Methods of producing cadmium selenide multi-pod nanocrystals

Patent metadata

Field	Value
Publication number	US-9493351-B2
Application number	US-201113811835-A
Country	US
Kind code	B2
Filing date	Dec 7, 2011
Priority date	Dec 7, 2011
Publication date	Nov 15, 2016
Grant date	Nov 15, 2016

Abstract

Methods for the non-hot-injection synthesis of semiconductor nanocrystals are described. For example, a multi-podal cadmium selenide nanocrystal may be produced by a method including heating a degassed mixture comprising cadmium oxide, selenium, trioctylphosphine, and a carboxylic acid in a non-coordinating solvent from about room temperature to about 210° C., where the multi-podal cadmium selenide nanocrystal may be a tetrapodal cadmium selenide nanocrystal.

First claim

What is claimed is:

1. A method of producing a semiconductor nanocrystal, the method comprising:
degassing a mixture comprising a first inorganic compound, a second inorganic compound, a nanocrystal-forming ligand, and a carboxylic acid in a non-coordinating solvent at a temperature of about 20° C. to about 120° C.;
wherein the first inorganic compound comprises a period II to period VI element and the second inorganic compound comprises a period IV to period VI element; and
heating the mixture to elevate the temperature of the mixture from the degassing temperature to a temperature of about 160° C. to about 300° C. to produce the semiconductor nanocrystal,
wherein the semiconductor nanocrystal comprises a multi-podal semiconductor nanocrystal.

2. The method of claim 1 , wherein the semiconductor nanocrystal is selected from the group consisting of zinc oxide, zinc sulfide, zinc telluride, zinc selenide, cadmium sulfide, cadmium selenide, cadmium telluride, lead sulfide, and lead selenide.

3. The method of claim 1 , wherein the first inorganic compound is selected from the group consisting of cadmium oxide, zinc oxide, and lead oxide.

4. The method of claim 1 , wherein the second inorganic compound includes an element selected from the group consisting of sulfur, selenium, and tellurium.

5. The method of claim 1 , wherein the semiconductor nanocrystal comprises a tetrapodal semiconductor nanocrystal.

6. The method of claim 1 , further comprising adding a solution comprising a shell material to the semiconductor nanocrystal to produce a core shell semiconductor nanocrystal.

7. The method of claim 6 , wherein the shell comprises zinc sulfide.

8. A method of producing a multi-podal cadmium selenide nanocrystal, the method comprising:
degassing a mixture comprising cadmium oxide, selenium, trioctylphosphine, and a carboxylic acid in a non-coordinating solvent at a temperature of about 20° C. to about 120° C.; and
heating the mixture to elevate the temperature of the mixture from the degassing temperature to a temperature of about 160° C. to about 300° C. to produce the multi-podal cadmium selenide nanocrystal.

9. The method of claim 8 , wherein the carboxylic acid is selected from the group consisting of formic acid, acetic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, oxalic acid, benzoic acid, methanoic acid, ethanoic acid, propanoic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, octadecanoic acid, icosanoic acid, myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linoelaidic acid, α-linolenic acid, arachidonic acid, eicosapentaenoic acid, erucic acid, and docosahexaenoic acid.

10. The method of claim 8 , wherein the carboxylic acid comprises oleic acid.

11. The method of claim 8 , wherein heating the mixture comprises heating at a rate of about 4° C. to about 30° C. per minute.

12. The method of claim 8 , further comprising maintaining the temperature of the mixture at about 190° C. to about 300° C. for about 2 minutes to about 120 minutes.

13. The method of claim 8 , further comprising:
cooling the heated mixture; and
adding a polar solvent to the cooled mixture to precipitate the multi-podal cadmium selenide nanocrystal in the polar solvent.

14. The method of claim 13 , further comprising:
centrifuging the liquid comprising the precipitated multi-podal cadmium selenide nanocrystal to produce a pellet comprising the precipitated multi-podal cadmium selenide nanocrystal in a supernatant;
decanting the supernatant to isolate the pellet comprising the precipitated multi-podal cadmium selenide nanocrystal; and
adding a non-polar solvent to the pellet comprising the precipitated multi-podal cadmium selenide nanocrystal to produce a dispersion of the multi-podal cadmium selenide nanocrystal in the solvent.

15. The method of claim 14 , further comprising:
centrifuging the dispersion of the multi-podal cadmium selenide nanocrystal to provide a pellet comprising a purified multi-podal cadmium selenide nanocrystal in the non-polar solvent;
decanting the non-polar solvent to isolate the pellet comprising the purified multi-podal cadmium selenide nanocrystal; and
adding a second non-polar solvent to the pellet comprising the purified multi-podal cadmium selenide nanocrystal to produce a dispersion of the purified multi-podal cadmium selenide nanocrystal in the second non-polar solvent.

16. The method of claim 8 , further comprising drying the multi-podal cadmium selenide nanocrystal under vacuum.

17. A method of producing a core shell multi-podal nanocrystal, the method comprising:
degassing a first mixture comprising cadmium oxide, selenium, trioctylphosphine, and a carboxylic acid in a first non-coordinating solvent at a temperature of about 20° C. to about 120° C.;
heating the first mixture to elevate the temperature of the first mixture from the degassing temperature to a temperature of about 160° C. to about 300° C.;
cooling the first mixture to a temperature of about 120° C. to about 160° C.;
adding to the cooled first mixture a second mixture comprising zinc dimethyldithiocarbamate and a first amine in a second non-coordinating solvent at a temperature of about 20° C. to about 100° C., a third mixture comprising zinc acetate and a second amine in a third non-coordinating solvent at a temperature of about 100° C. to about 160° C., and a portion of a third amine to produce a fourth mixture;
heating the fourth mixture from a temperature of about 140° C. to about 200° C.; and
maintaining the temperature of the fourth mixture a temperature of about 140° C. to about 200° C. for about 20 minutes to produce a core shell multi-podal nanocrystal.

18. The method of claim 17 , wherein heating the first mixture comprises heating at a rate of about 4° C. to about 30° C. per minute.

19. The method of claim 17 , further comprising:
cooling the fourth mixture to a temperature of about 120° C. to about 160° C.;
adding to the cooled fourth mixture a fifth mixture comprising zinc dimethyldithiocarbamate and a fourth amine in a fourth non-coordinating solvent at a temperature of about 20° C. to about 100° C., a sixth mixture comprising zinc acetate and a fifth amine in a fifth non-coordinating solvent at a temperature of about 100° C. to about 160° C., and a portion of a sixth amine to produce a seventh mixture;
heating the seventh mixture from a temperature of about 140° C. to about 200° C.; and
maintaining the temperature of the seventh mixture at a temperature of about 140° C. to about 200° C. for about 30 minutes to produce a core shell multi-podal nanocrystal.

20. The method of claim 19 , further comprising:
cooling at least one of the fourth or seventh mixtures; and
adding a polar solvent to the cooled fourth or seventh mixture to precipitate the core shell multi-podal nanocrystal in the polar solvent.

21. The method of claim 20 , further comprising:
centrifuging the liquid comprising the precipitated core shell multi-podal nanocrystal to provide a pellet comprising the precipitated core shell multi-podal nanocrystal in a supernatant;
decanting the supernatant to isolate the pellet comprising the precipitated core shell multi-podal nanocrystal; and
adding a non-polar solvent to the pellet comprising the precipitated core shell multi-podal nanocrystal to produce a

Assignees

• Zhong Xinhua
• Zhang Wenjin
• Univ East China Science & Tech

Inventors

• Zhong Xinhua
• Zhang Wenjin

Classifications

• C01B19/007 Primary

  Tellurides or selenides of metals (C01B19/002 takes precedence) · CPC title

• C30B29/62

  Whiskers or needles · CPC title

• C30B9/08 Primary

  using other solvents · CPC title

• C30B29/46

  Sulfur-, selenium- or tellurium-containing compounds · CPC title