Surface chemical modification of nanocrystals

• US 9,595,363 B2
• Filed: 11/12/2013
• Issued: 03/14/2017
• Est. Priority Date: 12/06/2012
• Status: Active Grant

• Current Assignee: Regents of the University of California (University of California)
• Original Assignee: Regents of the University of California (University of California)
• Inventors: Helms, Brett Anthony, Milliron, Delia Jane, Rosen, Evelyn Louise, Buonsanti, Raffaella, Llordes, Anna
• Primary Examiner(s): MC GINTY, DOUGLAS J
• Application Number:
  US14/078,340
• Publication Number:
  US 20140158950A1
• Time in Patent Office: 1,218 Days
• Field of Search: 252/521.1, 252/512, 252/519.4, 252/519.33, 252/519.34, 252/518.1, 359/265, 359/270, 359/275, 423/509, 423/561.1, 423/633, 423/622, 423/594.9, 423/263, 423/610, 427/58, 427/108, 427/164, 427/165, 420/507, 420/416, 420/466
• US Class Current: 1/1
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: B82Y 40/00 Manufacture or treatment of nanostructures
• CPC Class Codes: H01B 1/22 the conductive material comprising metals or alloys

Abstract

Nanocrystals comprising organic ligands at surfaces of the plurality of nanocrystals are provided. The organic ligands are removed from the surfaces of the nanocrystals using a solution comprising a trialkyloxonium salt in a polar aprotic solvent. The removal of the organic ligands causes the nanocrystals to become naked nanocrystals with cationic surfaces.

Claims

1. A method comprising:

providing a plurality of nanocrystals, wherein the plurality of nanocrystals comprise organic ligands at surfaces of the plurality of nanocrystals; and

removing the organic ligands from the surfaces of the plurality of nanocrystals using a solution comprising a trialkyloxonium salt in a polar aprotic solvent, wherein removal of the organic ligands causes the plurality of nanocrystals to become a plurality of naked nanocrystals with cationic surfaces.

2. The method of claim 1, further comprising:

providing a dispersion comprising the plurality of nanocrystals in a non-polar solvent; and

mixing the solution comprising the trialkyloxonium salt with the dispersion to remove the organic ligands from the surfaces of the plurality of nanocrystals in the dispersion.

3. The method of claim 2, wherein the non-polar solvent comprises at least one of hexane, toluene, or chloroform.

4. The method of claim 2, further comprising purifying the plurality of nanocrystals based on performing the following comprising:

mixing a first liquid into the dispersion comprising the plurality of naked nanocrystals, wherein the plurality of nanocrystals are all insolvent in the first liquid; and

precipitating out the plurality of naked nanocrystals from the dispersion.

5. The method of claim 4, further comprising:

re-dispersing the plurality of naked nanocrystals into a second liquid to form a new dispersion that acts as a stable dispersant for the plurality of naked nanocrystals, wherein the second liquid comprises at least one of N,N-dimethylformamide (DMF) or hexamethylphosporamide (HMPA).

6. The method of claim 5, further comprising:

depositing the new dispersion onto a substrate to form a film comprising the plurality of naked nanocrystals; and

evaporating out the second liquid from the film.

7. The method of claim 1, further comprising:

coating surfaces of the naked nanocrystals with a polymer comprising poly acrylic acid (PAA), wherein the polymer acts as a stabilizer in an aqueous buffer.

8. The method of claim 1, wherein the polar aprotic solvent comprises at least one of N,N-dimethylformamide (DMF), acetonitrile or dichloromethane.

9. The method of claim 1, wherein the trialkyloxonium salt comprises at least one of trimethyloxonium, triethyloxonium or tripropyloxonium.

10. The method of claim 1, wherein the solution further comprises at least one of tetrafluoroborate, hexafluoroborate, hexachloroantimonate, tetrachloroaurate, tetrabromoaurate, tetrachloroferrate or tetrabromoferrate to act as counter ions when the organic ligands are stripped from the surfaces of the plurality of nanocrystals.

11. The method of claim 1, further comprising:

depositing a dispersion comprising the plurality of nanocrystals having the organic ligands onto a substrate to form a film on the substrate; and

treating the film with the solution comprising the trialkyloxonium salt and the polar aprotic solvent to remove the organic ligands from the plurality of nanocrystals in the film.

12. A method comprising:

providing a dispersion comprising a plurality of nanocrystals in a polar aprotic solvent, wherein the plurality of nanocrystals are naked nanocrystals having cationic surfaces;

adding a polymer comprising a nanocrystal tethering domain and porogenic domain to the dispersion; and

forming an article having an ordered composite from the dispersion, the ordered composite comprising (i) a polymer matrix formed from the porogenic domain of the polymer and (ii) the plurality of nanocrystals embedded in the polymer matrix at the nanocrystal tethering domain.

13. The method of claim 12, further comprising:

thermally or chemically treating the article to remove the polymer and transform the ordered composite into a mesoporous architecture comprising the plurality of nanocrystals arranged in regular lattices that are ordered in all dimensions.

14. The method of claim 12, wherein:

the polymer comprises a block copolymer;

the nanocrystal tethering domain comprises a first polymer of the block copolymer, the first polymer comprising at least one of poly(N,N-dimethylacrylamide) (PDMA), poly(N,N-dimethylacrylamide-co-acrylic acid), polyoxazalines, polypeptoids, poly(vinylpyridines), or poly(acrylic acid); and

the porogenic domain comprises a second polymer of the block copolymer, the second polymer comprising at least one of homomeric polyisoprene, polybutadiene, polyacrylates, polymethacrylates, polystyrene (PS), polynorbornenes, polyesters, polyethers, polycarbonates, polyethylene, branched polyethylene, polypropylene, or a copolymer therefrom.

15. The method of claim 14, further comprising:

controlling a dimensionality of a wall of the article by controlling a first volume fraction of the first polymer in the block copolymer and a second volume fraction of the second polymer in the block copolymer, wherein the wall is increased in size by increasing the first volume fraction.

16. The method of claim 14, wherein the block copolymer is a block copolymer supramolecule, the method further comprising:

adding an initial block copolymer into a first solvent that is a solvent for both the first polymer and the second polymer; and

adding a second solvent that is a solvent for a first one of the first polymer and the second polymer but not for a second one of the first polymer and the second polymer to cause the initial block copolymer to preassemble into the block copolymer supramolecule.

17. The method of claim 16, wherein the first solvent comprises N,N-dimethylformamide (DMF) and the second solvent comprises one of water, methanol or ethanol.

18. The method of claim 16, wherein forming the article comprises:

mixing an additional liquid into the dispersion, wherein the plurality of nanocrystals, the first polymer and the second polymer are all insolvent in the additional liquid; and

wherein the article comprising the ordered composite of the polymer and the plurality of nanocrystals crashes out of the dispersion.

19. The method of claim 12, wherein forming the article comprises:

depositing the dispersion onto a substrate to form a film comprising the ordered composite.

20. The method of claim 19, wherein the polymer comprises a block copolymer, wherein the block copolymer has not been preassembled into a block copolymer supramolecule, and wherein after depositing the dispersion onto the substrate the polymer self assembles and arranges the plurality of nanocrystals as the polar aprotic solvent evaporates.

21. The method of claim 12, further comprising:

controlling a dimensionality of a wall of the article by controlling a first volume fraction of the nanocrystals to a second volume fraction of the polymer.

22. A composition comprising:

a plurality of inorganic nanocrystals, wherein the plurality of inorganic nanocrystals are naked nanocrystals comprising ligand-stripped cationic surfaces.

23. The composition of claim 22, further comprising:

a polar aprotic solvent, the plurality of inorganic nanocrystals forming a stable dispersion in the polar aprotic solvent.

24. The composition of claim 23, wherein the polar aprotic solvent comprises at least one of N,N-dimethylformamide (DMF), acetonitrile or dichloromethane.

25. The composition of claim 22, further comprising:

a film, the plurality of inorganic nanocrystals being a component of the film.

26. The composition of claim 22, further comprising:

a mesoporous architecture comprising the plurality of nanocrystals arranged in regular lattices that are ordered in all dimensions.

27. The composition of claim 22, further comprising:

an ordered composite comprising (i) a polymer matrix formed from a porogenic domain of a polymer and (ii) the plurality of nanocrystals embedded in the polymer matrix at a nanocrystal tethering domain of the polymer.

28. The composition of claim 27, wherein:

the polymer comprises a block copolymer;

the nanocrystal tethering domain comprises a first polymer of the block copolymer; and

the porogenic domain comprises a second polymer of the block copolymer.

29. The composition of claim 28, wherein the first polymer comprises at least one of poly(N,N-dimethylacrylamide) (PDMA), poly(N,N-dimethylacrylamide-co-acrylic acid), polyoxazalines, polypeptoids, poly(vinylpyridines) or poly(acrylic acid), and the second polymer comprises at least one of homomeric polyisoprene, polybutadiene, polyacrylates, polymethacrylates, polystyrene (PS), polynorbornenes, polyesters, polyethers, polycarbonates, polyethylene, branched polyethylene, polypropylene, or a copolymer therefrom.

30. The composition of claim 22, wherein the plurality of nanocrystals comprise at least one of CdSe, CdSe/CdS, CdSe/ZnS, CdTe, PbSe, PbS, PbTe, α

-Fe₂O₃, ZnO, Al-doped ZnO, doped NaYF₄;

Yb/Tm, Ag, doped In₂O₃, indium tin oxide (ITO), CeO₂, TiO₂, Yb, Er-doped NaYF₄ or FePt.