Surface Functionalised Nanoparticles

• US 20100068522A1
• Filed: 08/07/2009
• Published: 03/18/2010
• Est. Priority Date: 08/07/2008
• Status: Active Grant

• Current Assignee: Nanoco Technologies Limited (Nanoco Group Plc)
• Original Assignee: Nanoco Technologies Limited (Nanoco Group Plc)
• Inventors: Daniels, Steven M., Pickett, Nigel, Glarvey, Paul, McCairn, Mark C., Mushtaq, Imrana
• Granted Patent: US 8,597,730 B2
• Time in Patent Office: Days
• US Class Current: 428/402
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C01P 2002/82 by IR- or Raman-data
• CPC Class Codes: C01P 2004/64 Nanometer sized, i.e. from 1-100 nanometer
• CPC Class Codes: C07F 19/00 Metal compounds according to more than one of main groups C07F1/00 - C07F17/00
• CPC Class Codes: C07F 9/02 Phosphorus compounds sugar phosphates C07H11/04; nucleotides C07H19/00, C07H21/00; nucleic acids C07H21/00
• CPC Class Codes: C09C 3/006 Combinations of treatments provided for in groups C09C3/04 - C09C3/12
• CPC Class Codes: C09C 3/063 Coating
• CPC Class Codes: C09C 3/08 Treatment with low-molecular-weight non-polymer organic compounds C09C3/006, C09C3/048 take precedence
• CPC Class Codes: C09C 3/10 Treatment with macromolecular organic compounds C09C3/006 takes precedence
• CPC Class Codes: C09K 11/02 Use of particular materials as binders, particle coatings or suspension media therefor
• CPC Class Codes: C09K 11/025 non-luminescent particle coatings or suspension media
• CPC Class Codes: C09K 11/565 with zinc cadmium
• CPC Class Codes: C09K 11/70 containing phosphorus
• CPC Class Codes: Y10T 428/2982 Particulate matter [e.g., sphere, flake, etc.]
• CPC Class Codes: Y10T 428/2991 Coated

Abstract

A process for the production of surface functionalised nanoparticles, such as the production of semiconductor quantum dot nanoparticles incorporating surface-bound functional groups that increase the ease with which the dots can be employed in applications, such as incorporation into solvents, inks, polymers, glasses, metals, electronic materials and devices, bio-molecules and cells. Embodiments of the method include reacting first and second nanoparticle precursor species in the presence of a nanoparticle surface binding ligand X—Y—Z where X is a nanoparticle surface binding group, Y is a linker group, and Z is a functional group, in which Y comprises a polyethyleneglycol group and/or Z comprises an aliphatic group incorporating a terminal unsaturated group, the reaction being effected under conditions permitting binding of said surface binding ligand to the growing nanoparticles to produce said surface functionalised nanoparticles.

Claims

1. A method for producing surface functionalised nanoparticles comprising:

reacting first and second nanoparticle precursor species in the presence of a nanoparticle surface binding ligand having the formula X—

Y—

Z,

wherein X is a nanoparticle surface binding group, Y is a linker group, and Z is a functional group, in which Y comprises a polyethyleneglycol group and/or Z comprises an aliphatic group incorporating a terminal unsaturated group, said reaction being effected under conditions permitting binding of said surface binding ligand to growing nanoparticles to produce said surface functionalised nanoparticles.

2. A method according to claim 1, wherein said first nanoparticle precursor species is contacted by said nanoparticle surface binding ligand so as to effect binding of said surface binding ligand to said first nanoparticle precursor species prior to reacting said first nanoparticle precursor species with said second nanoparticle precursor species.

3. A method according to claim 1, wherein the first nanoparticle precursor species contains a first ion to be incorporated into the growing nanoparticles and the second nanoparticle precursor species contains a second ion to be incorporated into the growing nanoparticles.

4. A method according to claim 3, wherein the first ion is selected from group 11, 12, 13, or 14 of the periodic table and the second ion is selected from group 14, 15, or 16 of the periodic table.

5. A method according to claim 3, wherein the first and second nanoparticle precursor species are reacted in the presence of a molecular cluster compound.

6. A method according to claim 5, wherein said molecular cluster compound contains third and fourth ions, at least one of said third and fourth ions being different from said first and second ions contained in the first and second nanoparticle precursor species respectively.

7. A method according to claim 6, wherein the third ion and fourth ion are each separately selected from group 11, 12, 13, 14, 15, or 16 of the periodic table.

8. A method according to claim 5, wherein said molecular cluster compound is contacted by said first nanoparticle precursor species prior to being contacted by said second nanoparticle precursor species.

9. A method according to claim 1, wherein during the reaction the first nanoparticle precursor species is added in one or more portions and the second nanoparticle precursor species is added in one or more portions.

10. A method according to claim 9, wherein the first nanoparticle precursor species is added in two or more portions and a temperature of a reaction mixture containing the first and second nanoparticle precursor species and the nanoparticle surface binding ligand is increased between the addition of each portion of the first nanoparticle precursor species.

11. A method according to claim 9, wherein the second nanoparticle precursor species is added in two or more portions and a temperature of a reaction mixture containing the first and second nanoparticle precursor species and the nanoparticle surface binding ligand is increased between the addition of each portion of the second nanoparticle precursor species.

12. A method according to claim 1, wherein the first nanoparticle precursor species is a core nanoparticle and the second nanoparticle precursor species contains a first ion to form at least part of a shell to be deposited on a surface of said core nanoparticle.

13. A method according to claim 1, wherein the second nanoparticle precursor species is a core nanoparticle and the first nanoparticle precursor species contains a first ion to form at least part of a shell to be deposited on a surface of said core nanoparticle.

14. A method according to claim 12 or 13, wherein during the reaction the first nanoparticle precursor species is added in one or more portions and the second nanoparticle precursor species is added in one or more portions.

15. A method according to claim 14, wherein the first nanoparticle precursor species is added in two or more portions and a temperature of a reaction mixture containing the first and second nanoparticle precursor species and the nanoparticle surface binding ligand is increased between the addition of each portion of the first nanoparticle precursor species.

16. A method according to claim 14, wherein the second nanoparticle precursor species is added in two or more portions and a temperature of a reaction mixture containing the first and second nanoparticle precursor species and the nanoparticle surface binding ligand is increased between the addition of each portion of the second nanoparticle precursor species.

17. A method according to claim 12 or 13, wherein the method further comprises reacting said core nanoparticle and said nanoparticle precursor species with a third nanoparticle precursor species containing a second ion to form at least a portion of the shell to be deposited on the surface of said core nanoparticle.

18. A method according to claim 17, wherein during the reaction the third nanoparticle precursor species is added in one or more portions.

19. A method according to claim 18, wherein the third nanoparticle precursor species is added in two or more portions and a temperature of a reaction mixture containing the first, second and third nanoparticle precursor species and the nanoparticle surface binding ligand is increased between the addition of each portion of the third precursor species.

20. A method according to claim 1, wherein the functional group of the surface binding ligand is a charged or polar group, or a crosslinkable or polymerizable group.

21. A method according to claim 1, wherein the functional group of the surface binding ligand is selected from the group consisting of a hydroxide salt, alkoxide salt, carboxylate salt, ammonium salt, sulfonate salt, and phosphate salt.

22. A method according to claim 1, wherein said nanoparticle surface binding ligand is a polymeric compound.

23. A method according to claim 22, wherein said polymeric compound is a polyether.

24. A method according to claim 22, wherein said polymeric compound comprises an alkoxide group and a carboxylate group.

25. A method according to claim 1, wherein said terminal unsaturated group is a vinyl group.

26. A method according to claim 1, wherein X comprises at least one carboxylic acid group or at least one thiol group.

27. A method according to claim 1, wherein Y comprises a straight or branched aliphatic group, or an aromatic group.

28. A method according to claim 1, wherein the nanoparticle surface binding ligand is poly(oxyethylene glycol)_n monomethyl ether acetic acid with n=1 to 5000.

29. A method according to claim 1, wherein the nanoparticle surface binding ligand is selected from the group consisting of 10-Undecylenic acid and 11-mercapto-undecene.

30. A method according to claim 1, wherein the nanoparticle surface binding ligand has a formula

37. A surface functionalised nanoparticle produced using the method according to claim 1, 31 or 33, said surface functionalised nanoparticle comprising a nanoparticle bound to a nanoparticle surface binding ligand, said ligand incorporating a nanoparticle binding group and a functional group.

31. A method for producing surface functionalised core semiconductor nanoparticles, the method comprising:

reacting a first core nanoparticle precursor species containing a first ion to be incorporated into growing nanoparticles with a second core nanoparticle precursor species containing a second ion to be incorporated into the growing nanoparticles,

wherein said reaction is effected in the presence of a nanoparticle surface binding ligand incorporating a nanoparticle binding group and a functional group, under conditions permitting binding of said surface binding ligand to the growing nanoparticles to produce said surface functionalised core semiconductor nanoparticles.

32. A method according to claim 31, wherein the first and second core nanoparticle precursor species are reacted in the presence of a molecular cluster compound.

33. A method for producing surface functionalised core-shell semiconductor nanoparticles, the method comprising:

reacting a core semiconductor nanoparticle with a first nanoparticle precursor species containing a first ion to form at least a portion of a shell to be deposited on a surface of said core semiconductor nanoparticle, thereby growing a core-shell nanoparticle,

wherein said reaction is effected in the presence of a nanoparticle surface binding ligand incorporating a nanoparticle binding group and a functional group, said reaction being effected under conditions permitting binding of said surface binding ligand to the surface of the growing core-shell semiconductor nanoparticles to produce said surface functionalised core-shell semiconductor nanoparticles.

34. A method according to claim 33, wherein said core semiconductor nanoparticle is contacted by said nanoparticle surface binding ligand so as to effect binding of said surface binding ligand to said core semiconductor nanoparticle prior to reacting said core semiconductor nanoparticle with said first nanoparticle precursor species.

35. A method according to claim 34, wherein said first nanoparticle precursor species is contacted by said nanoparticle surface binding ligand so as to effect binding of said surface binding ligand to said first nanoparticle precursor species prior to reacting said first nanoparticle precursor species with said core semiconductor nanoparticle.

36. A method according to claim 33, wherein the method further comprises reacting said core semiconductor nanoparticle and said first nanoparticle precursor species with a second nanoparticle precursor species containing a second ion to form at least a portion of the shell to be deposited on the surface of said core semiconductor nanoparticle.