In situ patterning of electrolyte for molecular information storage devices

• US 7,312,100 B2
• Filed: 04/30/2004
• Issued: 12/25/2007
• Est. Priority Date: 05/27/2003
• 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: North Carolina State University (University of North Carolina System)
• Inventors: Lindsey, Jonathan S., Misra, Veena, Kuhr, Werner G., Bocian, David F.
• Primary Examiner(s): Elms; Richard T.
• Assistant Examiner(s): Lulis; Michael
• Application Number:
  US10/837,028
• Publication Number:
  US 20050207208A1
• Time in Patent Office: 1,334 Days
• Field of Search: 977/DIG.1, 977/896, 977/943, 429/30, 429/303, 429/33, 429/42, 429/43, 524/200, 524/790, 530/391.3, 530/391.5, 530/391.9, 257/E21.007, 257/40, 365/151, 365/153, 205/334, 361/523, 424/1.53, 525/919, 840/8, 438/99
• 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 13/0009 RRAM elements whose operation depends upon chemical change
• CPC Class Codes: G11C 13/0014 comprising cells based on organic memory material
• CPC Class Codes: H10K 10/701 Organic molecular electronic devices
• CPC Class Codes: H10K 71/60 Forming conductive regions or layers, e.g. electrodes
• CPC Class Codes: H10K 85/30 Coordination compounds
• CPC Class Codes: H10K 85/60 Organic compounds having low molecular weight H10K85/10 - H10K85/50 take precedence
• CPC Class Codes: Y10S 977/896 Chemical synthesis, e.g. chemical bonding or breaking
• CPC Class Codes: Y10S 977/943 Information storage or retrieval using nanostructure

Abstract

This invention pertains to methods assembly of organic molecules and electrolytes in hybrid electronic. In one embodiment, a method is provided that involves contacting a surface/electrode with a compound of formula: R-L²-M-L¹-Z¹ where Z¹ is a surface attachment group; L¹ and L² are independently linker or covalent bonds; M is an information storage molecule; and R is a protected or unprotected reactive site or group; where the contacting results in attachment of the redox-active moiety to the surface via the surface attachment group; and ii) contacting the surface-attached information storage molecule with an electrolyte having the formula: J-Q where J is a charged moiety (e.g., an electrolyte); and Q is a reactive group that is reactive with the reactive group (R) and attaches J to the information storage molecule thereby patterning the electrolyte on the surface.

Claims

1. A method of patterning an electrolyte on a surface, said method comprising:

i) contacting said surface with a compound having the formula;

R-L²-M-L¹-Z¹

wherein

Z¹ is a surface attachment group;

L¹ and L² are independently selected linkers or covalent bonds;

M is an information storage molecule comprising a redox active moiety; and

R is a protected or unprotected reactive site or group;

whereby said contacting is under conditions that result in attachment of said redox-active moiety to said surface via said surface attachment group; and

ii) contacting the surface-attached redox-active moiety with an electrolyte having the formula;

J-Q

wherein

J is a charged moiety; and

Q is a reactive group that is reactive with said reactive group (R) under conditions that result in the covalent attachment of said charged moiety (J) to said information storage molecule thereby patterning said electrolyte on said surface.

2. The method of claim 1, wherein said surface attachment group (Z¹) reacts on contact with said surface.

3. The method of claim 1, wherein said surface attachment group (Z¹) is photo activated.

4. The method of claim 1, wherein said surface attachment group (Z¹) is heat activated.

5. The method of claim 1, wherein said surface attachment group (Z¹) is activated by electromagnetic radiation.

6. The method of claim 1, wherein J is positively charged.

7. The method of claim 1, wherein J is negatively charged.

8. The method of claim 1, wherein said redox-active moiety (M) is selected from the group consisting of a porphyrinic macrocycle, a porphyrin, a sandwich coordination compound of porphyrinic macrocycles, and a metallocene.

9. The method of claim 1, wherein said redox-active moiety is selected from the group consisting of a linear polyene, a cyclic polyene, a heteroatom-substituted linear polyene, a heteroatom-substituted cyclic polyene, a tetrathiafulvalene, a tetraselenafulvalene, a metal coordination complex, a buckyball, a triarylamine, a 1,4-phenylenediamine, a xanthene, a flavin, a phenazine, a phenothiazine, an acridine, a quinoline, a 2,2′

-bipyridyl, a 4,4′

-bipyridyl, a tetrathiotetracene, and a peri-bridged naphthalene dichalcogenide.

10. The method of claim 1, wherein Z¹ is a protected or unprotected reactive site or group selected from the group consisting of a carboxylic acid, an alcohol, a thiol, a selenol, a tellurol, a phosphonic acid, a phosphonothioate, an amine, and a nitrile.

11. The method of claim 1, wherein -L¹-Z¹ is selected from the group consisting of

4-carboxyphenyl, 2-(4-carboxyphenyl)ethynyl, 4-(2-(4-carboxyphenyl)ethynyl)phenyl,

4-carboxymethylphenyl, 4-(3-carboxypropyl)phenyl, 4-(2-(4-carboxymethylphenyl)ethynyl) phenyl,

4-hydroxyphenyl, 2-(4-hydroxyphenyl)ethynyl, 4-(2-(4-hydroxyphenyl)ethynyl)phenyl,

4-hydroxymethylphenyl, 4-(2-hydroxyethyl)phenyl, 4-(3-hydroxypropyl)phenyl,

4-(2-(4-hydroxymethylphenyl)ethynyl)phenyl, 4-mercaptophenyl,

2-(4-mercaptophenyl)ethynyl, 4-(2-(4-mercaptophenyl)ethynyl)phenyl,

4-mercaptomethylphenyl, 4-(2-mercaptoethyl)phenyl, 4-(3-mercaptopropyl)phenyl,

4-(2-(4-mercaptomethylphenyl)ethynyl)phenyl, 4-selenylphenyl,

2-(4-selenylphenyl)ethynyl, 4-selenylmethylphenyl, 4-(2-selenylethyl)phenyl,

4-(3-selenylpropyl)phenyl, 4-selenylmethylphenyl, 4-(2-(4-selenylphenyl)ethynyl)phenyl,

4-tellurylphenyl, 2-(4-tellurylphenyl)ethynyl, 4-(2-(4-tellurylphenyl)ethynyl)phenyl,

4-tellurylmethylphenyl, 4-(2-tellurylethyl)phenyl, 4-(3-tellurylpropyl)phenyl,

4-(2-(4-tellurylmethylphenyl)ethynyl)phenyl, 4-(dihydroxyphosphoryl)phenyl,

2-[4-(dihydroxyphosphoryl)phenyl]ethynyl,

4-[2-[4-(dihydroxyphosphoryl)phenyl]ethynyl]phenyl,

4-[(dihydroxyphosphoryl)methyl]phenyl, 4-[2-(dihydroxyphosphoryl)ethyl]phenyl,

4-[2-[4-(dihydroxyphosphoryl)methylphenyl]ethynyl]phenyl,

4-(hydroxy(mercapto)phosphoryl)phenyl,

2-[4-(hydroxy(mercapto)phosphoryl)phenyl]ethynyl,

4-[2-[4-(hydroxy(mercapto)phosphoryl)phenyl]ethynyl]phenyl,

4-[(hydroxy(mercapto)phosphoryl)methyl]phenyl,

4-[2-(hydroxy(mercapto)phosphoryl)ethyl]phenyl,

4-[2-[4-(hydroxy(mercapto)phosphoryl)methylphenyl]ethynyl]phenyl, 4-cyanophenyl,

2-(4-cyanophenyl)ethynyl, 4-[2-(4-cyanophenyl)ethynyl]phenyl, 4-(cyanomethyl)phenyl,

4-(2-cyanoethyl)phenyl, 4-[2-[4-(cyanomethyl)phenyl]ethynyl]phenyl;

4-cyanobiphenyl,

4-aminophenyl, 2-(4-aminophenyl)ethynyl, 4-[2-(4-aminophenyl)ethynyl]phenyl,

4-aminobiphenyl, 1,1,1-tris[4-(S-acetylthiomethyl)phenyl]methyl,

4-{1,1,1-tris[4-(S-acetylthiomethyl)phenyl]methyl}phenyl,

1,1,1-tris[4-(dihydroxyphosphoryl)phenyl]methyl,

4-{1,1,1-tris[4-(dihydroxyphosphoryl)phenyl]methyl}phenyl,

1,1,1-tris[4-(dihydroxyphosphorylmethyl)phenyl]methyl, and

4-{1,1,1-tris[4-(dihydroxyphosphorylmethyl)phenyl]methyl}phenyl.

12. The method of claim 1, wherein L¹ and L² are independently selected from the group consisting of a covalent bond, 1,4-phenylene, 4,4′

-diphenylethyne, 4,4′

-diphenylbutadiyne, 4,4′

-biphenyl, 4,4′

-stilbene, 1,4-bicyclooctane, 4,4′

-azobenzene, 4,4′

-benzylideneaniline, and 4,4″

-terphenyl.

13. The method of claim 1, wherein said electrolyte bearing a reactive site (Q) is selected from the group consisting of an acyl hydrazide, an amine, a dipyrrin, acac, a phenol, an alcohol, a diol, a thiol, an azide, a phenanthroline, alkyl, halide, aldehyde, a zirconium dichloride, and a zirconium hydroxide.

14. The method of claim 1, wherein R is selected from the group consisting of a carboxaldehyde, a ketone, an o-hydroxycarboxaldehyde, a dipyrrin, an amine, and acac.

15. The method of claim 1, wherein R is a carboxaldehyde or ketone and Q is an acylhydrazide.

16. The method of claim 1, wherein R is a carboxaldehyde or ketone and Q is an amine.

17. The method of claim 1, wherein R is an o-hydroxycarboxaldehyde and Q is an amine.

18. The method of claim 1, wherein R is an o-hydroxycarboxaldehyde and Q is an acyl hydrazide.

19. The method of claim 1, wherein R is a dipyrrin and Q is a dipyrrin.

20. The method of claim 1, wherein R is acac and Q is acac.

21. The method of claim 1, further comprising contacting said charged moiety with a reagent having formula

Z²-L³-K Y

wherein

K comprises a group having a charge complementary to the charge of J;

L³ is a covalent bond or a linker;

Z² is a surface attachment group; and

Y is a counterion;

whereby K electrostatically associates with J thereby providing a counterion group associated with said information storage molecule where said counterion group comprises said surface attachment group Z².

22. The method of claim 21, further comprising constructing a counter-electrode by binding an electrode to said surface attachment group Z².

23. The method of claim 22, wherein said electrode comprises a conductive material.

24. The method of claim 22, wherein said electrode comprises a semiconductive material.

25. The method of claim 21, wherein Z² is a protected or unprotected reactive site or group selected from the group consisting of a carboxylic acid, an alcohol, a thiol, a selenol, a tellurol, a phosphonic acid, a phosphonothioate, an amine, and a nitrile.

26. The method of claim 21, wherein -L³-Z² is selected from the group consisting of:

4-carboxyphenyl, 2-(4-carboxyphenyl)ethynyl, 4-(2-(4-carboxyphenyl)ethynyl)phenyl,

4-carboxymethylphenyl, 4-(3-carboxypropyl)phenyl, 4-(2-(4-carboxymethylphenyl)ethynyl) phenyl,

4-hydroxyphenyl, 2-(4-hydroxyphenyl)ethynyl, 4-(2-(4-hydroxyphenyl)ethynyl)phenyl,

4-hydroxymethylphenyl, 4-(2-hydroxyethyl)phenyl, 4-(3-hydroxypropyl)phenyl,

4-(2-(4-hydroxymethylphenyl)ethynyl)phenyl, 4-mercaptophenyl,

2-(4-mercaptophenyl)ethynyl, 4-(2-(4-mercaptophenyl)ethynyl)phenyl,

4-mercaptomethylphenyl, 4-(2-mercaptoethyl)phenyl, 4-(3-mercaptopropyl)phenyl,

4-(2-(4-mercaptomethylphenyl)ethynyl)phenyl, 4-selenylphenyl,

2-(4-selenylphenyl)ethynyl, 4-selenylmethylphenyl, 4-(2-selenylethyl)phenyl,

4-(3-selenylpropyl)phenyl, 4-selenylmethylphenyl, 4-(2-(4-selenylphenyl)ethynyl)phenyl,

4-tellurylphenyl, 2-(4-tellurylphenyl)ethynyl, 4-(2-(4-tellurylphenyl)ethynyl)phenyl,

4-tellurylmethylphenyl, 4-(2-tellurylethyl)phenyl, 4-(3-tellurylpropyl)phenyl,

4-(2-(4-tellurylmethylphenyl)ethynyl)phenyl, 4-(dihydroxyphosphoryl)phenyl,

2-[4-(dihydroxyphosphoryl)phenyl]ethynyl,

4-[2-[4-(dihydroxyphosphoryl)phenyl]ethynyl]phenyl,

4-[(dihydroxyphosphoryl)methyl]phenyl, 4-[2-(dihydroxyphosphoryl)ethyl]phenyl,

4-[2-[4-(dihydroxyphosphoryl)methylphenyl]ethynyl]phenyl,

4-(hydroxy(mercapto)phosphoryl)phenyl,

2-[4-(hydroxy(mercapto)phosphoryl)phenyl]ethynyl,

4-[2-[4-(hydroxy(mercapto)phosphoryl)phenyl]ethynyl]phenyl,

4-[(hydroxy(mercapto)phosphoryl)methyl]phenyl,

4-[2-(hydroxy(mercapto)phosphoryl)ethyl]phenyl,

4-[2-[4-(hydroxy(mercapto)phosphoryl)methylphenyl]ethynyl]phenyl, 4-cyanophenyl,

2-(4-cyanophenyl)ethynyl, 4-[2-(4-cyanophenyl)ethynyl]phenyl, 4-(cyanomethyl)phenyl,

4-(2-cyanoethyl)phenyl, 4-[2-[4-(cyanomethyl)phenyl]ethynyl]phenyl;

4-cyanobiphenyl,

4-aminophenyl, 2-(4-aminophenyl)ethynyl, 4-[2-(4-aminophenyl)ethynyl]phenyl,

4-aminobiphenyl, 1,1,1-tris[4-(S-acetylthiomethyl)phenyl]methyl,

4-{1,1,1-tris[4-(S-acetylthiomethyl)phenyl]methyl}phenyl,

1,1,1-tris[4-(dihydroxyphosphoryl)phenyl]methyl,

4-{1,1,1-tris[4-(dihydroxyphosphoryl)phenyl]methyl}phenyl,

1,1,1-tris[4-(dihydroxyphosphorylmethyl)phenyl]methyl, and

4-{1,1,1-tris[4-(dihydroxyphosphorylmethyl)phenyl]methyl}phenyl.

27. The method of claim 21, wherein L³ is selected from the group consisting of a covalent bond, 1,4-phenylene, 4,4′

-diphenylethyne, 4,4′

-diphenylbutadiyne, 4,4′

-biphenyl, 4,4′

-stilbene, 1,4-bicyclooctane, 4,4′

-azobenzene, 4,4′

-benzylideneaniline, and 4,4″

-terphenyl.

28. The method of claim 21, wherein the counterion (K) is selected from the group consisting of a halogen, an alkali earth metal, PF₆, and ClO₄.

29. The method of claim 21, wherein Z²-L³-K-Y⁺ is selected from the group consisting of 11-mercaptoundecanoic acid, 16-mercaptohexadecanoic acid, 3-mercapto-1-propanoic acid, (2-mercaptoethyl)trimethylammonium bromide, and 4-(mercaptomethyl)benzenesulfonic acid.

30. The method of claim 21, wherein said counterion is altered by an ion-exchange process.