Attachment of organic molecules to group III, IV or V substrates

• US 6,943,054 B2
• Filed: 07/28/2003
• Issued: 09/13/2005
• Est. Priority Date: 07/25/2003
• Status: Expired due to Fees

• Current Assignee: Califonria University of The Regents of The, North Carolina State University (University of North Carolina System)
• Original Assignee: Regents of the University of California (University of California)
• Inventors: Bocian, David F., Lindsey, Jonathan S., Liu, Zhiming, Yasseri, Amir A., Loewe, Robert S.
• Primary Examiner(s): WILSON, CHRISTIAN D
• Application Number:
  US10/628,868
• Publication Number:
  US 20050019500A1
• Time in Patent Office: 778 Days
• Field of Search: 257/40, 438/99, 438/502
• US Class Current: 438/99
• CPC Class Codes: B82Y 10/00 Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
• CPC Class Codes: G11C 13/0014 comprising cells based on organic memory material
• CPC Class Codes: G11C 13/0016 comprising polymers
• CPC Class Codes: H01M 14/005 Photoelectrochemical storage cells light sensitive devices H01G9/20, semiconductors sensitive to light H01L31/00
• CPC Class Codes: H01M 4/60 of organic compounds
• CPC Class Codes: H10K 10/701 Organic molecular electronic devices
• CPC Class Codes: H10K 30/10 comprising heterojunctions between organic semiconductors and inorganic semiconductors
• CPC Class Codes: H10K 71/10 Deposition of organic active material
• CPC Class Codes: H10K 71/12 using liquid deposition, e.g. spin coating
• CPC Class Codes: H10K 71/16 using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering
• CPC Class Codes: H10K 71/40 Thermal treatment, e.g. annealing in the presence of a solvent vapour
• CPC Class Codes: H10K 85/30 Coordination compounds
• CPC Class Codes: H10K 85/701 Langmuir Blodgett films
• CPC Class Codes: Y02E 10/549 Organic PV cells
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

This invention provides a new procedure for attaching molecules to semiconductor surfaces, in particular silicon. The molecules, which include, but are not limited to porphyrins and ferrocenes, have been previously shown to be attractive candidates for molecular-based information storage. The new attachment procedure is simple, can be completed in short times, requires minimal amounts of material, is compatible with diverse molecular functional groups, and in some instances affords unprecedented attachment motifs. These features greatly enhance the integration of the molecular materials into the processing steps that are needed to create hybrid molecular/semiconductor information storage devices.

Claims

1. A method of covalently coupling an organic molecule to a surface of a Group III, IV, or V element or to a semiconductor comprising a Group III, IV, or V element, said method comprising:

providing a heat resistant organic molecule derivatized with an attachment group; and

contacting the derivatized heat resistant organic molecule with a surface of said Group III, IV, or V element or semiconductor comprising a Group III, IV, or V element; and

heating the surface to a temperature of at least about 200°

C. whereby said attachment group forms a covalent bond with said surface.

2. The method of claim 1, wherein said surface is heated to a temperature of at least about 300°

C.

3. The method of claim 1, wherein said surface is heated to a temperature of at least about 400°

C.

4. The method of claim 1, wherein said organic molecule is a redox-active molecule.

5. The method of claim 1, wherein said organic molecule is selected from the group consisting of a porphyrin, a porphyrinic macrocycle, an expanded porphyrin, a contracted porphyrin, a linear porphyrin polymer, a porphyrinic sandwich coordination complex, and a porphyrin array.

6. The method of claim 1, wherein said organic molecule comprises a porphyrinic macrocycle substituted at a β

-position or at a meso-position.

7. The method of claim 1, wherein said organic molecule comprises a porphyrinic macrocycle containing at least two porphyrins of equal energies held apart from each other at a spacing less than about 50 Å

such that said molecule has an even or an odd hole oxidation where the hole hops between said two porphyrins, and wherein said odd hole oxidation state is different from and distinguishable from another oxidation state of said porphyrinic macrocycle.

8. The method of claim 1, wherein said attachment group is selected from the group consisting of 4-(hydroxymethyl)phenyl, 4-(S-acetylthiomethyl)phenyl, 4-(Se-acetylselenomethyl)phenyl, 4-(mercaptomethyl)phenyl, 4-(hydroselenomethyl)phenyl, 4-formylphenyl, 4-(bromomethyl)phenyl, 4-vinylphenyl, 4-ethynylphenyl, 4-allylphenyl, 4-[2-(trimethylsilyl)ethynyl]phenyl, 4-[2-(triisopropylsilyl)ethynyl]phenyl, 4-bromophenyl, 4-iodophenyl, 4-hydroxyphenyl, 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl bromo, iodo, hydroxymethyl, S-acetylthiomethyl, Se-acetylselenomethyl, mercaptomethyl, hydroselenomethyl, formyl, bromomethyl, chloromethyl, ethynyl, vinyl, allyl, 4-[2-(4-(hydroxymethyl)phenyl)ethynyl]phenyl, 4-(ethynyl)biphen-4′

-yl, 4-[2-(triisopropylsilyl)ethynyl]biphen-4′

-yl, 3,5-diethynylphenyl, and 2-bromoethyl.

9. The method of claim 1, wherein the organic molecule derivatized with the attachment group is selected from the group consisting of 5-[4-(S-acetylthiomethyl)phenyl]-10,15,20-trimesitylporphinatozinc(II), 5-[4-(mercaptomethyl)phenyl]-10,15,20-trimesitylporphinatozinc(II), 5-[4-(hydroxymethyl)phenyl]-10,15,20-trimesitylporphinatozinc(II), 5-[4-(hydroxymethyl)phenyl]-10,15,20-tri-p-tolylporphinatozinc(II), 5-(4-allylphenyl)-10,15,20-trimesitylporphinatozinc(II), 5-(4-formylphenyl)-15-phenyl-10,20-di-p-tolylporphinatozinc(II), 5-(4-bromomethylphenyl)-10,15,20-trimesitylporphinatozinc(II), 5-(4-ethynylphenyl)-10,15,20-trimesitylporphinatozinc(II), 5-(4-iodophenyl)-10,15,20-trimesitylporphinatozinc(II), 5-(4-bromophenyl)-10,15,20-tri-p-tolylporphinatozinc(II), 5-(4-hydroxyphenyl)-10,15,20-trimesitylporphinatozinc(II), 5,10-bis(4-ethynylphenyl)-15,20-dimesitylporphinatozinc(II), 5-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-10,20-bis(3,5-di-tert-butylphenyl)-15-mesitylporphinatozinc(II), 5-iodo-10,20-bis(3,5-di-tert-butylphenyl)-15-mesitylporphinatozinc(II), 5,10-bis(4-iodophenyl)-15,20-dimesitylporphinatozinc(II), 5-[4-(2-(trimethylsilyl)ethynyl)phenyl]-10,15,20-trimesitylporphinatozinc(II), 5,15-bis(4-ethynylphenyl)-10,20-dimesitylporphinatozinc(II), 5,15-bis(4-iodophenyl)-10,20-dimesitylporphinatozinc(II), 5,10,15-tris(4-ethynylphenyl)-20-mesitylporphinatozinc(II), 5,15-bis(4-ethynylphenyl)-10,20-bis(4-tert-butylphenyl)porphinatozinc(II), 5,15-bis(4-ethynylphenyl)porphinatozinc(II), 5,15-bis(3-ethynylphenyl)-10,20-dimesitylporphinatozinc(II), 5,10,15,20-tetrakis(4-ethynylphenyl)porphinatozinc(II), 5,10-bis[4-(2-(trimethylsilyl)ethynyl)phenyl]-15,20-dimesitylporphinatozinc(II), 5-(3,5-diethynylphenyl)-10,15,20-trimesitylporphinatozinc(II), 3,7-dibromo-10,20-bis(3,5-di-tert-butylphenyl)-15-mesitylporphinatozinc(II), 5-[4-(2-(trimethylsilyl)ethynyl)phenyl]-10,15,20-tri-p-tolylporphinatozinc(II), 5-[4-(Se-acetylselenomethyl)phenyl]-10,15,20-trimesitylporphinatozinc(II), 5-(4-iodophenyl)-10,20-bis(3,5-di-tert-butylphenyl)-15-mesitylporphinatozinc(II), 5,10-bis(4-ethynylphenyl)-15,20-bis(4-tert-butylphenyl)porphinatozinc(II), 5,10-bis(4-ethynylbiphen-4′

-yl)-15,20-bis(4-tert-butylphenyl)porphinatozinc(II), 5-(4-vinylphenyl)-10,15,20-trimesitylporphinatozinc(II), 5-(4-vinylphenyl)-10,15,20-tri-p-tolylporphinatozinc(II), 5-(hydroxymethyl)-10,15,20-trimesitylporphinatozinc(II), 5-(4-allylphenyl)-10,15,20-tri-p-tolylporphinatozinc(II), 5-(4-allylphenyl)-10,15,20-tri-p-tolylporphinatocopper(II), type c triple decker [(tert-butyl)₄phthalocyaninato]Eu[(tert-butyl)₄phthalocyaninato]Eu[5,15-bis(4-ethynylphenyl)-10,20-bis(4-tert-butylphenyl)porphyrin], type c triple decker [(tert-butyl)₄phthalocyaninato]Eu[(tert-butyl)₄phthalocyaninato]Eu[5-[4-[2-(4-(hydroxymethyl)phenyl)ethynyl]phenyl]-10,15,20-tri-p-tolylporphyrin] 5,10-bis[4-(2-(triisopropylsilyl)ethynyl)biphen-4′

-yl]-15,20-bis(4-tert-butylphenyl)porphinatozinc(II), and 5,10-bis[4-(2-(triisopropylsilyl)ethynyl)phenyl]-15,20-bis(4-tert-butylphenyl)porphinatozinc(II).

10. The method of claim 1, wherein said Group III, IV, or V element is a Group IV element or a doped Group IV element.

11. The method of claim 10, wherein said Group III, IV, or V element is selected from the group consisting of silicon, germanium, doped silicon, and doped germanium.

12. The method of claim 11, wherein said surface is a doped germanium surface.

13. The method of claim 11, wherein said surface is a doped silicon surface.

14. The method of claim 13, wherein said surface is an n-doped silicon surface.

15. The method of claim 13, wherein said surface is a p-doped silicon surface.

16. The method of claim 11, wherein said surface is a hydrogen passivated surface.

17. The method of claim 1, wherein said contacting comprises selectively applying said organic molecule to certain regions of said surface and not to other regions.

18. The method of claim 17, wherein said contacting comprises:

placing a protective coating on said surface in regions where said organic molecule is not to be attached;

contacting said solution with the surface; and

removing the protective coating to provide regions of the surface without said organic molecule.

19. The method of claim 17, wherein said contacting comprises contact printing of a solution comprising said organic molecule onto said surface.

20. The method of claim 17, wherein said contacting comprises inkjet printing a solution comprising said organic molecule onto said surface.

21. The method of claim 17, wherein said contacting comprises spraying or dropping a solution comprising said organic molecule onto said surface.

22. The method of claim 11, wherein said contacting comprises coating said surface with a solution comprising said organic molecule.

23. The method of claim 22, wherein said method further comprises etching regions of said surface to remove said organic molecule.

24. A surface of a Group III, IV, or V element or a surface of a semiconductor comprising a Group III, IV, or V element having an organic molecule coupled thereto through a covalent bond, wherein said organic molecule is coupled to said surface by the method of claim 1.

25. The method of claim 24, wherein said organic molecule is a redox-active molecule.

26. The method of claim 25, wherein said organic molecule is selected from the group consisting of a porphyrin, a porphyrinic macrocycle, an expanded porphyrin, a contracted porphyrin, a linear porphyrin polymer, a porphyrinic sandwich coordination complex, and a porphyrin array.

27. The method of claim 25, wherein said organic molecule comprises a porphyrinic macrocycle substituted at a β

-position or at a meso-position.

28. The method of claim 25, wherein said organic molecule comprises a porphyrinic macrocycle containing at least two porphyrins of equal energies held apart from each other at a spacing less than about 50 Å

such that said molecule has an odd hole oxidation state permitting the hole to hop between said two porphyrins and wherein said odd hole oxidation state is different from and distinguishable from another oxidation state of said porphyrinic macrocycle.

29. The method of claim 24, wherein the attachment group is selected from the group consisting of -4-(hydroxymethyl)phenyl, 4-(S-acetylthiomethyl)phenyl, 4-(Se-acetylselenomethyl)phenyl, 4-(mercaptomethyl)phenyl, 4-(hydroselenomethyl)phenyl, 4-formylphenyl, 4-(bromomethyl)phenyl, 4-vinylphenyl, 4-ethynylphenyl, 4-allylphenyl, 4-[2-(trimethylsilyl)ethynyl]phenyl, 4-[2-(triisopropylsilyl)ethynyl]phenyl, 4-bromophenyl, 4-iodophenyl, 4-hydroxyphenyl, 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl bromo, iodo, hydroxymethyl, S-acetylthiomethyl, Se-acetylselenomethyl, mercaptomethyl, hydroselenomethyl, formyl, bromomethyl, chloromethyl, ethynyl, vinyl, allyl, 4-[2-(4-(hydroxymethyl)phenyl)ethynyl]phenyl, 4-(ethynyl)biphen-4′

-yl, 4-[2-(triisopropylsilyl)ethynyl]biphen-4′

-yl, 3,5-diethynylphenyl, and 2-bromoethyl.

30. The method of claim 24, wherein the organic molecule derivatized with the attachment group, before coupling to the surface is selected from the group consisting of 5-[4-(S-acetylthiomethyl)phenyl]-10,15,20-trimesitylporphinatozinc(II), 5-[4-(mercaptomethyl)phenyl]-10,15,20-trimesitylporphinatozinc(II), 5-[4-(hydroxymethyl)phenyl]-10,15,20-trimesitylporphinatozinc(II), 5-[4-(hydroxymethyl)phenyl]-10,15,20-tri-p-tolylporphinatozinc(II), 5-(4-allylphenyl)-10,15,20-trimesitylporphinatozinc(II), 5-(4-formylphenyl)-15-phenyl-10,20-di-p-tolylporphinatozinc(II), 5-(4-bromomethylphenyl)-10,15,20-trimesitylporphinatozinc(II), 5-(4-ethynylphenyl)-10,15,20-trimesitylporphinatozinc(II), 5-(4-iodophenyl)-10,15,20-trimesitylporphinatozinc(II), 5-(4-bromophenyl)-10,15,20-tri-p-tolylporphinatozinc(II), 5-(4-hydroxyphenyl)-10,15,20-trimesitylporphinatozinc(II), 5,10-bis(4-ethynylphenyl)-15,20-dimesitylporphinatozinc(II), 5-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-10,20-bis(3,5-di-tert-butylphenyl)-15-mesitylporphinatozinc(II), 5-iodo-10,20-bis(3,5-di-tert-butylphenyl)-15-mesitylporphinatozinc(II), 5,10-bis(4-iodophenyl)-15,20-dimesitylporphinatozinc(II), 5-[4-(2-(trimethylsilyl)ethynyl)phenyl]-10,15,20-trimesitylporphinatozinc(II), 5,15-bis(4-ethynylphenyl)-10,20-dimesitylporphinatozinc(II), 5,15-bis(4-iodophenyl)-10,20-dimesitylporphinatozinc(II), 5,10,15-tris(4-ethynylphenyl)-20-mesitylporphinatozinc(II), 5,15-bis(4-ethynylphenyl)-10,20-bis(4-tert-butylphenyl)porphinatozinc(II), 5,15-bis(4-ethynylphenyl)porphinatozinc(II), 5,15-bis(3-ethynylphenyl)-10,20-dimesitylporphinatozinc(II), 5,10,15,20-tetrakis(4-ethynylphenyl)porphinatozinc(II), 5,10-bis[4-(2-(trimethylsilyl)ethynyl)phenyl]-15,20-dimesitylporphinatozinc(II), 5-(3,5-diethynylphenyl)-10,15,20-trimesitylporphinatozinc(II), 3,7-dibromo-10,20-bis(3,5-di-tert-butylphenyl)-15-mesitylporphinatozinc(II), 5-[4-(2-(trimethylsilyl)ethynyl)phenyl]-10,15,20-tri-p-tolylporphinatozinc(II), 5-[4-(Se-acetylselenomethyl)phenyl]-10,15,20-trimesitylporphinatozinc(II), 5-(4-iodophenyl)-10,20-bis(3,5-di-tert-butylphenyl)-15-mesitylporphinatozinc(II), 5,10-bis(4-ethynylphenyl)-15,20-bis(4-tert-butylphenyl)porphinatozinc(II), 5,10-bis(4-ethynylbiphen-4′

-yl)-15,20-bis(4-tert-butylphenyl)porphinatozinc(II), 5-(4-vinylphenyl)-10,15,20-trimesitylporphinatozinc(II), 5-(4-vinylphenyl)-10,15,20-tri-p-tolylporphinatozinc(II), 5-(hydroxymethyl)-10,15,20-trimesitylporphinatozinc(II), 5-(4-allylphenyl)-10,15,20-tri-p-tolylporphinatozinc(II), 5-(4-allylphenyl)-10,15,20-tri-p-tolylporphinatocopper(II), type c triple decker [(tert-butyl)₄phthalocyaninato]Eu[(tert-butyl)₄phthalocyaninato]Eu[5,15-bis(4-ethynylphenyl)-10,20-bis(4-tert-butylphenyl)porphyrin], type c triple decker [(tert-butyl)₄phthalocyaninato]Eu[(tert-butyl)₄phthalocyaninato]Eu[5-[4-[2-(4-(hydroxymethyl)phenyl)ethynyl]phenyl]-10,15,20-tri-p-tolylporphyrin] 5,10-bis[4-(2-(triisopropylsilyl)ethynyl)biphen-4′

-yl]-15,20-bis(4-tert-butylphenyl)porphinatozinc(II), and 5,10-bis [4-(2-(triisopropylsilyl)ethynyl)phenyl]-15,20-bis(4-tert-butylphenyl)porphinatozinc(II).

31. The method of claim 24, wherein said Group III, IV, or V element is a Group IV element or a doped Group IV element.

32. The method of claim 31, wherein said Group III, IV, or V element is selected from the group consisting of silicon, germanium, doped silicon, and doped germanium.

33. The method of claim 31, wherein said surface is a doped germanium surface.

34. The method of claim 31, wherein said surface is a doped silicon surface.

35. The method of claim 34, wherein said surface is an n-doped silicon surface.

36. The method of claim 34, wherein said surface is a p-doped silicon surface.

37. The method of claim 24, wherein said surface comprises a surface in a transistor.

38. The method of claim 24, wherein said surface comprises a surface in a memory device.

39. A method of fabricating an ordered molecular assembly, said method comprising:

providing a solution comprising a heat resistant organic molecule derivatized with an attachment group;

contacting said solution with a surface comprising a Group III, IV, or V element at a plurality of discrete locations on said surface; and

heating said surface to a temperature of at least about 200°

C. whereby the attachment groups form covalent bonds with said surface at said plurality of discrete locations.

40. The method of claim 39, wherein said surface is heated to a temperature of at least about 300°

C.

41. The method of claim 39, wherein said surface is heated to a temperature of at least about 400°

C.

42. A kit for coupling an organic molecule to the surface of a type III, IV, or V material, said kit comprising:

a container containing a heat resistant organic molecule derivatized with an attachment group, and instructional materials teaching coupling the organic molecule to the surface by heating the surface to a temperature of a out 200°

C. or more.