Semiconductor nanocrystals covalently bound to solid inorganic surfaces using self-assembled monolayers

• US 5,751,018 A
• Filed: 04/29/1994
• Issued: 05/12/1998
• Est. Priority Date: 11/22/1991
• Status: Expired due to Term

• Current Assignee: Regents of the University of California (University of California)
• Original Assignee: Regents of the University of California (University of California)
• Inventors: Alivisatos, A. Paul, Colvin, Vicki L.
• Primary Examiner(s): PASCAL, ROBERT J
• Assistant Examiner(s): PASCAL, ROBERT J
• Application Number:
  US08/235,265
• Time in Patent Office: 1,474 Days
• Field of Search: 148/33.4, 148/225, 148/228, 148/233, 257/40, 257/642, 257/64, 257/200, 257/614
• US Class Current: 257/64
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: H01L 21/02422 Non-crystalline insulating materials, e.g. glass, polymers
• CPC Class Codes: H01L 21/02425 Conductive materials, e.g. metallic silicides
• CPC Class Codes: H01L 21/02439 Materials
• CPC Class Codes: H01L 21/02499 Monolayers
• CPC Class Codes: H01L 21/02538 Group 13/15 materials
• CPC Class Codes: H01L 21/02543 Phosphides
• CPC Class Codes: H01L 21/02546 Arsenides
• CPC Class Codes: H01L 21/02551 Group 12/16 materials
• CPC Class Codes: H01L 21/02557 Sulfides
• CPC Class Codes: H01L 21/0256 Selenides
• CPC Class Codes: H01L 21/02601 Nanoparticles fullerenes H10K85/211

Abstract

Methods are described for attaching semiconductor nanocrystals to solid inorganic surfaces, using self-assembled bifunctional organic monolayers as bridge compounds. Two different techniques are presented. One relies on the formation of self-assembled monolayers on these surfaces. When exposed to solutions of nanocrystals, these bridge compounds bind the crystals and anchor them to the surface. The second technique attaches nanocrystals already coated with bridge compounds to the surfaces. Analyses indicate the presence of quantum confined clusters on the surfaces at the nanolayer level. These materials allow electron spectroscopies to be completed on condensed phase clusters, and represent a first step towards synthesis of an organized assembly of clusters. These new products are also disclosed.

Claims

1. A semiconductor assembly comprising:

a) a solid inorganic substrate surface;

b) a self-assembled monolayer of heterobifunctional bridging moieties covalently bonded thereto, each of said bridging moieties having two functional groups, with one of said functional groups covalently bonded to said substrate surface; and

c) semiconductor nanocrystals covalently bonded to said bridging moieties through a second of said two functional groups on each of said bridging moieties.

2. The semiconductor assembly of claim 1 wherein the solid inorganic substrate surface is an oxidic surface.

3. The semiconductor assembly of claim 2 wherein the solid inorganic substrate surface is a silicon oxide surface.

4. The semiconductor assembly of claim 2 wherein the solid inorganic substrate surface is an aluminum oxide surface.

5. The semiconductor assembly of claim 1 wherein the solid inorganic substrate surface is a solid metal substrate surface.

6. The semiconductor assembly of claim 5 wherein the solid metal substrate surface is a solid gold surface.

7. The semiconductor assembly of claim 5 wherein the solid metal substrate surface is a solid aluminum surface.

8. The semiconductor assembly of claim 1 wherein the semiconductor nanocrystals are III-V semiconductors.

9. The semiconductor assembly of claim 1 wherein the semiconductor hanocrystals are II-VI semiconductors.

10. The semiconductor assembly of claim 1 wherein the semiconductor is CdS.

11. The semiconductor assembly of claim 1 wherein the semiconductor is CdSe.

12. The semiconductor assembly of claim 1 wherein the semiconductor is ZnS.

13. The semiconductor assembly of claim 1 wherein the semiconductor is ZnSe.

14. The semiconductor assembly of claim 1 wherein the semiconductor is GaAs.

15. The semiconductor assembly of claim 1 wherein the semiconductor is InAs.

16. The semiconductor assembly of claim 1 wherein the semiconductor is GaP.

17. A semiconductor assembly comprising:

a) semiconductor nanocrystals;

b) one or more bridging moieties, each comprising an organic molecule having at least two functional groups and from 4 to 8 carbons between said functional groups, covalently bonded to said semiconductor nanocrystals through one of said least two functional groups; and

c) a surface covalently bonded to said one or more bridging moieties through another of said at least two functional groups on said bridging moieties.

18. The semiconductor assembly of claim 17 wherein each of said one or more bridging moieties comprises a dithiol having the formula H--S--R--S--H, wherein R is an organic group having from 4 to 8 carbons.

19. The semiconductor assembly of claim 17 wherein each of said one or more bridging moieties comprises a difunctional molecule having a thiol group and a carboxyl group.

20. The semiconductor assembly of claim 17 wherein said surface comprises a solid surface of a material selected from the group consisting of silicon oxide, aluminum oxide, and a metal.

21. The semiconductor assembly of claim 17 wherein said semiconductor nanocrystals are III-V semiconductors.

22. The semiconductor assembly of claim 17 wherein said semiconductor nanocrystals are II-VI semiconductors.

23. A semiconductor assembly comprising:

a) semiconductor nanocrystals;

b) a monolayer comprising a plurality of organic bridging moieties, each having at least two functional groups spaced apart by from 4 to 8 carbon atoms, and covalently bonded to said semiconductor nanocrystals through one of said at least two functional groups; and

c) a solid support surface covalently bonded to said monolayer of organic bridging moieties through another of said at least two or more functional groups on each of said plurality of bridging moieties comprising said monolayer.

24. The semiconductor assembly of claim 23 wherein each of said organic bridging moieties comprises a dithiol.

25. The semiconductor assembly of claim 23 wherein each of said organic bridging moieties comprises a difunctional molecule having a thiol group and a carboxyl group.

26. A semiconductor assembly comprising:

a) a solid inorganic substrate surface;

b) a self-assembled monolayer of homobifunctional bridging moieties covalently bonded thereto, each of said bridging moieties having two functional groups, with one of said functional groups covalently bonded to said substrate surface; and

c) semiconductor nanocrystals covalently bonded to said bridging moieties through a second of said two functional groups on each of said bridging moieties.

27. The semiconductor assembly of claim 26 wherein the solid inorganic substrate surface is an oxidic surface.

28. The semiconductor assembly of claim 27 wherein the solid inorganic substrate surface is a silicon oxide surface.

29. The semiconductor assembly of claim 27 wherein the solid inorganic substrate surface is an aluminum oxide surface.

30. The semiconductor assembly of claim 26 wherein the solid inorganic substrate surface is a solid metal surface.

31. The semiconductor assembly of claim 30 wherein the solid inorganic substrate surface is a solid gold surface.

32. The semiconductor assembly of claim 30 wherein the solid metal substrate surface is a solid aluminum surface.

33. The semiconductor assembly of claim 26 wherein the semiconductor nanocrystals are III-V semiconductors.

34. The semiconductor assembly of claim 26 wherein the semiconductor nanocrystals are II-VI semiconductors.

35. The semiconductor assembly of claim 26 wherein the semiconductor is CdS.

36. The semiconductor assembly of claim 26 wherein the semiconductor is CdSe.

37. The semiconductor assembly of claim 26 wherein the semiconductor is ZnS.

38. The semiconductor assembly of claim 26 wherein the semiconductor is ZnSe.

39. The semiconductor assembly of claim 26 wherein the semiconductor is GaAs.

40. The semiconductor assembly of claim 26 wherein the semiconductor is InAs.

41. The semiconductor assembly of claim 26 wherein the semiconductor is GaP.