CNT-based sensors: devices, processes and uses thereof

• US 8,907,384 B2
• Filed: 01/26/2007
• Issued: 12/09/2014
• Est. Priority Date: 01/26/2006
• Status: Expired due to Fees

• Current Assignee: Nanoselect, Inc.
• Original Assignee: Nanoselect, Inc.
• Inventors: Pace, Salvatore J., Man, Piu Francis, Patil, Ajeeta Pradip, Tan, Kah Fatt
• Primary Examiner(s): Such, Matthew W
• Assistant Examiner(s): Kalam, Abul
• Application Number:
  US12/161,294
• Publication Number:
  US 20110163296A1
• Time in Patent Office: 2,874 Days
• Field of Search: 977745-749
• US Class Current: 257/253
• CPC Class Codes: B82Y 15/00 Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: G01N 27/414 Ion-sensitive or chemical field-effect transistors, i.e. ISFETS or CHEMFETS
• CPC Class Codes: G01N 27/4145 specially adapted for biomolecules, e.g. gate electrode with immobilised receptors
• CPC Class Codes: G01N 27/4146 involving nanosized elements, e.g. nanotubes, nanowires
• CPC Class Codes: H10K 85/221 Carbon nanotubes
• CPC Class Codes: Y10S 977/742 Carbon nanotubes, CNTs
• CPC Class Codes: Y10S 977/748 Modified with atoms or molecules bonded to the surface
• CPC Class Codes: Y10S 977/749 Modified with dissimilar atoms or molecules substituted for carbon atoms of the cnt, e.g. impurity doping or compositional substitution
• CPC Class Codes: Y10S 977/752 Multi-walled

Abstract

Disclosed herein are methods of preparing and using doped MWNT electrodes, sensors and field-effect transistors. Devices incorporating doped MWNT electrodes, sensors and field-effect transistors are also disclosed.

Claims

1. An antennae assembly electrode, comprising:

an electrically conductive layer at least partially surmounting a substrate;

a planar protective layer, said protective layer having a plurality of contact holes; and

an assembly of doped antennae vertically oriented with respect to the electrically conductive layer and electrically connected with the electrically conductive layer through the contact holes, wherein each of the doped antennae comprises a doped MWNT comprising;

a base end attached to the electrically conductive layer,

a mid-section comprising an outer surface surrounding a lumen, wherein a majority of the outer surface of the mid-section is in fluidic contact with an environment in contact with a top end of the antennae;

the top end disposed opposite to the base end, wherein neither the mid-section nor the top end are connected to the electrically conductive layer; and

a dopant attached to or contained within the lumen, a dopant attached to or contained within the outer surface, a dopant attached to or contained within the top end, or any combination thereof.

2. The antennae assembly electrode of claim 1, further comprising a catalyst at least partially surmounting the electrically conductive layer, wherein at least a portion of the doped MWNT are attached at their ends to the catalyst.

3. The antennae assembly electrode of claim 2, wherein the assembly of doped MWNT comprise a plurality of MWNT having one or more fill molecules.

4. The antennae assembly electrode of claim 3, wherein the fill molecules include molecules, molecular ions, atoms, atomic ions, or any combination thereof.

5. The antennae assembly electrode of claim 3, wherein the fill molecules comprise one or more fullerenes, doped fullerenes, ionophores, ion exchangers, redox molecules, conductive polymers, metals, or any combination thereof.

6. The antennae assembly electrode of claim 5, wherein the ionophores include cyclic polyethers, antibiotics, linear chain ligands or any combination thereof.

7. The antennae assembly electrode of claim 6, wherein the cyclic polyethers comprise 12-crown-4 to 24-crown-8 polyethers, or any combination thereof.

8. The antennae assembly electrode of claim 6, wherein the ionophores includes one or more cryptands, calixarenes, rotaxanes, or any combination thereof.

9. The antennae assembly electrode of claim 5, wherein the fullerenes include one or more of C₆₀, C₇₀, C₈₀, C₉₀, or any combination thereof.

10. The antennae assembly electrode of claim 5, wherein the fullerenes are doped fullerenes.

11. The antennae assembly electrode of claim 10, wherein the doped fullerenes are filled, coated, chemically functionalized, or any combination thereof.

12. The antennae assembly electrode of claim 5, wherein the ion exchangers include quaternized PVC, sulfonated PI′

FE, or any combination thereof.

13. The antennae assembly electrode of claim 6, wherein the antibiotics include valinomycin, nonactin, monensin, iosin, or any combination thereof.

14. The antennae assembly electrode of claim 6, wherein the linear chain ligands include poly-oxyethylene, tri-n-alkylammonium halide, N,N,N′

,N′

-tetrabutyl-3,6-dioxaoctanedi(thioamide), N,N,N′

,N′

-tetracyclohexyl-3-oxapentadienediamide, alkyl-4-trifluoroacetylbenzoate, triidodecylamine, or any combination thereof.

15. The antennae assembly electrode of claim 3, wherein the fill molecules are semiconductor polymers comprising donor-acceptor pairs.

16. The antennae assembly electrode of claim 15, wherein the semiconductor polymers comprise donor-acceptor pairs including semicarbazole/TCNQ, ionene/iodine, or any combination thereof.

17. The antennae assembly electrode of claim 3, wherein the fill molecules comprise conductive polymers.

18. The antennae assembly electrode of claim 17, wherein the conductive polymers comprise a polypyrrole, a polyaniline, a polythiophene, a poly-p-phenylene, a polyacetylene, or any combination thereof.

19. The antennae assembly electrode of claim 3, wherein at least two of the doped MWNT comprise different fill molecules.

20. The antennae assembly electrode of claim 3, wherein the fill molecules include a chemical agent capable of responding to a chemical or an electrical signal.

21. The antennae assembly electrode of claim 2, wherein the assembly of doped MWNT comprise a plurality of MWNT having a cladding.

22. The antennae assembly electrode of claim 21, wherein the cladding includes a dielectric, an ion conducting polymer, an electron conducting polymer, an ionophore polymer dopant, a redox-mediator dopant, or any combination thereof.

23. The antennae assembly electrode of claim 22, wherein the dielectric includes a polyolefin polymer, a polyaliphatic polymer, a polysiloxane polymer, a polyurethane polymer, a polyvinylchloride polymer, alumina, or any combination thereof.

24. The antennae assembly electrode of claim 22, wherein the ion conducting polymer includes nafion, polystyrene sulfonate, polyvinylpyridinium, or any combination thereof.

25. The antennae assembly electrode of claim 22, wherein the electron conducting polymer includes a chemically doped polymer, an electrochemically doped polymer, a redox electroactive polymer, or any combination thereof.

26. The antennae assembly electrode of claim 25, wherein the doped polymer includes a polyionine, a polysilicon, a polysemicarbazole, a polyphenylene, a polyacetylene, a polyphenylene sulfide, a polythiophene, or any combination thereof.

27. The antennae assembly electrode of claim 26, wherein the doped polymer includes a dopant, the dopant comprising AsF₅, I₂, Li, K, BF₆₋

, PF₆₋

, or any combination thereof.

28. The antennae assembly electrode of claim 25, wherein the electrochemically doped polymer includes a polypyrrole, a polythiophene, a polyphenylquinone, a polyaniline, or any combination thereof.

29. The antennae assembly electrode of claim 25, wherein the redox electroactive polymers include polyviologen, polyvinylferrocene, poly-Ru(bpy)3++, or any combination thereof.

30. The antennae assembly electrode of claim 22, wherein the ionophore polymer dopant includes a crown ether, a cryptand, a sphereand, a rotaxane, an antibiotic, a non-cyclic ligand, or any combination thereof.

31. The antennae assembly electrode of claim 22, wherein the redox-mediator dopant includes Ru(bpy)3++, Br2/Br−

, Fe(phen)3+++, Co(terpy)2+++, Fe(CN)6(3−

), Ru(NH.sub.3)6+++, quinone, hydroquinone, methylviologen, tetracyanoquinodimethane, benzophenone, ferrocene, tetramethyl-p-phenylenediamine, tetrathiafulvalene, tri-N-p-tolylamine, or any combination thereof.

32. The antennae assembly electrode of claim 21, wherein the cladding comprises one or more functional reactive groups residing upon a surface of the cladding.

33. The antennae assembly of claim 32, wherein the functional reactive groups include an oxide, a hydroxide, a carboxylic acid, an ester, an ether, a carbonyl, an amine, an amide, an epoxide, a halide, or any combination thereof.

34. The antennae assembly of claim 21, wherein the cladding includes a linker attaching the cladding to the doped MWNT.

35. The antennae assembly of claim 34, wherein the linker includes a Schiff base, a carbodi-imide, an amide, or any combination thereof.

36. The antennae assembly of claim 21, wherein the cladding is linked to a selective functionality on the surface of one or more of the MWNT.

37. The antennae assembly of claim 36, wherein the selective functionality on the surface of one or more of the MWNT includes a protein, a phospholipid, a nucleic acid, an electron mediator, an ionophore, or any combination thereof.

38. The antennae assembly of claim 37, wherein the protein includes an enzyme, an antibody, or any combination thereof.

39. The antennae assembly of claim 37, wherein the nucleic acid includes an oligonucleotide, DNA, RNA, or any combination thereof.

40. The antennae assembly electrode of claim 21, wherein at least two of the doped MWNT comprise different claddings.

41. The antennae assembly electrode of claim 21, wherein the cladding includes a chemical agent capable of responding to a chemical or an electrical signal.

42. The antennae assembly electrode of claim 2, wherein the MWNT comprise one or more functional reactive groups covalently attached to the graphene surface of the MWNT.

43. The antennae assembly of claim 42, wherein the functional reactive groups include an oxide, a hydroxide, a carboxylic acid, an ester, an ether, a carbonyl, an amine, an amide, an epoxide, a halide, or any combination thereof.

44. The antennae assembly of claim 42, wherein the functional reactive groups covalently attached to the graphene surface includes a linker attached to the doped MWNT.

45. The antennae assembly of claim 44, wherein the linker includes a Schiff base, a carbodi-imide, an amide, or any combination thereof.

46. The antennae assembly of claim 42, wherein the functional reactive groups covalently attached to the graphene surface includes a selective functionality.

47. The antennae assembly of claim 46, wherein the selective functionality includes a protein, a phospholipids, a nucleic acid, an electron mediator, an ionophore, or any combination thereof.

48. The antennae assembly of claim 47, wherein the protein includes an enzyme, an antibody, an antigen, or any combination thereof.

49. The antennae assembly of claim 47, wherein the nucleic acid includes an oligonucleotide, DNA, RNA, or any combination thereof.

50. The antennae assembly electrode of claim 2, wherein the electrically conductive layer comprises a metal, an electrically conductive polymer, a carbon film, n-type or p-type doped polysilicon, or any combination thereof.

51. The antennae assembly electrode of claim 50, wherein the electrically conductive layer is a lead conductor residing between the substrate and the catalyst.

52. The antennae assembly electrode of claim 2, wherein the electrically conductive layer comprises Pt, Au, Ti, W, V, Mo, or any combination thereof.

53. The antennae assembly electrode of claim 2, wherein the electrically conductive layer comprises a CVD-deposited metal.

54. The antennae assembly electrode of claim 53, wherein the CVD-deposited metal comprises TiW, Mo, TiN, or any combination thereof.

55. The antennae assembly electrode of claim 2, wherein the electrically conductive layer is characterized as having a layer thickness in the range of from about 1 nanometer to about 1000 nanometers.

56. The antennae assembly electrode of claim 2, wherein the electrically conductive layer is characterized as having a layer thickness in the range of from about 10 nanometers to about 100 nanometers.

57. The antennae assembly electrode of claim 2, wherein the electrically conductive layer is characterized as having a layer thickness in the range of from about 50 nanometers to about 100 nanometers.

58. The antennae assembly electrode of claim 2, wherein the catalyst comprises Ni, Co, Fe, Ru, Rh, Pd, Os, Ir, metal alloys or any combination thereof.

59. The antennae assembly electrode of claim 58, wherein the catalyst is derived from an organo-metallic precursor, an iron-phthalocyanine, a cobalt-phthalocyanine, or any combination thereof.

60. The antennae assembly electrode of claim 58, wherein the catalyst comprises a catalyst capable of growing MWNT.

61. The antennae assembly electrode of claim 60, wherein the catalyst capable of growing MWNT includes nickel, cobalt, iron, or any combination thereof.

62. The antennae assembly electrode of claim 2, wherein the catalyst is characterized as having a layer thickness in the range of from about 1 nanometer to about 10,000 nanometers.

63. The antennae assembly electrode of claim 2, wherein the catalyst is characterized as having a layer thickness in the range of from about 500 nanometers to about 1000 nanometers.

64. The antennae assembly electrode of claim 2, wherein the catalyst is characterized as having a layer thickness in the range of from about 700 nanometers to about 900 nanometers.

65. The antennae assembly electrode of claim 2, wherein the doped antennae assembly comprises a plurality of doped MWNT perpendicularly oriented to the substrate.

66. The antennae assembly electrode of claim 65, wherein the doped MWNTs are oriented parallel to each other.

67. The antennae assembly electrode of claim 2, wherein the doped antennae assembly comprises a doped MWNT carpet, a doped MWNT array, or any combination thereof.

68. The antennae assembly electrode of claim 67, wherein the electrically conductive layer comprises a single contiguous conductive layer, and the doped MWNT carpet is in electrical communication with the single contiguous conductive layer.

69. The antennae assembly electrode of claim 67, wherein the doped MWNT array comprises an aligned array of nanotubes of a defined geometry and pitch oriented with respect to the electrically conductive layer.

70. The antennae assembly electrode of claim 2, wherein the assembly of doped MWNT comprises an array of doped MWNT.

71. The antennae assembly electrode of claim 2, wherein the catalyst is patterned on the electrically conductive layer, and the assembly of doped MWNT is attached to the patterned catalyst.

72. The antennae assembly electrode of claim 2, wherein the catalyst is patterned as an array of islands, stripes, circles, squares, rings, triangles, polygons, or any combination thereof.

73. The use of the antennae assembly electrode of claim 1 as a working electrode in an electrolytic cell or sensor.

74. The antennae assembly electrode of claim 1, wherein the substrate comprises quartz, aluminum oxide, alumina, silicon, a ceramic, chromium, iridum, aluminum, niobium, tantalum, titanium, tungsten, carbon, silicon oxide, silicon carbide, brass, bronze, silver, gold, glass, indium tin oxide, graphite, platinum, magnesium aluminum oxide, platinum crucible, magnesium aluminate spinel, or any oxide, alloy, or combination thereof.

75. The antennae assembly electrode of claim 1, further comprising one or more layers of quartz, aluminum oxide, alumina, silicon, a ceramic, chromium, iridum, aluminum, niobium, tantalum, titanium, tungsten, carbon, silicon oxide, silicon carbide, brass, bronze, silver, gold, glass, indium tin oxide, graphite, platinum, magnesium aluminum oxide, platinum crucible, magnesium aluminate spinel, or any oxide, alloy, or combination thereof.

76. A sensor comprising the antennae assembly electrode of claim 1.

77. A field effect transistor comprising the antennae assembly electrode of claim 1.

78. The antennae assembly electrode of claim 21, wherein the electrode includes a linear chain ligand.

79. The antennae assembly electrode of claim 78, wherein the linear chain ligand comprises poly(oxyethylene), tri-n-alkylammonium, or a combination thereof.

80. The antennae assembly of claim 45, wherein the linker comprises a tether.

81. The antennae assembly of claim 80, wherein tether comprises an alkane, an olefin, a linear hydrocarbon, a branched hydrocarbon, or any combination thereof.

82. The antennae assembly electrode of claim 69, wherein the pitch is defined as the ratio of the center to center distance of the MWNTs to the diameter of a MWNT, the pitch being in the range of from about 1:

1 to about 100;

1.

83. The antennae assembly electrode of claim 69, wherein the length to diameter aspect ratio of the MWNTs is in the range of from about 1:

1 to about 10,000;

1.

84. An antennae assembly electrode, comprising:

an electrically conductive layer at least partially surmounting a substrate;

a planar protective layer, said protective layer having a plurality of contact holes; and

an assembly of antennae vertically oriented with respect to the electrically conductive layer and electrically connected with the electrically conductive layer through the contact holes, wherein each of the antennae comprises a MWNT comprising;

a base end attached to the electrically conductive layer,

a mid-section comprising an outer surface surrounding a lumen, wherein a majority of the outer surface of the mid-section is in fluidic contact with an environment in contact with a top end of the antennae; and

the top end disposed opposite to the base end, wherein neither the mid-section nor the top end are connected to the electrically conductive layer.

85. A sensor comprising the antennae assembly electrode according to claim 84.

86. A field-effect transistor comprising the antennae assembly electrode according to claim 84.

87. An antennae assembly electrode, comprising:

an electrically conductive layer at least partially surmounting a substrate, said electrically conductive layer having a surface defining a first plane;

a planar protective layer disposed parallel to the first plane, said protective layer having a plurality of contact holes; and

an assembly of doped antennae, wherein each of the doped antennae is normal to said first plane, electrically connected with the electrically conductive layer through the contact holes, and comprises a doped MWNT comprising;

a base end attached to the electrically conductive layer,

a mid-section comprising an outer surface surrounding a lumen, wherein said mid-section extends from said base end to a top end and wherein a majority of the outer surface of the mid-section is in fluidic contact with an environment in contact with the top end of the antennae;

the top end disposed opposite to the base end, wherein neither the mid-section nor the top end are connected to the electrically conductive layer; and

a dopant attached to or contained within the lumen, a dopant attached to or contained within the outer surface, a dopant attached to or contained within the top end, or any combination thereof.