Multistate triple-decker dyads in three distinct architectures for information storage applications

• US 6,728,129 B2
• Filed: 02/19/2002
• Issued: 04/27/2004
• Est. Priority Date: 02/19/2002
• 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)
• Inventors: Schweikart, Karl-Heinz, Kuhr, Werner G., Bocian, David F., Lindsey, Jonathan S.
• Primary Examiner(s): LE, THONG QUOC
• Application Number:
  US10/079,938
• Publication Number:
  US 20030169618A1
• Time in Patent Office: 798 Days
• Field of Search: 365/151, 365/106, 365/153, 365/173
• US Class Current: 365/151
• 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 11/34 using semiconductor devices
• CPC Class Codes: G11C 11/5664 using organic memory material storage elements
• 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: G11C 13/025 using fullerenes, e.g. C60, or nanotubes, e.g. carbon or silicon nanotubes
• CPC Class Codes: G11C 2213/77 Array wherein the memory element being directly connected to the bit lines and word lines without any access device being used

Abstract

This invention provides novel high density memory devices that are electrically addressable permitting effective reading and writing, that provide a high memory density (e.g., 10¹⁵ bits/cm³), that provide a high degree of fault tolerance, and that are amenable to efficient chemical synthesis and chip fabrication. The devices are intrinsically latchable, defect tolerant, and support destructive or non-destructive read cycles. In a preferred embodiment, the device comprises a fixed electrode electrically coupled to a storage medium having a multiplicity of different and distinguishable oxidation states wherein data is stored in said oxidation states by the addition or withdrawal of one or more electrons from said storage medium via the electrically coupled electrode. The storage medium typically comprises a storage molecule that is a triple-decker sandwich heterodimer. Such dimers can provide 8 or more oxidation states and permit the storage of at least 3 bits per molecule.

Claims

1. An apparatus for storing data, said apparatus comprising:

a fixed electrode electrically coupled to

a storage medium having a plurality of different and distinguishable oxidation states wherein data is stored in said oxidation states by the addition or withdrawal of one or more electrons from said storage medium via the electrically coupled electrode;

said storage medium comprising a storage molecule having a plurality of different and distinguishable oxidation states wherein said storage molecule comprises a first triple-decker sandwich coordination compound covalently linked to a second triple-decker sandwich coordination compound wherein the first compound and the second compound are different triple-decker sandwich coordination compounds;

wherein said storage molecule comprises a triple-decker sandwich coordination compound having a formula selected from the group consisting of Por¹M¹Por²M²Por³, Por¹M¹Pc¹M²Por², Pc¹M¹Pc²M² Por¹, Pc¹M¹Pc²M²Pc³, Pc^N1M¹Por¹M²Por², and Pc¹M¹Por¹M²Pc² wherein;

M¹, and M² are the same or different and each is a metal;

Por¹, Por², and Por³ are the same or different and each is a porphyrinato species; and

Pc¹, Pc², and Pc³ are the same or different and each is a phthalocyaninato species.

2. The apparatus of claim 1, wherein M¹ and M², when present, are independently selected from metals of the lanthanide series.

3. The apparatus of claim 1, wherein said storage molecule has a vertical architecture.

4. The apparatus of claim 1, wherein said storage molecule has a horizontal architecture.

5. The apparatus of claim 4, wherein said storage molecule is covalently coupled to said electrode by at least two linkers.

6. The apparatus of claim 1, wherein said storage molecule comprises a triple-decker sandwich coordination compound having the formula:

7. The apparatus of claim 1, wherein said storage molecule comprises a triple-decker sandwich coordination compound having the formula:

8. The apparatus of claim 1, wherein said storage molecule comprises a triple-decker sandwich coordination compound having the formula:

9. The apparatus of any one of claims 1, 7, 8, wherein Ln is selected from the group consisting of Eu, and Ce.

10. The apparatus of claim 1, wherein said storage molecule has a formula selected from the group consisting of:

wherein

M¹, M², M³, and M⁴ are metals independently selected from the lanthanide series or the actinide series;

Por¹, Por², Por³ are are the same or different and each is a porphyrinato species;

Pc¹, Pc², Pc³, and Pc⁴ are the same or different and are each phthalocyaninato species; and

J is a covalent bond or a linker.

11. The apparatus of claim 10, wherein said storage molecule has a formula:

wherein;

R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R¹² are independently selected from the group consisting of a covalent bond, a linker, aryl, phenyl, cycloalkyl, alkyl, halogen, alkoxy, alkylthio, perfluoroalkyl, perfluoroaryl, pyridyl, cyano, thiocyanato, nitro, amino, alkylamino, acyl, sulfoxyl, sulfonyl, amido, and carbamoyl;

X¹, X², X³, X⁴, X⁵, X⁶, X⁷, X⁸, X⁹, and X¹⁰ are independently selected from the group consisting of a covalent bond, a linker, aryl, phenyl, cycloalkyl, alkyl, halogen, alkoxy, alkylthio, perfluoroalkyl, perfluoroaryl, pyridyl, cyano, thiocyanato, nitro, amino, alkylamino, acyl, sulfoxyl, sulfonyl, amido, and carbamoyl;

at least one R or X is a covalent bond or a linker;

J is a covalent bond or a linker; and

M¹, M², M³, and M⁴ are independently selected metals from the lanthanide series.

12. The apparatus of claim 11, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R¹² are independently selected from the group consisting of a linker, methyl, t-butyl, butoxy, fluoro, and H.

13. The apparatus of claim 11, wherein X¹, X², X³, X⁴, X⁵, X⁶, X⁷, X⁸, X⁹, and X¹⁰ are independently selected from the group consisting of a linker, 4-methylphenyl, 4-t-butylphenyl, 4-trifluoromethylphenyl, pentyl, and H.

14. The apparatus of claim 11, wherein M¹, M², and M⁴ are the same.

15. The apparatus of claim 11, wherein M¹, M², and M⁴ are Eu, and M³ is Ce.

16. The apparatus of claim 11, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸ R⁹, R¹⁰, R¹¹, and R¹² are the same.

17. The apparatus of claim 11, wherein X⁵ is a linker.

18. The apparatus of claim 11, wherein X³ and X⁴ are linkers.

19. The apparatus of claim 11, wherein X² and X⁴ are linkers.

20. The apparatus of claim 11, wherein X¹, X², and X³ are the same, and X⁵ is a linker.

21. The apparatus of any one of claims 17 through 20, wherein said linker is selected from the goup consisting of 4-carboxyphenyl, 2-(4-carboxyphenyl)ethynyl, 4-(2-(4-carboxyphenyl)ethynyl)phenyl, 4-carboxymethylphenyl, 4-(2-(4-carboxymethylphenyl)ethynyl)phenyl, 4-hydroxyphenyl, 2-(4-hydroxyphenyl)ethynyl, 4-(2-(4-hydroxyphenyl)ethynyl)phenyl, 4-hydroxymethylphenyl, 4-(2-(4-hydroxymethylphenyl)ethynyl)phenyl, 4-mercaptophenyl, 2-(4-mercaptophenyl)ethynyl, 4-(2-(4-mercaptophenyl)ethynyl)phenyl, 4-mercaptomethylphenyl, 4-(2-(4-mercaptomethylphenyl)ethynyl)phenyl, 4-selenylphenyl, 2-(4-selenylphenyl)ethynyl, 4-selenylmethylphenyl, 4-(2-(4-selenylphenyl)ethynyl)phenyl, 4-tellurylphenyl, 2-(4-tellurylphenyl)ethynyl, 4-(2-(4-tellurylphenyl)ethynyl)phenyl, 4-tellurylmethylphenyl, and 4-(2-(4-tellurylmethylphenyl)ethynyl)phenyl.

22. The apparatus of claim 11, wherein J is a linker selected from the group consisting of 4,4′

-diphenylethyne, 4,4′

-diphenylbutadiyne, 4,4′

-biphenyl, 1,4-phenylene, 4,4′

-stilbene, 1,4-bicyclooctane, 4,4′

-azobenzene, 4,4′

-benzylideneaniline, and 4,4″

-terphenyl.

23. The apparatus of claim 11, wherein said storage molecule has the formula of a dyad selected from the group consisting of dyad2, dyad3, dyad4, and dyad5.

24. The apparatus of claim 10, wherein said storage molecule has a formula:

wherein;

R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ are selected from the group consisting of a covalent bond, a linker, aryl, phenyl, cycloalkyl, alkyl, halogen, alkoxy, alkylthio, perfluoroalkyl, perfluoroaryl, pyridyl, cyano, thiocyanato, nitro, amino, alkylamino, acyl, sulfoxyl, sulfonyl, amido, a and carbamoyl;

X¹, X², X³, X⁴, X⁵, and X⁶ are independently selected from the group consisting of a covalent bond, a linker, aryl, phenyl, cycloalkyl, alkyl, halogen, alkoxy, alkylthio, perfluoroalkyl, perfluoroaryl, pyridyl, cyano, thiocyanato, nitro, amino, alkylamino, acyl, sulfoxyl, sulfonyl, amido, and carbamoyl;

at least one R or X is a covalent bond or a linker;

J is a covalent bond or a linker; and

M¹, M², M³, and M⁴ are independently selected metals from the lanthanide series.

25. The apparatus of claim 24, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ are independently selected from the group consisting of a linker, methyl, t-butyl, butoxy, fluoro, and H.

26. The apparatus of claim 24, wherein X¹, X², X³, X⁴, X⁵, and X⁶ are independently selected from the group consisting of a linker, 4-methylphenyl, 4-t-butylphenyl, 4-trifluoromethylphenyl, pentyl, and H.

27. The apparatus of claim 24, wherein M¹, M², and M⁴ are the same.

28. The apparatus of claim 24, wherein M¹, M², and M⁴ are Eu, and M³ Ce.

29. The apparatus of claim 24, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸,R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ are the same.

30. The apparatus of claim 24, wherein X⁵ a linker.

31. The apparatus of claim 24, wherein X³ and X⁴ are linkers.

32. The apparatus of claim 24, wherein X³ and X⁴ are linkers.

33. The apparatus of claim 24, wherein X¹, X², and X³ are the same, and X⁵ is a linker.

34. The apparatus of any one of claims 30 through 33, wherein said linker is selected from the goup consisting of 4-carboxyphenyl, 2-(4-carboxyphenyl)ethynyl, 4-(2-(4-carboxyphenyl)ethynyl)phenyl, 4-carboxymethylphenyl, 4-(2-(4-carboxymethylphenyl)ethynyl)phenyl, 4-hydroxyphenyl, 2-(4-hydroxyphenyl)ethynyl, 4-(2-(4-hydroxyphenyl)ethynyl)phenyl, 4-hydroxymethylphenyl, 4-(2-(4-hydroxymethylphenyl)ethynyl)phenyl, 4-mercaptophenyl, 2-(4-mercaptophenyl)ethynyl, 4-(2-(4-mercaptophenyl)ethynyl)phenyl, 4-mercaptomethylphenyl, 4-(2-(4-mercaptomethylphenyl)ethynyl)phenyl, 4-selenylphenyl, 2-(4-selenylphenyl)ethynyl, 4-selenylmethylphenyl, 4-selenylmethylphenyl, 4-(2-(4-selenylphenyl)ethynyl)phenyl, 4-tellurylphenyl, 2-(4-tellurylphenyl)ethynyl, 4-(2-(4-tellurylphenyl)ethynyl)phenyl, 4-tellurylmethylphenyl, and 4-(2-(4-tellurylmethylphenyl)ethynyl)phenyl.

35. The apparatus of claim 24, wherein J is a linker selected from the group consisting of 4,4′

-diphenylethyne, 4,4′

-diphenylbutadiyne, 4,4′

-biphenyl, 1,4-phenylene, 4,4′

-stilbene, 1,4-bicyclooctane, 4,4′

-azobenzene, 4,4′

-benzylideneaniline, and 4,4″

-terphenyl.

36. The apparatus of claim 24, wherein said storage molecule has the formula of dyad1.

37. The apparatus of claim 1, wherein said storage medium has a memory storage density of at least about 10 gigabits per cm² in a sheet-like device.

38. The apparatus of claim 1, wherein said storage medium is covalently linked to said electrode.

39. The apparatus of claim 1, wherein said storage molecule is covalently linked to said electrode by a thiol linker.

40. The apparatus of claim 1, wherein said storage molecule is covalently linked to said electrode by a linker wherein the coupling to the electrode has the form:

41. The apparatus of claim 1, wherein said storage molecule is juxtaposed in the proximity of said electrode such that electrons can pass from said storage molecule to said electrode.

42. The apparatus of claim 1, wherein said storage medium is juxtaposed to a dielectric material embedded with counterions.

43. The apparatus of claim 1, wherein said storage medium and said electrode are fully encapsulated in an integrated circuit.

44. The apparatus of claim 1, wherein said storage medium is electronically coupled to a second electrode that is a reference electrode.

45. The apparatus of claim 1, wherein said storage medium is present on a single plane in said device.

46. The apparatus of claim 1, wherein said storage medium is present at a multiplicity of storage locations.

47. The apparatus of claim 1, wherein said apparatus comprises multiple planes and said storage locations are present on multiple planes of said apparatus.

48. The apparatus of claim 47, wherein said storage locations range from about 1024 to about 4096 different locations.

49. The apparatus of claim 47, wherein each location is addressed by a single electrode.

50. The apparatus of claim 47, wherein each location is addressed by at least two electrodes.

51. The apparatus of claim 1, wherein said electrode is connected to a voltage source.

52. The apparatus of claim 51, wherein said voltage source is the output of an integrated circuit.

53. The apparatus of claim 1, wherein said electrode is connected to a device to read the oxidation state of said storage medium.

54. The apparatus of claim 53, wherein said device is selected from the group consisting of a voltammetric device, an amperometric device, and a potentiometric device.

55. The apparatus of claim 54, wherein said device is a sinusoidal voltammeter.

56. The apparatus of claim 53, wherein said device provides a Fourier transform of the output signal from said electrode.

57. The apparatus of claim 53, wherein said device refreshes the oxidation state of said storage medium after reading said oxidation state.

58. The apparatus of claim 1, wherein said different and distinguishable oxidation states of said storage medium can be set by a voltage difference no greater than about 2 volts.

59. A method of storing data, said method comprising:

(i) providing an apparatus according to claim 1; and

(ii) applying a voltage to said electrode at sufficient current to set an oxidation state of said storage medium.

60. The method of claim 59, wherein said voltage ranges up to about 2 volts.

61. The method of claim 59, wherein said voltage is the output of an integrated circuit.

62. The method of claim 59, further comprising detecting the oxidation state of said storage medium and thereby reading out the data stored therein.

63. The method of claim 62, wherein said detecting the oxidation state of the storage medium further comprises refreshing the oxidation state of the storage medium.

64. The method of claim 62, wherein said detecting comprises analyzing a readout signal in the time domain.

65. The method of claim 62, wherein said detecting comprises analyzing a readout signal in the frequency domain.

66. The method of claim 62, wherein said detecting comprises performing a Fourier transform on said readout signal.

67. The method of claim 62, wherein said detecting utilizes a voltammetric method.

69. In a computer system, a memory device, said memory device comprising the apparatus of claim 1.

70. A computer system comprising a central processing unit, a display, a selector device, and a memory device, said memory device comprising the apparatus of claim 1.

68. A porphyrin half-sandwich complex comprising a cis-A2BC porphyrin complexed with a metal.

71. A method of making a triple-decker sandwich, said method comprising:

providing a metal-porphyrin half-sandwich complex comprising a cis-A₂BC type porphyrin complexed with a metal or an ABCD type porphyrin complexed with a metal; and

reacting said half-sandwich complex with a double-decker sandwich complex to form a triple-decker sandwich.

72. The method of claim 71, wherein said porphyrin is a cis-A2BC type porphyrin.

73. The method of claim 71, wherein said porphyrin has the formula:

wherein R¹, R², R³, and R⁴ are independently selected from the group consisting of p-tolyl, n-pentyl, 4-bromophenyl, 4-iodophenyl, trimetbylsilylethynyl, bromo, iodo, 1,3,2-dioxaborolan-2-yl, 4-(1,3,2-dioxaborolan-2-yl)phenyl, 4-(2-trimethylsilylethynyl)phenyl, 4-formylphenyl, 4-aminophenyl, and 4-iodobicyclo[2.2.2]octan-1-yl.

74. The method of claim 71 wherein said double decker sandwich complex is selected from the group consisting of Por-M-Pc and Pc-M-Pc.

75. An information storage medium, said storage medium comprising a storage molecule having at least eight different and distinguishable non-zero oxidation states wherein said storage molecule has a formula selected from the group consisting of:

wherein

M¹, M², M³, and M⁴ are metals independently selected from the lanthanide series or the actinide series;

Por¹, Por², Por³, and Por⁴ are are the same or different and each is a porphyrinato species;

Pc¹, Pc², Pc³, and Pc⁴ are the same or different and are each phthalocyaninatol; and

J is a covalent bond or a linker.

76. The storage medium of claim 75, wherein said storage molecule has a formula:

wherein;

R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R¹² are independently selected from the group consisting of a covalent bond, a linker, aryl, phenyl, cycloalkyl, alkyl, halogen, alkoxy, alkylthio, perfluoroalkyl, perfluoroaryl, pyridyl, cyano, thiocyanato, nitro, amino, alkylamino, acyl, sulfoxyl, sulfonyl, amido, and carbamoyl;

X¹, X², X³, X⁴, X⁵, X⁶, X⁷, X⁸, X⁹, and X¹⁰ are independently selected from the group consisting of a covalent bond, a linker, aryl, phenyl, cycloalkyl, alkyl, halogen, alkoxy, alkylthio, perfluoroalkyl, perfluoroaryl, pyridyl, cyano, thiocyanato, nitro, amino, alkylamino, acyl, sulfoxyl, sulfonyl, amido, and carbamoyl;

at least one R or X is a covalent bond or a linker;

J is a covalent bond or a linker, and

M¹, M², M³, and M⁴ are independently selected metals from the lanthanide series.

77. The storage medium of claim 76, wherein R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, and R12 are independently selected from the group consisting of a linker, methyl, t-butyl, butoxy, fluoro, and H.

78. The storage medium of claim 76, wherein X¹, X², X³, X⁴, X⁵, X⁶, X⁷, X⁸, X⁹, and X¹⁰ are independently selected from the group consisting of a linker, 4-methylphenyl, 4-t-butylphenyl, 4-trifluoromethylphenyl, pentyl, and H.

79. The storage medium of claim 76, wherein M¹, M², and M⁴ are the same.

80. The storage medium of claim 76, wherein M¹, M², and M⁴ are Eu, and M³ is Ce.

81. The storage medium of claim 76, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R¹² are the same.

82. The storage medium of claim 76, wherein X⁵ a linker.

83. The storage medium of claim 76, wherein X³ and X⁴ are linkers.

84. The storage medium of claim 76, wherein X² and X⁴ are linkers.

85. The storage medium of claim 76, wherein X¹, X², and X³ are the same, and X⁵ is a linker.

86. The storage medium of claim 76, wherein J is a linker selected from the group consisting of 4,4′

-diphenylethyne, 4,4′

-diphenylbutadiyne, 4,4′

-biphenyl, 1,4-phenylene, 4,4′

-stilbene, 1,4-bicyclooctane, 4,4′

-azobenzene, 4,4′

-benzylideneaniline, and 4,4″

-terphenyl.

87. The storage medium of claim 76, wherein said storage molecule has the formula of a dyad selected from the group consisting of dyad2, dyad3, dyad4, and dyad5.

88. The storage medium of claim 76, wherein said storage molecule has a formula:

wherein;

R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ are selected from the group consisting of a covalent bond, a linker, aryl, phenyl, cycloalkyl, alkyl, halogen, alkoxy, alkylthio, perfluoroalkyl, perfluoroaryl, pyridyl, cyano, thiocyanato, nitro, amino, alkylamino, acyl, sulfoxyl, sulfonyl, amido, a and carbamoyl;

X¹, X², X³, X⁴, X⁵, and X⁶ are independently selected from the group consisting of a covalent bond, a linker, aryl, phenyl, cycloalkyl, alkyl, halogen, alkoxy, alkylthio, perfluoroalkyl, perfluoroaryl, pyridyl, cyano, thiocyanato, nitro, amino, alkylamino, acyl, sulfoxyl, sulfonyl, amido, and carbamoyl;

at least one R or X is a covalent bond or a linker;

J is a covalent bond or a linker; and

M¹, M², M³, and M⁴ are independently selected metals from the lanthanide series.

89. The storage medium of claim 88, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ are independently selected from the group consisting of a linker, methyl, t-butyl, butoxy, fluoro, and H.

90. The storage medium of claim 88, wherein X¹, X², X³, X⁴, X⁵, and X⁶ are independently selected from the group consisting of a linker, 4-methylphenyl, 4-t-butylphenyl, 4-trifluoromethylphenyl, pentyl, and H.

91. The storage medium of claim 88, wherein M¹, M², and M⁴ are the same.

92. The storage medium of claim 88, wherein M¹, M², and M⁴ are Eu, and M³ is Ce.

93. The storage medium of claim 88, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹² R¹³, R¹⁴, R¹⁵, and R¹⁶ are the same.

94. The storage medium of claim 88, wherein X⁵ is a linker.

95. The storage medium of claim 88, wherein X³ and X⁴ are linkers.

96. The storage medium of claim 88, wherein X² and X⁴ are linkers.

97. The storage medium of claim 88, wherein X¹, X², and X³ are the same, and X⁵ is a linker.

98. The storage medium of claim 88, wherein J is a linker selected from the group consisting of 4,4′

-diphenylethyne, 4,4′

-diphenylbutadiyne, 4,4′

-biphenyl, 1,4-phenylene, 4,4′

-stilbene, 1,4-bicyclooctane, 4,4′

-azobenzene, 4,4′

-benzylideneaniline, and 4,4″

-terphenyl.

99. The storage medium of claim 88, wherein said storage molecule has the formula of dyad1.