High-temperature attachment of organic molecules to substrates

• US 8,529,996 B2
• Filed: 03/19/2007
• Issued: 09/10/2013
• Est. Priority Date: 07/25/2003
• Status: Expired due to Fees

• Current Assignee: Regents of the University of California (University of California), North Carolina State University (University of North Carolina System)
• Original Assignee: Regents of the University of California (University of California), North Carolina State University (University of North Carolina System)
• Inventors: Bocian, David F., Lindsey, Jonathan S., Liu, Zhiming, Yasseri, Amir A., Misra, Veena, Zhao, Qian, Li, Qiliang, Surthi, Shyam, Loewe, Robert S.
• Primary Examiner(s): TUROCY, DAVID P
• Application Number:
  US11/688,194
• Publication Number:
  US 20070212897A1
• Time in Patent Office: 2,367 Days
• Field of Search: 427/372.2, 427/384, 427/388.1, 427/331
• US Class Current: 427/255.6
• CPC Class Codes: B82Y 10/00 Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
• CPC Class Codes: G11B 9/14 using microscopic probe means , i.e. recording or reproducing by means directly associated with the tip of a microscopic electrical probe as used in Scanning Tunneling Microscopy [STM] or Atomic Force Microscopy [AFM] for inducing physical or electrical perturbations in a recording medium; Record carriers or media specially adapted for such transducing of information marking using electrical current B41M5/20; measuring roughness or irregularity of surfaces G01B7/34; details of scanning-probe microscopes G01Q
• CPC Class Codes: G11B 9/149 characterised by the memorising material or structure
• 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 71/16 using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering
• CPC Class Codes: H10K 71/164 using vacuum deposition
• 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 coupling a redox-active molecule to a surface to form a self-assembled monolayer, said method comprising:

heating a heat-resistant organic redox-active molecule bearing an attachment group and/or said surface to a temperature of at least about 100°

C., wherein said redox active 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; and

contacting said molecule in a gas phase to said surface whereby said molecule couples to said surface forming said monolayer, and where the attached molecule remains stable and can sustain setting and resetting of its oxidation state through thousands of cycles.

2. The method of claim 1, wherein said organic molecule is electrically coupled to said surface.

3. The method of claim 1, wherein said heating is under an inert atmosphere.

4. The method of claim 1, wherein said heating comprises heating said molecule to a gas phase.

5. The method of claim 1, wherein said heating comprises heating said molecule and/or said surface while said molecule is in contact with said surface.

6. The method of claim 1, wherein said heating comprises applying said molecule to said surface and then simultaneously or subsequently heating the molecule and/or surface.

7. The method of claim 1, wherein said heating said molecule comprises heating said molecule to a temperature of at least about 200°

C.

8. The method of claim 1, wherein said heating said molecule comprises heating said molecule to a temperature of at least about 300°

C.

9. The method of claim 1, wherein said heating said molecule comprises heating said molecule to a temperature of at least about 400°

C.

10. The method of any of claims 1 through 9, wherein said molecule couples to said surface via a covalent linkage.

11. The method of claim 1, wherein said heating occurs in a CVD device.

12. The method of claim 1, wherein said heating occurs in an MBE device.

13. The method of claim 1, wherein said surface comprises a material selected from the group consisting of a Group III element, a Group IV element, a Group V element, a semiconductor comprising a Group III element, a semiconductor comprising a Group IV element, a semiconductor comprising a Group V element, a transition metal, and a transition metal oxide.

14. The method of claim 13, wherein said Group III, IV, or V element is a Group IV element or a doped Group IV element.

15. The method of claim 14, wherein said Group III, IV, or V element is selected from the group consisting of silicon, germanium, doped silicon, and doped germanium.

16. The method of claim 1, wherein said surface comprises a transition metal or an oxide of a transition metal selected from the group consisting of tungsten, tantalum, and niobium.

17. The method of claim 1, wherein said surface comprises an element, alloy, oxide or nitride of a metal selected from the group consisting of Ga, Au, Ag, Cu, Al, Ta, Ti, Ru, Ir, Pt, Pd, Os, Mn, Hf, Zr, V, Nb, La, Y, Gd, Sr, Ba, Cs, Cr, Co, Ni, Zn, Ga, In, Cd, Rh, Re, W, and Mo.

18. The method of claim 1, wherein said surface comprises a metal selected from the group consisting of Ga, Au, Ag, Cu, Al, Ta, Ti, Ru, Ir, Pt, Pd, Os, Mn, Hf, 20 Zr, V, Nb, La, Y, Gd, Sr, Ba, Cs, Cr, Co, Ni, Zn, Ga, In, Cd, Rh, Re, W, and Mo.

19. The method of claim 1, wherein said surface is a hydrogen passivated surface.

20. The method of claim 1, wherein said redox-active molecule comprises a porphyrinic macrocycle substituted at a β

-position or at a meso-position.

21. The method of claim 1, wherein said redox-active 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.

22. The method of claim 1, wherein said attachment group comprises an aryl functional group.

23. The method of claim 22, wherein said aryl functional group comprises a functional group selected from the group consisting of bromo, iodo, hydroxy, hydroxymethyl, formyl, bromomethyl, vinyl, allyl, S-acetylthiomethyl, Seacetylselenomethyl, ethynyl, 2-(trimethylsilyl)ethynyl, mercapto, mercaptomethyl, 4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl, and dihydroxyphosphoryl.

24. The method of claim 1, wherein said attachment group comprises an alkyl functional group.

25. The method of claim 24, wherein said alkyl attachment group comprises a functional group selected from the group consisting of bromo, iodo, hydroxy, formyl, vinyl, mercapto, selenyl, S-acetylthio, Se-acetylseleno, ethynyl, 2-(trimethylsilyl)ethynyl, 4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl, and dihydroxyphosphoryl.

26. The method of claim 1, wherein said attachment group comprises an alcohol or a phosphonate.

27. 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, 44244-(hydroxymethyl)phenyl)ethynyl]phenyl, 4-(ethynyl)biphen-4′

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

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

28. The method of claim 1, wherein said heat-resistant organic molecule bearing an 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), 544-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).

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

30. The method of claim 29, wherein said contacting comprises:

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

contacting said molecule with the surface; and

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

31. The method of claim 29, wherein said contacting comprises contacting said surface with said molecule and subsequently etching selected regions of said surface to remove said organic molecule.

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

33. The method of claim 1, wherein said contacting comprises plasma-assisted vapor deposition.

34. The method of claim 1, wherein said contacting comprises sputtering.

35. The method of claim 1, wherein said heat-resistant organic molecule comprises a mixture at least two different species of heat-resistant organic molecule.