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

• US 7,230,268 B2
• Filed: 05/26/2005
• Issued: 06/12/2007
• Est. Priority Date: 07/25/2003
• Status: Active Grant

• 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: Lindsey, Jonathan S, Liu, Zhiming, Yasseri, Amir A, Loewe, Robert S, Bocian, David F
• Primary Examiner(s): Baumeister, B. William
• Assistant Examiner(s): Such, Matthew W.
• Application Number:
  US11/140,011
• Publication Number:
  US 20050217559A1
• Time in Patent Office: 747 Days
• Field of Search: 257/40, 257/E51.041, 438/99, 540/145
• US Class Current: 257/40
• 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 redox-active substrate comprising a Group III, IV, or V element having attached thereto a redox-active molecule where:

said redox-active molecule is covalently attached to the surface of said Group III, IV, or V element through an attachment group;

said redox-active molecule is stable at a temperature of at least about 300°

C.;

said redox-active molecule is an organic molecule 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

said covalent attachment is not by a silane.

2. The substrate of claim 1, wherein said redox-active molecule is coupled to the surface through a linker comprising an atom of carbon, oxygen, sulfur, or selenium.

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

-position or at a meso-position.

4. The substrate 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 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.

5. The substrate 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.

6. The substrate of claim 1, wherein the organic molecule and attachment group, before coupling to said 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)₄phthaloxcaninato]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).

7. The substrate of claim 1, wherein said Group III, IV, or V element is a Group IV element.

8. The substrate of claim 1, wherein said Group III, IV, or V element is silicon or germanium.

9. The method of claim 8, wherein said surface is a doped germanium surface.

10. The method of claim 8, wherein said surface is a doped silicon surface.

11. The method of claim 10, wherein said surface is an n-doped silicon surface.

12. The method of claim 10, wherein said surface is a p-doped silicon surface.

13. The substrate of claim 1, wherein said substrate comprises an electrochemical cell.

14. The substrate of claim 1, wherein said substrate comprises a plurality of memory elements.

15. The substrate of claim 1, wherein said substrate further comprises one or more integrated circuit elements.

16. The substrate of claim 15, wherein said circuit elements are selected from the group consisting of a transistor, a diode, a logic gate, and a rectifier.

17. The substrate of claim 1, wherein a redox-active molecule on said substrate is electrically coupled to a device that reads or sets the oxidation state of that molecule.

18. The substrate of claim 1, wherein a redox-active molecule on said substrate is coupled to a device selected from the group consisting of a voltammetric device, an amperometric device, a potentiometric device, a coulometric device, and impedance spectrometer.

19. The substrate of claim 1, wherein a redox-active molecule on said substrate is coupled to a sinusoidal voltammeter.