US
Kind code	B2
Filing date	Sep 24, 2014
Priority date	Sep 26, 2013
Publication date	Dec 5, 2017
Grant date	Dec 5, 2017

Abstract

A nanocrystal particle including at least one semiconductor material and at least one halogen element, the nanocrystal particle including: a core comprising a first semiconductor nanocrystal; and a shell surrounding the core and comprising a crystalline or amorphous material, wherein the halogen element is present as being doped therein or as a metal halide.

First claim

What is claimed is:

1. A nanocrystal particle comprising at least one semiconductor material and at least one halogen element,
wherein the nanocrystal particle has a core-shell structure including a core comprising a first semiconductor nanocrystal; and
a shell surrounding the core and comprising a crystalline or amorphous semiconductor material, and
wherein the at least one halogen element is present as being doped therein or as a metal halide,
wherein the at least one halogen element comprises fluorine,
wherein the fluorine is included in an interface between the core and the shell, in the shell, or in the interface between the core and the shell and in the shell,
wherein the semiconductor nanocrystal of the core comprises InP,
wherein the crystalline or amorphous semiconductor material of the shell comprises ZnS, ZnSe, ZnSeS, or a combination thereof,
wherein the nanocrystal particle comprises a bond between the zinc and the fluorine,
wherein the nanocrystal particle has a quantum yield of greater than or equal to about 50%, and
wherein the nanocrystal particle does not include cadmium.

2. The nanocrystal particle of claim 1 , wherein the fluorine is present at an interface of the core and the shell, and in the shell.

3. The nanocrystal particle of claim 1 , wherein the shell is a multi-layered shell comprising an inner shell, an outer shell on the inner shell, a first interface between the core and the inner shell, and a second interface between the inner shell and the outer shell, each comprising a composition different from one another and wherein each is independently crystalline or amorphous, and
wherein the halogen element is included in a region selected from the inner shell, the outer shell, the first interface, and the second interface, and a combination thereof.

4. The nanocrystal particle of claim 1 , wherein the at least one halogen element is included in an amount of greater than or equal to about 0.05 mole percent, based on the molar amount of the metal included in the core of the nanoparticle.

5. The nanocrystal crystal particle of claim 1 , wherein the shell comprises a material having a composition different from the first semiconductor nanocrystal and having a bandgap which is larger than a bandgap of the first semiconductor nanocrystal.

6. The nanocrystal particle of claim 1 , wherein the nanoparticle further comprises a ligand compound coordinating a surface of the nanocrystal particle.

7. The nanocrystal particle of claim 6 , wherein the ligand compound comprises a compound represented by RCOOH, RNH 2 , R 2 NH, R 3 N, RSH, R 3 PO, R 3 P, ROH, RCOOR′, RPO(OH) 2 , or R 2 P(O)OH, or a combination thereof,
wherein R and R′ are each independently selected from a C1 to C24 alkyl group, a C2 to C24 alkenyl group, and a C6 to C20 aryl group.

8. A process for synthesizing a nanocrystal particle of claim 1 , the process comprising:
obtaining a first mixture including a first precursor comprising the second metal, a ligand compound, and a solvent;
heating the first mixture;
contacting a source of fluorine, a second precursor, and the core comprising the first semiconductor nanocrystal with the first mixture, which is heated, to obtain a second mixture; and
heating the second mixture to a reaction temperature to react the first precursor and the second precursor to obtain a nanocrystal particle comprising a semiconductor material and the fluorine.

9. The process of synthesizing a nanocrystal particle of claim 8 , wherein the first precursor comprising the second metal is in a form of an elemental metal, an alkylated metal compound, a metal alkoxide, a metal carboxylate, a metal nitrate, a metal perchlorate, a metal sulfate, a metal acetylacetonate, a metal halide, a metal cyanide, a metal hydroxide, a metal oxide, a metal peroxide, or a combination thereof, and
wherein the second precursor comprises sulfur or selenium, a compound comprising sulfur or selenium, or a combination thereof.

10. The process of synthesizing a nanocrystal particle of claim 8 , wherein the second precursor is selected from sulfur (S), selenium (Se), selenide, hexanethiol, octanethiol, decanethiol, dodecanethiol, hexadecanethiol, mercaptopropylsilane, sulfur-trioctylphosphine, sulfur-tributylphosphine, sulfur-triphenylphosphine, sulfur-trioctylamine, bis(trimethylsilyl)sulfide, ammonium sulfide, sodium sulfide, selenium-trioctylphosphine, selenium-tributylphosphine, selenium-triphenylphosphine, and a combination thereof.

11. The process of synthesizing a nanoparticle of claim 8 , wherein the ligand compound comprises a compound represented by a formula selected from RCOOH, RNH 2 , R 2 NH, R 3 N, RSH, R 3 PO, R 3 P, ROH, RCOOR′, RPO(OH) 2 , or R 2 POOH, and a combination thereof, wherein R and R′ are independently selected from a C1 to C24 alkyl group, a C2 to C24 alkenyl group, and a C6 to C20 aryl group.

12. The process of synthesizing a nanocrystal particle of claim 8 , wherein the source of the halogen element is selected from HF, NH 4 F, HBF 4 , an ionic liquid including a halogen, and a combination thereof.

13. The process of synthesizing a nanocrystal particle of claim 8 , wherein the source of the halogen element is added in the first mixture in an amount of greater than or equal to about 0.5 mole percent, based on a total moles of the metal of the first precursor.

14. The process of synthesizing a nanoparticle of claim 8 , wherein contacting the source of the halogen element with the first mixture comprises dissolving the source of the halogen element in a carrier solvent to obtain a solution and adding the solution to the first mixture, and
wherein the carrier solvent is selected from water, a ketone, a primary amine, a secondary amine, a tertiary amine, a heterocyclic compound having a nitrogen atom, a C6 to C40 olefin, a C6 to C40 aliphatic hydrocarbon, a C6 to C30 aromatic hydrocarbon substituted with a C1 to C20 alkyl group, a primary, secondary, or tertiary phosphine substituted with a C6 to C22 alkyl group, a primary, secondary, or tertiary phosphine oxide substituted with a C6 to C22 alkyl group, an aromatic ether, an aromatic alcohol, and a combination thereof.

15. The process of synthesizing a nanocrystal particle of claim 14 , wherein the solution has a molar concentration of the source of the halogen element of greater than or equal to about 0.001 moles per liter.

16. A device including the nanocrystal particle of claim 1 .

17. The device of claim 16 , wherein the device is a light emitting diode, an organic light emitting diode, a sensor, a solar cell, an imaging sensor, or a liquid crystal display.

18. The nanoparticle of claim 1 , wherein the nanocrystal particle comprises an In—F 2 bond and a Zn—F bond, as determined by time-of-flight secondary-ion mass spectrometry.

19. The nanocrystal particle of claim 1 , wherein the nanocrystal particle has a quantum yield of greater than or equal to about 60%.

Assignees

• Samsung Electronics Co Ltd

Inventors

• Kim Hyunki
• Jun Shin Ae
• Jang Eun Joo
• Kim Yongwook
• Kim Tae Gon
• Won Yuho
• Kim Taekhoon
• Jang Hyo Sook

Classifications

• Y10S977/892

  Liquid phase deposition · CPC title

• B82Y40/00

  Manufacture or treatment of nanostructures · CPC title

• Y10S977/774

  Exhibiting three-dimensional carrier confinement, e.g. quantum dots · CPC title

• C09K11/61

  containing fluorine, chlorine, bromine, iodine or unspecified halogen elements · CPC title

• C09K11/883 Primary

  with zinc or cadmium · CPC title