Method of preparing nanocrystals

• US 7,229,497 B2
• Filed: 08/19/2004
• Issued: 06/12/2007
• Est. Priority Date: 08/26/2003
• Status: Active Grant

• Current Assignee: Massachusetts Institute of Technology
• Original Assignee: Massachusetts Institute of Technology
• Inventors: Yen, Brian K. H., Bawendi, Moungi G., Jensen, Klavs F., Stott, Nathan E.
• Primary Examiner(s): HITESHEW, FELISA CARLA
• Application Number:
  US10/921,306
• Publication Number:
  US 20050112849A1
• Time in Patent Office: 1,027 Days
• Field of Search: 117/68, 117/3, 117/11, 117/75, 977/762, 977/720, 428/402
• US Class Current: 117/68
• CPC Class Codes: C30B 29/48 AIIBVI compounds wherein A is Zn, Cd or Hg, and B is S, Se or Te
• CPC Class Codes: C30B 29/605 Products containing multiple oriented crystallites, e.g. columnar crystallites
• CPC Class Codes: C30B 7/14 the crystallising materials being formed by chemical reactions in the solution
• CPC Class Codes: Y10S 977/72 On an electrically conducting, semi-conducting, or semi-insulating substrate

Abstract

A population of nanocrystals having a narrow and controllable size distribution and can be prepared by a continuous flow method.

Claims

1. A method of manufacturing a population of nanocrystals, comprising:

heating a mixture of an M-source and an X donor in a fluid in a reaction zone to a growth temperature for a preselected amount of time; and

cooling the mixture below the growth temperature to stop growth of the nanocrystals.

2. A method of manufacturing a population of nanocrystals, comprising:

combining an M-source and an X donor in a fluid in a mixing region to form a mixture;

transporting the mixture through a reaction zone, the mixture being heated in the reaction zone to a temperature for a time sufficient to grow a nanocrystal; and

transporting the mixture from the reaction zone to a growth stopping zone to form the population of nanocrystals.

3. The method of claim 2 wherein the M-source is an M-containing salt.

4. The method of claim 3, wherein M is Cd, Zn, Mg, Hg, Al, Ga, In, or Tl and X is O, S, Se, Te, N, P, As, or Sb.

5. The method of claim 3, wherein the M-containing salt is a halide, carboxylate, carbonate, hydroxide, or diketonate.

6. The method of claim 3, wherein the M-containing salt is cadmium acetylacetonate, cadmium iodide, cadmium bromide, cadmium chloride, cadmium hydroxide, cadmium carbonate, cadmium acetate, cadmium oxide, zinc acetylacetonate, zinc iodide, zinc bromide, zinc chloride, zinc hydroxide, zinc carbonate, zinc acetate, zinc oxide, magnesium acetylacetonate, magnesium iodide, magnesium bromide, magnesium chloride, magnesium hydroxide, magnesium carbonate, magnesium acetate, magnesium oxide, mercury acetylacetonate, mercury iodide, mercury bromide, mercury chloride, mercury hydroxide, mercury carbonate, mercury acetate, aluminum acetylacetonate, aluminum iodide, aluminum bromide, aluminum chloride, aluminum hydroxide, aluminum carbonate, aluminum acetate, gallium acetylacetonate, gallium iodide, gallium bromide, gallium chloride, gallium hydroxide, gallium carbonate, gallium acetate, indium acetylacetonate, indium iodide, indium bromide, indium chloride, indium hydroxide, indium carbonate, indium acetate, thallium acetylacetonate, thallium iodide, thallium bromide, thallium chloride, thallium hydroxide, thallium carbonate, or thallium acetate.

7. The method of claim 6, further comprising cooling the mixture in the growth stopping zone.

8. The method of claim 2, wherein the mixture includes an amine.

9. The method of claim 8, wherein the amine is a primary amine.

10. The method of claim 9, wherein the primary amine is a C₈–

C₂₀ alkyl amine.

11. The method of claim 8, wherein the primary amine is a C₈–

C₂₀ alkyl amine, the 1,2-diol is a C₆–

C₂₀ alkyl diol, and the M-source is an M-containing salt, the M-containing salt being a halide, carboxylate, carbonate, hydroxide, or diketonate.

12. The method of claim 11, wherein the X donor includes a phosphine chalcogenide, a bis(silyl) chalcogenide, dioxygen, an ammonium salt, or a tris(silyl) pnictide.

13. The method of claim 2, wherein combining the M-source and the X donor includes contacting a metal, M, or an M-containing salt, and a reducing agent to form an M-containing precursor.

14. The method of claim 13, wherein the reducing agent includes an alkyl phosphine, a 1,2-diol or an aldehyde.

15. The method of claim 14, wherein the 1,2-diol is a C₆–

C₂₀ alkyl diol or the aldehyde is a C₆–

C₂₀ aldehyde.

16. The method of claim 2, wherein a nanocrystal in the population photoluminesces with a quantum efficiency of at least 10%.

17. The method of claim 2, further comprising selecting a ratio of the M-source and the X donor to grow the population of nanocrystals to have a predetermined average size.

18. The method of claim 2, further comprising selecting the temperature of reaction zone to grow the population of nanocrystals to have a predetermined average size.

19. The method of claim 2, further comprising selecting a ratio of the M-source and the X donor and the temperature of reaction zone to grow the population of nanocrystals to have a predetermined average size.

20. The method of claim 2, wherein the population of nanocrystals has an average particle size in the range of about 20 Å

to about 125 Å

.

21. The method of claim 2, wherein the fluid includes a coordinating solvent.

22. The method of claim 2, wherein the population of nanocrystals is monodisperse.

23. The method of claim 2, further comprising forming an overcoating of a semiconductor material on a surface of a nanocrystal in the population.

24. The method of claim 2, wherein the population emits light in a spectral range of no greater than about 75 nm full width at half max (FWHM).

25. The method of claim 2, wherein the population exhibits less than a 15% rms deviation in diameter of the nanocrystal.

26. The method of claim 2, wherein transporting the mixture includes flowing the mixture through a conduit.

27. The method of claim 2, further comprising introducing a gas phase into the mixture during transport.

28. The method of claim 2, wherein transporting the mixture includes segmented flowing of the mixture through a conduit.

29. The method of claim 2, wherein the temperature is between 150 and 350°

C.

30. The method of claim 2, wherein the time is less than 5 minutes.